J. Korean Soe: App. Biol Chem. 4714). 422-425 (2008) AS ABAWORFE Beale] BMY XML THB (Erigeron annuus L.) R2ZFE| triterpenoid2| 22] HSH SSM - Yas SIA - Wee! Ass’: Ace’: sole. agate Aa AIF BY Baia eael, Vasa Basler, AISIAFA, “GAs heheh, “el Feho]ss 20088 118 19 4; 2008 Ie 981 Fe) AVR HE Wo MeOH BLS FEIT, ME HOA, BOW YES Be, Fes. ol S HWOAc ¥H-E silica gel, octadecylsilica gel(ODS) column chromatography % high performance liquid chromatography(HPLO® Malate} 35S] SHER Heleisich. 2p SNES] Beh FRe NMR, MS SE IRE | AAEY MOVES IACI}, aamyrenone(1), aamyring) 3 BamyringyOZ EAHA. oS IGS] titerpenoidt= ABATE AS VII. Key words: 799238, atamyrenone, ccamyrin, Bramyrin A WB (Erigeron annuus LS *3I2HCompositaeyl 48S Sohal} 8] FBAEEA, $2) Uap als Zee] Yop AS AQT ARS Pelt. Wy ZuCALSZ sol 30-100 emol3t B7= BHO] Batol Be Go} gen} 7 Ah Ho] ZEAL. VE ATOMS SMAAK) Vo} gle} 7 elie Hal) OE AAC aly WHS Apatshw, 6-walot Way Tse Ce ARMS] Slo] wR ole}. -PBhAAIE NS 7h A Ba} VE) So) MMV Sell, AAG 2m AES ashaukieyt Sepa. Deb, eyes BRS] BB EIS Gol] Aste, gato lt AM, awa Z a, Ula 8 Bajeo} Zu. HRs] Fa AOR ast G71RHE a She} Woy ly BAS 7H a hydroxycinnamie acid 2 3,4-dihydroxycinnamic acid methyl esters} 2-RFE] Shydroxy-pyrantone 8 S-butyl-3-o10-2,3- Ginydrofuran-2-y1 acetic acid} #2} 485rS}0} 312 GAL a ©] al BG 7H 35-di-O-caffeoylquinic acid? methyl 35-di-O-caffeoylquinate? $9] alo] We}sIo] BIEL ve sey. BHATRE = 9] BHEHOY cHatohe IRAP oFO}a}2] ate BAGS) Aah Ee RB MeOH FEES WAC HLSHC] 3S) iterpenoid SHAS Hes. Lele) 389) titerpenoid SHES ARROWS A Belsiateh. 2 SHINES] chromatogaphyS ¢1-¢ tz], ial 3! NMR SS O18 He SAO} ae vst} eich, sa Phoue: 82-31-201-2661, Fax: 82-31-201-2157 E-mail: niback@khuaeke 42 Ae Oe JV SAIS NMR 29} G2 Varian Inova AS. 400 (Varian, USA}&E, IR 24RERS Spectrum One(Perkin-Elmer, USA)S, polarimeter P-1010{JASCO, Japan)°.=, EVMS= JMSAX 505-WAGEOL, Japan) 33491}. HPLC LC- 1OAT(Shimudza, JapanjE, EAL FisherJohw’s Ming Point ApparanusFisher Scientific, USAJE A}8-81e} 473a}sts!, P]w abst. Column chromatography silica gek2 Kiese gel 6O(Merck, Germany) octadecylsilica geODS)® LiChroprep RP-18(Merck, Germany) AHB}2\CH. TLC Kieselgel 60 Fd RPS Fa, BA, Aol 1 VE ASS FAS Aso. BAR, G2) Ao}-als] viva] BS Aa azIeh AT, ER RKHUMMINE AIR ITH ae soho wztslo} ste. BABA) ASD MET. IRB 12kee 80% MeOH BAUS X23 789} BLOM AL HET F oh are sist. Goial ahs sca BahsSeh, of SSES EL |st ethyl acetae(BOAc, 2X I= EM) FESt S120}, BEE OA] mbuanoln BOK, 212% AH Est SU. 2 SS AP SAslo} BOA Gg), mBUOH ES) 15g) B BHIZO ge WAC. SHINE 19] #2]. BOAc FEEEAE)E slica gel column (@9%20em) _chromatography(w-hesane : OAC =7: 1-+5: 1 S:boL Da AAs} 2H) VAR EAEL-EAEDE Ws. = & EAEN99T mg) 4281 sla gel column chromatography (cc., mehexane : EtOAc = 40: 1-930: 1, 5.5% 11 emysle] 1279) 9] 23}E(BAIS-1-EAES129% BSL, BAE3-6(46 mg) O) (ODS co(MeOH :H,0=35:1, 38%9 cme AA] SE HEAES-6-7, 21 mgd #2121}PABZ9) witerpenoi as * d(ecamyrenone) : R= = 2(o-amyrin) =0oH AD) sy, “ 3(G-amyrin) Fig. 1. Chemical structures of trterpenotds from the Mower of Brigeran anmuus 1. SVRLE A: White powdenCHCl-MeOH), mp. 125-126C, BUMS n/c: 424M), 218; [aly $960 (¢=0:7, CHCl): IR, (CHCA, en) 1715, 1385, 1370; HENMROO MHz, CDCL, 8) SASUH, da, J=40, 32 Hz, 112), LOTGH, s, 123), LOGE, s, H25, 27), LOGGH, d, J=68 Hz, 1-29), 108 GOH, 5, 124, 26), O88GH, d, J=68 Hr, 130), 079GH, s, H28), "C-NMR(00 MHz, CDC. 8.) 2165(C3), 1396 (C3), AUC, CIB), SACS), 46909, 42.5C- 1, A1.5C-2), 4008), 39.1C-19), 39.6(C-20), 39.5(C-1), 36ACIO}, MAC, BCID, 325(C7), VOC, BDAC), WSC), WACAS), OKC), 2371-16), ROC), 26KC29), SC28), ACID, 19.1C-6), 169C-1), 164C26). 155(C25) SHE 25} 36) 2], EAEO(TOA mg) US sien gel cx (robexane: EIOAC=10:1, 45% 16em)sF°) 10789] ET (EAE6-1~EAB6-10}2 G51, EAE6-S(456 mg) cH) silica, gel ce(vbexane EIOAe : MoOH=70: 1:1, 35% 15 emp} 11719] 251 EAEG SA-EAESS.1S 29124, = 3 EABS- 5$-4(217 mg)® ODS c.c.(MeOH : H,0 = 10: 1-*20: 1730: 1, 35% 13emis, BAS EABSS-49(108 mg\ee ETAT. AIS. EAES-S4.905 ma)54] HPLC ol88s] SHES welebatch Bele WHS Lana Su C,(250% 46 mms AE SIL, E224) MeOH: HOO: 8) Boh RANE AH 5) SEAM. FES LomMminde abe Bae refractive index detector(RID-10A, Shimadzu, Japan) Ab8-3} ‘ACH, | ASH retention time?) Z}2} 26'- OR} Wit STH 71 VHS] peak7t BASIC Zt peaks WH BA BF, St SHIN SHE IEALGS49-1, 1omgs} BES 3 (EAESS-4.9.2, 6mgye Hels}ateh. SHIHE 2 White powde(CHCLMcOM), mp 18318", EUMS m/z: 426(M0), 218; [Gly +880 (C=04, CHCL): IR, (CHC, cnr") 3320, 1645; 'H-NMR(4O0 MHz, CDCI, 5) S2IUH, dd, J=40, 40 Hz, 1-12), 34411, dad, J=100, 60 Hr, H3), LO83H, s H27, 1023H, 5, 126), 1.00 GH, 5, 1-23), O98GH, s, 1125), O903H, d, J=64 Hz, 14.30), O81GH, s, H24, 28), OSIGH, d, J=64 Hz, 1-29 NENMR(OO MHz, CDC), 8) 139.313), 1244-12), TIAC3), SBKCI8), S53C-5), 416(C-9), 4.4C-14), 414 (C2, WAC), 39.4C-2), 39.4(C-19), ONC), 38.1C- D, 67C10}, BACID, RHCT, ILUC2H, 26(C-15), BHC2®, BAC), THC, 25C16, 232C2M, 21 (C29), 21.2130), I84C6), IACI), 167C26), 15.6(C- 25), 15624) SHEE. 3: White powderCHCl-MeOH), mp. 193-194C, EUMS m/z: 426(M), 218; [@]p +890 (€=03, CHCL): IR, (CHC, env!) 3300, 1663; "HENMR(4OO Miz, CDCI, 8) S2SUIH, dd, J=40, 40 Hr, HeI2, 3520H, m, 13), L22GH, s H27, LOUGH, s H26), O96GH, s, H23), O9MGH, , H25), OBNGH, s, 1-29, 30), O8ZGH, 5, 128), OJTGH, s, H-24;, "CNMR(OD MHz, CDC, 3). 144.64C- 13), 121812), THC), SSCS), 4THC9), 47.1(C-18), 466C-19), ALC), 39.44), 39.0C8, 38.NCA), 37.0 (C2), 368(C10), HSICLD, 33.MC2, 32.HCD, 32.H1C- 11), 308C20, 284-28), 2821623), 268(C2), 26.81. 16), 26.UC-15), 258C-2, 234(C-30), 235(C-1), 184C- 6), 1671C-26), ISAACS), 15.41C-24) aa De AEST] Io}! MeOH FEA slo} Soke] 4-o} WH} BtOAc, nBUOH HOS 3} RSL 7 ALIS SHeSe}o} she) WHS Vee} BOC LAE sitca gel column chromatography $1 ODS column chromatography = Salclo} SHE 1S BALSIRLy, ANE 2h 3] aha Eel EAE6S-49 Q91c} SINE 12 Qale) BE HNMR 2st Sofy 85.13 AH, dd} signat®4*€) olefinic methine proton? 2% gh + S151, 6257-81.0091°1 8F2) methylenes} methine proton Sun S218 = USMCh ER LOTGH, 9, LOGI, »), 1.03(6H, s) $2 0.79(3H, sje] 6799] singlet, L06(3H, d)2 0.883H, dl] 2712] doublet methyl proton signal 21413} AH. HPT SPS 1S SA VAS 7} pentacyclic teritepenoia -95)2¢. “C-NMR 245 el] G4 3072) Eb: signal] Fels] BLM, 2165094 ketone signalo} 4.5] RT}. 3139.619+ B11} We] oPSABS Helsiast, 85914-81689 Ah]a BER BM WS BU AE WHS + AS - Hole - uel 14 HF] methine2+ methylene signal Gb + aston}, 528.82, 26.64, 23.60, 23.60, 21.57, 21.45, 1689 3 15.50-l] A SASL methyl signalel BSAC. WY SHE 1S oubiet methyl?) 2792 singlet methy!7] 6S 7P8 ursane BAS teterpenoid SHB: AS ARF asta. ©] Sh AS ARES SPs] NMR spectrum vate ash" gh TNE 12 pentacyclic triterpenoid?) c-amyrin®] 3%] hydroxyl 27} Absa} Ketone?17F IE ocamyrenone®-2. evs. WY, EABG-S-4-9(103.2mg)= thin layer chromstorephy (1c) Ho} Gal Bale Selslo| NMR AoE gS BAlal % Aah DiS) SNS) Sse} Me AS e+ se. of 24 WPLCE lBsie] AR DBI WG eIse retention time®| 2}2} 26% 30%:9} 284 S7%2) peak Bol ¥AS Valea] OE 2 2 98 Heese. SHINE 2te 49) BEA) SNE 1(ccamyrenone)st |W, PCNMR AAS Mstoke 23} SHHE 19] 38 ketone ald on Sasisle. ov Se 14% BolA| Be oxygenated methine proton signslo] 340H, 409141 2495120, "ONMR AME BOE 321652) ketone signi] AH A 877560141 oxygenated mebine carbone] WSIS. WHY AIRE 2 ursnerls| ccamyrin® = Sah SNE 32-24 EUS HNMR AAS Vols) 8525(1H, 4}} signali2°22) olefinic methine protons} 83.520H, dal Signal¥€} oxygenated methine proton e}Reh. EE 82.03-81.0294] O42) methylenes} methine proton signal B63, 51.22GH, 8), 1.003H, 8), 0.963H, s), 0.94GH, s), 0.87(6H, s), 0.82(6H, s) 2 0.773H, 8141 87112} singlet methyl proton signal ®212}9%e, 9]2}¢- methyi712} coping GH SHIE Ihe GE Woe ae 3e womeshs HE BAS 7 ache AS a + aateh. NCNMR As elA} GAP 30712) Ga signal #215] SLM, 6144.60 5121809141 AS) ola, 87750014 1 22} oxygenated methine signal Aele}sich. EE 833.08, 2835, 2821, 2581, 2343, 1666, 1539 8 153994 879] methyl sign) BSSI6ICh EQ DEPT AHO SF CAS PEON, sit G47E TH AL AS Me + asleh, apeha) ge WE 38 GA) BS) medyi712} coupling Bes} 3-43 2) NGS VHS} oleaane BAO|HE WE A = etch. oF WS 32 ERAS] LAN Lalo} singlet methyl) PEE 71 ANZ 38 ALA hydroxyl717F BAP oleanane Z212) pentacylic tenterpenoid®! Bamyrinoe Saisie olelol 2212 tterpenoid SHEE Isodon japonicus H.° 5} Aliberia macroplyla? ‘83 2% APE} B21, WPS|SL Ou} WYRE AS LEYLA ceamyrinsh Be amyrin®: 2 7S-SE aM |7He AY) Wot el oh sh 2 Fe] Ue obs: Gal Fe + seks Bol, IR) SMS 17S AVIS ale. Ee of aeloly Be} 2 3S) witepenoidst ve FAS 711 unolie acids oleanolic acid} Yat SY UAS” ao] ¥relalo-sat o} So} HAR Ho) AIS AEW War} le wee eo. aA = 2 are ETSY Meloaeia 8 aah F FeSMMEARI ald Atala zaehpA| zat 5) 2 qasigte. a22h 1. Jung, B.S, and Shin, M. K, (1990) In Hoang Yak Due Sa Jun Young Lim Sa (Se el) Seoul, Korea. 2.0h, H.C, Lee, S, U, Lee, H. 8, Lee, D. H, Lee, 8. ¥, Chung, H., Kim. 8. and Kwon, T: 0, (2002) Germination inhibitory constituents fom Erigeron anus. Phytochemistry 1, 175.179. 2.08, H.C, Kang, D. G, Les, 8. ¥. and Lee, H. S. (2002) Angiotensin comerting enzyme inhibitors fom Cuscuta Japonica Choisy. J. Eiinopharmacol. 83, 105-108 4.Seo, 8, Tomita, ¥. and Tos, K. (1975) Carbon NMR specra of urs-I2-enes and application «9 strctl assignments ‘of components of Isodon japonicus HL tissue cultures Tetrahedron let. 1, 7-10 5. Hinge, V. K, Wagh, A. D., Palka, 8. K and Bhattacharyy2, S. C. (1968) Terpencid+LXXI Constnens of Indian black ‘amar resin. Terahedron 21, 3197-3203. 6.Mlu, W. HL, Ko, PD. S, Lee, ¥. Cy Li, MoM and Antu HL R, (1975) Titerpeoids from tea Lithocarpus species of Hong Kong. Phyochemisiy 14, 1063-1066, 7.Bolani, V. D. 8, Tevisan L. M. V. and Young, M. C. M. (1991) Cafe acid esters and witepenes of Alibeia macrophylla, Phyochemisiry 3, 2089-2091 8 Oliveira, F A, Litme-Junior,R. CP, Cori, W. M,, Viia- Junior, G. ML, Chaves, M. H, Almda, FR. C., Silva, R. M. Sas, FA. and Rao, Vi SN. 2004) Pentayclic crtespeooids,ceB-amytins, suppress the sctaching behavior in a mous model of pris. Pharmacol. Biochem. Be. 78, 719- ms. 9. Hah, J.C, Rhew, TH. Choe, E. 8, Chong, HY. and Park, K. ¥. (1982) Anitomor effect of ursoic acid against inbred Inpatoma in CBA mouse. J. Korean Cancer 24, 790-74 10.Li, 1. (1995) Phamacology of oleanoic acid and solic aid J. Ethnopharmacol. $9, 5768.HAI! witrpenoid Development of Biologically Active Compounds from Kdible Plant Sourees XIIL. Isolation of ‘riterpenoids from the Flower of Erigeron annuus L. Dong-Hyun Kim, Sung Je Jung, Myun- Ho Bang, InSik Chung, Sung-Hoon Kim’, Byoung-Mog Kwon’, Dae-Keun Kin’, MicHyun Pai and Nam-In Beek (Graduate School of Biotechnology & Plant Metabolism Reserch Center; ‘Graduate School of East-West Medical Science, Kyung Hee University, Swvon, 449-701; *Korea Research Institute of Bioscience and Biotechnology, KIST, Taejon 305-333: ‘Department of Pharmacy, Woosuk University, Jeunbuk 565, 701; “Ewom Life Co. Lid, Seoul 135-825, Korea) Abstract: The flower of Erigeron annuus L. was extracted with 80% agueous MeOH, and the concentrated extract, was partidoned with EIOAc, 1-BuOH and HO, successively. From the E1OAc fraction, three compounds. were isolated through the repeated silica gel, ODS column and high performance liguid chromatographies, From the result of physico chemical data including NMR, MS and IR, the chemical structures of the compounds were determined as ceamyrenone, ocamyrin and Beamyrin, These three compounds were isolated forthe fist time from the flower of rigeron anus Le ‘Key words: Erigeron annuus L,, ocamyrenone, dcamyrin, Beamyrin *Coresponding author 5