全 文 ：AnewtriterpenoidsaponinfromthefruitsofPolygonumorientale
YANGZhi-yun1, 2 , QIANShi-hui2＊ , QINMin-jian1＊
(1.DepartmentofTraditionalChineseMedicinalResources, ChinaPharmaceuticalUniversity, Nanjing210038 , China;2.Department
ofTraditionalChineseMedicinalResources, JiangsuProvincialInstituteofTraditionalChineseMedicine, Nanjing210028 , China)
Abstract:TostudythechemicalconstituentsofthefruitsofPolygonumorientaleL., silicageland
ODScolumnchromatographymethodswereusedtoseparateandpurifytheconstituents.Theirstructures
wereelucidatedonthebasisofphysicochemicalpropertiesandspectralanalysis.Threecompoundswere
identifiedas28-O-β-D-glucopyranosyl-3β, 7β-dihydroxy-lup-20(29)-en-28-oate(1), 5, 7-dihydroxychro-
mone(2)andnaringenin(3).Compound1 isanewtriterpenoidsaponinandotherswereisolatedfrom
thefruitsofthisplantforthefirsttime.
Keywords:Polygonumorientale;triterpenoidsaponin;28-O-β-D-glucopyranosyl-3β, 7β-dihydroxy-
lup-20(29)-en-28-oate
CLCnumber:R284.1;R284.2　　　Documentcode:A　　　ArticleID:0513-4870(2008)04-0388-04
Received2007-10-18.
ProjectsupportedbyCommonwealFoundationofJiangsuProvince
(BM2006104).
＊Corespondingauthor　Tel:86-25-85639644,
Fax:86-25-85639640,
E-mail:njqsh2005@126.com
Tel:86-25-85391290,
Fax:86-25-85301528,
E-mail:minjianqin@ 163.com
红蓼果实中的一个新三萜皂苷
杨志云 1, 2 , 钱士辉 2＊ , 秦民坚 1＊
(1.中国药科大学 中药资源学研究室 , 江苏 南京 210038;
2.江苏省中医药研究院 中药资源化学研究室 , 江苏 南京 210028)
摘要:为了研究红蓼果实的化学成分 , 利用硅胶和反相柱色谱方法进行分离纯化 , 根据理化性质和光谱数据鉴
定其化合物结构 ,分离并鉴定了 3个化合物:28-O-β-D-glucopyranosyl-3β, 7β-dihydroxy-lup-20(29)-en-28-oate(1), 5,
7-二羟基色原酮(2)和柚皮素(3)。化合物 1为新化合物 ,化合物 2, 3为首次从该植物中分离得到。
关键词:红蓼;三萜皂苷;28-O-β-D-glucopyranosyl-3β, 7β-dihydroxy-lup-20(29)-en-28-oate
　 　 The fruits of Polygonum orientale L.
(Polygonaceae), caled“Shuihonghuazi”, havebeen
usedastraditionalChinesemedicinetotreatgastralgia,
hepatitis, hepatocirrhosisanddiabetes[ 1, 2] .Previous
phytochemicalinvestigationrevealedthatthefruitsof
P.orientaleL.containedflavonoidsandcinnamicester
derivatives[ 3-5] . In thispaper, wereported the
characterizationofanewtriterpenoidsaponin, 28-O-β-
D-glucopyranosyl-3β, 7β-dihydroxy-lup-20(29)-en-28-
oate(1), togetherwithtwoknowncompounds, 5, 7-
dihydroxychromone(2)andnaringenin(3).
Resultsanddiscussion
Compound1 wasobtainedaswhitecrystal.
TheHR-ESI-MSshowedamolecularionatm/z:
657.399 6 (calcdforC36H58O9Na, 657.397 3).The
IRspectrumshowedabsorptionsat3 483 (OH)and
1 732cm-1(ester).The13CNMRandDEPTspectra
revealed36carbonsignals, includingsixmethyls, ten
methylenes, oneofwhichwasoxygenatedatδ62.4,
twelvemethines, sevenofwhichwereoxygenatedat
δ:71.3, 74.2, 74.8, 78.1, 79.0, 79.3 and95.5,
fivequaternarycarbons, twoolefiniccarbonsatδ:
151.3(s)and109.9(t)andonecarbonylatδ175.2
·388· 药学学报 ActaPharmaceuticaSinica2008, 43(4):388-391
(s).Inspectionof1Dand2DNMRspectraof1
proposedthatitpossesedalupanetriterpeneglycoside
andtheaglyconewassimilarto3β, 7β-dihydroxy-lup-
20(29)-en-28-oicacid[ 6] .Therelativestereochemistry
ofthetwohydroxylgroupsatC-3 andC-7wasasigned
asβ basedonNOESY experiments.TheNOESY
spectrumshowedNOEenhancementsbetweenH-3 and
protonsH-1, H-5, andCH3 -23, indicatingthatH-3
shouldbeα.Inaddition, NOEenhancementswere
observedbetweenH-7 andprotonsH-5, H-9, and
CH3-27, confirmingthatH-7 shouldbeα(Figure1).
TheappearanceofaCH2 groupatδ62.4andfiveCH
groupsatδ:95.5, 79.3, 79.0 , 74.2, 71.3 are
characteristicofD-glucose[ 7] .Itwasalsoconfirmedby
TLCcomparingtheacidhydrolysateof1 withglucose
authenticsample.TheanomericprotonH-1′ofthe
glucosemoietyresonatedasadoubletatδ6.45.A
couplingconstantof8.1 HzforH-1′indicatedthatthe
stereochemistryoftheglucosidiclinkageatC-1′of
glucoseisβ.Comparisonsofthe13CNMRspectrumof
1 and3β, 7β-dihydroxy-lup-20(29)-en-28-oicacid
indicatedthat1 isaglucopyranosylesterof3β, 7β-
dihydroxy-lup-20(29)-en-28-oicacidatC-28, based
ontheupfieldshiftofC-28 fromδ:179.5 to175.2
(Table1).FurtherevidencecamefromtheHMBC
spectrum, inwhichthecarbonsignalatδ175.2
showedcorelationwithH-1′(Figure2).Basedonal
theevidenceabove, compound1 wascharacterizedas
28-O-β-D-glucopyranosyl-3β, 7β-dihydroxy-lup-20(29)-
en-28-oate.13Cand1HNMRchemicalshiftassignments
ofcompound1werebasedonDEPT, HMBC, HSQC,
1H-1HCOSYandNOESYspectra.
Previousassignmentsof 13C signals led to
divergencebetweentheC-18andC-19 chemicalshifts
ofsimilarcompounds[ 8] .Pengindicatedthe 13C
assignmentsofC-18 andC-19 ofbetulinicacidwere
eroneously interchanged in earlier reports[ 9] .
Accordingtoourresults, the13CassignmentsofC-18
andC-19 of3β, 7β-dihydroxy-lup-20(29)-en-28-oic
acidmaybeinterchanged.Thisconclusionwasin
accordance with many reports[ 10 -13] . The 13C
assignmentsofC-18 andC-19 of1 wereconfirmedby
HMBC and NOESY experiments. In the HMBC
spectrum, C-19 (δ47.7)showedcrosspeaksbetween
H-29α(δ4.90), H-29β (δ4.75), CH3 -30 (δ
1.76).Moreover, H-18 (δ1.84)exhibitedcross
peakswithC-17(δ57.0), C-28(δ175.2), C-16(δ
32.8), C-14 (δ44.2)(Figure2).Furthermore, the
NOESY spectrum showedNOE enhancementswere
observedbetweenH-19(δ3.47)andprotonH-13(δ
2.80).Inaddition, NOEenhancementswereobserved
betweenH-18 (δ1.84)andprotonH-16α(δ1.60)
andCH3-27 (δ1.25)(Figure1).
Figure1　KeyNOESYcorelationsofcompound1
Figure2　KeyHMBC(H※C)corelationsof
compound1
Experimental
Generalexperimentalprocedures　Almelting
pointsweredeterminedbyaXT-4Amicromeltingpoint
apparatusand areuncorected. IR spectrawere
recordedbyaFTIR-8900(KBr)spectrometer.1Dand
2DNMR spectrawererunonaBruckerAV 500
spectrometerwithTMSasinternalstandardandvalues
weregiveinδ.HR-ESI-MSandESI-MSmeasurements
wereperformedonanAPEXmassspectrometerandan
Agilent 1100 series LC/MS Trap apparatus,
respectively.Columnchromatographywascariedout
onsilicagel(200 -300 mesh)(QingdaoHaiyang
ChemicalCo., Ltd), polyamide(Taizhou), ODS
(JiangsuHanbonScienceandTechnologyCo., Ltd),
andSephadexLH-20 (PharmaciaBiotech).
Plantmaterial　ThefruitsofP.orientaleL.
werecolectedfromJiangsuinJune2006.Theplant
materialwasidentifiedbyProfessorQianShihui.A
voucher specimen (SHHZ-2006-07) has been
depositedintheDepartmentofTraditionalChinese
MedicinalResources, JiangsuProvincialInstituteof
TraditionalChineseMedicine.
·389·YANGZhi-yun, etal:AnewtriterpenoidsaponinfromthefruitsofPolygonumorientale
Table1　1HNMRand13CNMRdataofcompound1
inC5D5N
No. δH δC δCa
1 1.66(m), 0.94(m) 39.4(t) 39.8(t)
2 1.84(m) 28.4(t) 28.9(t)
3 3.45(dd, J=5.2, 10.5Hz) 78.1(d) 78.5(d)
4 39.4(s) 39.8(s)
5 0.94(m) 53.4(d) 53.7(d)
6 2.46(m) 33.9(t) 34.6(t)
7 4.11(dd, J=5.2, 10.3Hz) 74.8(d) 75.5(d)
8 47.6(s) 47.8(s)
9 1.35(m) 51.4(d) 51.7(d)
10 37.8(s) 38.2(s)
11 1.50(m), 1.35(m) 21.5(t) 21.9(t)
12 1.97(m) 26.6(t) 26.9(t)
13 2.80(m) 39.4(d) 39.9(d)
14 44.2(s) 44.3(s)
15 2.15(m), 1.35(m) 31.0(t) 31.7(t)
16 2.70(m), 1.60(m) 32.8(t) 33.8(t)
17 57.0(s) 57.1(s)
18 1.84(m) 49.9(d) 48.5(d)
19 3.47(m) 47.7(d) 50.2(d)
20 151.3(s) 152.1(s)
21 1.97(m), 1.84(m) 30.4(t) 30.8(t)
22 2.15(m), 1.50(m) 37.1(t) 38.2(t)
23 1.22(s) 28.6(q) 29.1(q)
24 1.01(s) 16.4(q) 16.8(q)
25 0.86(s) 16.4(q) 16.8(q)
26 1.42(s) 10.9(q) 11.5(q)
27 1.25(s) 15.2(q) 15.7(q)
28 175.2(s) 179.5(s)
29 4.90(s), 4.75(s) 109.9(t) 110.3(t)
30 1.76(s) 19.6(q) 20.1(q)
Glucose
1 6.45(d, J=8.1Hz) 95.5(d)
2 4.20(m) 74.2(d)
3 4.30(m) 79.0(d)
4 4.38(m) 71.3(d)
5 4.05(m) 79.3(d)
6 4.45(m), 4.38(m) 62.4(t)
a3β, 7β-Dihydroxy-lup-20(29)-en-28-oicacidinC5D5N
Extractionandisolation　19 kgdriedfruitsof
P.orientaleL.wereextractedtwotimeswith80%
EtOH atreflux.Theextractswerecombinedand
concentratedunderreducedpressure, andtheresidue
wasdissolvedinhotwater, andthensuccessively
partitionedwithpetroleum ether, EtOAc, andn-
butanol.Then-butanolfraction(356 g)wasabsorbed
onD101 resinusingagradientfromH2Oto95%
EtOH.Thefractionelutedwith70% EtOH(223 g)
waschromatographedoversilicagelcolumneluting
withCHCl3-MeOH(ingradient, 95∶5 to0∶100)to
yield9majorfractions, combinedonthebasisofTLC.
Fraction5(CHCl3 -MeOH8∶2)wasseparatedbysilica
gelcolumnchromatographyelutedwithCHCl3 -MeOH
(95∶5to6∶4)togivesubfractions5a-5j.Subfraction
5ewaspurifiedbyODScolumnelutedwith70%
MeOHtoafordcompound1 (9 mg).TheEtOAc
fraction(110 g)wassubjectedtopolyamidecolumn
usingagradientfromH2Oto95% EtOHtoobtain8
majorfractions.Fraction4 wasseparatedbySephadex
LH-20 withMeOHtoafordcompound2 (12 mg).
Fraction6 waschromatographedoversilicagelcolumn
elutingwithCHCl3-MeOH (ingradient, 100∶1 to
8∶2)togivesubfractions6a-6m.Subfraction6dwas
purifiedbySephadexLH-20 withMeOH toaford
compound3 (12 mg).
Identification
Compound1　whitecrystal;mp204-206 ℃;
IR(KBr)νmax:3 483, 2 961, 1 732, 1 038, 879
cm-1;HR-ESI-MSm/z:657.399 6 (C36 H58 O9Na;
calcd.657.397 3);ESI-MSm/z:633 [ M-H] -,
652[ M+NH4 ] +.1HNMR(500 MHz, C5D5N)and
13CNMR(125 MHz, C5D5N)datawerelistedin
Table1.
Compound2　whitecrystal;mp272-273 ℃;
ESI-MSm/z:177[ M-H] -, 179[ M+H] +.1HNMR
(500 MHz, DMSO-d6)δ:6.20(1H, d, J=2.0 Hz,
H-6), 6.27(1H, d, J=6.0 Hz, H-3), 6.36(1H, d,
J=2.0 Hz, H-8), 8.18(1H, d, J=6.0 Hz, H-2),
10.85(1H, s, 7-OH), 12.69(1H, s, 5-OH).13CNMR
(125 MHz, DMSO-d6)δ:157.5(C-2), 110.6(C-3),
181.4(C-4), 161.7(C-5), 99.1(C-6), 164.4(C-7),
94.0(C-8), 157.9(C-9), 105.0(C-10).Thesedata
wereidenticaltotheliteraturevaluesof5, 7-dihydroxy-
chromone[ 14, 15] .
Compound3　whitecrystal;mp255-256 ℃;
ESI-MSm/z:271[ M-H] -, 273[ M+H] +.1HNMR
(500 MHz, DMSO-d6)δ:2.70(1H, dd, J=17.1,
3.0 Hz, H-3 cis), 3.26(1H, dd, J=17.1, 12.8 Hz,
H-3 trans), 5.45(1H, dd, J=3.0, 12.8 Hz, H-2),
5.88(2H, s, H-6, 8), 6.79(2H, d, J=8.5 Hz, H-3′,
5′), 7.31(2H, d, J=8.5 Hz, H-2′, 6′), 12.14(1H,
s, 5-OH).13CNMR(125 MHz, DMSO-d6)δ:78.5
(C-2), 42.1(C-3), 196.4(C-4), 163.6(C-5),
95.9(C-6), 166.7 (C-7), 95.0 (C-8), 163.0
(C-9), 101.9(C-10), 129.0(C-1′), 128.3(C-2′),
·390· 药学学报 ActaPharmaceuticaSinica2008, 43(4):388-391
115.2(C-3′), 157.8(C-4′), 115.2(C-5′), 128.3
(C-6′).Thesedatawereidenticaltotheliterature
valuesofnaringenin[ 16] .
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