全 文 ：天然产物研究与开发 NatProdResDev2009, 21:593-599
文章编号:1001-6880(2009)04-0593-07
　
　
　ReceivedMarch25, 2008;AcceptedMay15, 2008
＊CorrespondingauthorTel:86-28-85225401;E-mail:zhanggl@cib.ac.
cn
野桂花化学成分研究
马晓莉 1, 2 ,林文彬 1, 2 ,张国林 1＊
1中国科学院成都生物研究所 , 成都 610041;2中国科学院研究生院 , 北京 100039
摘　要:从野桂花(Osmanthusyunnanensis)地上部分 95%乙醇提取物中首次分离得到 18个化合物 ,应用波谱方
法及与已知品对照的手段鉴定它们为:E-阿魏酸二十烷基酯(1)、β-谷甾醇(2)、羽扇豆醇(3)、齐墩果酸(4)、 7-
oxo-β-sitosterol(5)、乙酰齐墩果酸(6)、(6′-O-palmitoyl)-sitosterol-3-O-β-D-glucoside(7)、rotundioicacid(8)、地榆
糖甙Ⅱ (9)、 3β-hydroxy-27-p-(E)-coumaroyloxyolean-12-en-28-oicacid(10)、 3β-hydroxy-27-p-(Z)-coumaroyloxy-
olean-12-en-28-oicacid(11)、hycandinicacidester(12)、绿原酸丁酯(13)、4, 5-二咖啡酰奎尼酸丁酯(14)、 28-O-β-
D-glucopyranosylrotundioicacid(16)以及三个半萜类化合物:4, 5-dihydroxyprenylcaffeate(15)、4-(6-O-cafeoyl-β-
D-glucopyranosyloxy)-5-hydroxyprenylcaffeate(17)、4-β-D-glucopyranosyloxy5-hydroxyprenylcafeate(18)。
关键词:野桂花;甾体;三萜;咖啡酰奎尼酸丁酯;半萜
中图分类号:R284.1;Q946.91 文献标识码:A
ChemicalConstituentsofOsmanthusyunnanensis
MAXiao-li1, 2 , LINWen-bing1, 2 , ZHANGGuo-lin1＊
1ChengduInstituteofBiology, ChineseAcademyofSciences, Chengdu610041 , China;
2GraduateSchoolofChineseAcademyofSciences, Beijing100039 , China
Abstract:Eighteencompoundswereisolatedfromthe95% ethanolextractoftheaerialpartsofOsmanthusyunnanensis
forthefirsttime.Onthebasisofspectraldataorcomparisonwithauthenticsamples, theywereidentifiedasE-ferulic
acideicosylester(1), β-sitosterol(2), lupenol(3), oleanolicacid(4), 7-oxo-β-sitosterol(5), acetyloleanolicacid(6),
(6′-O-palmitoyl)-sitosterol-3-O-β-D-glucoside(7), rotundioicacid(8), ziyuglycosideⅡ (9), 3β-hydroxy-27-p-(E)-
coumaroyloxyolean-12-en-28-oicacid(10), 3β-hydroxy-27-p-(Z)-coumaroyloxyolean-12-en-28-oicacid(11), hycandin-
icacidester(12), chlorogenicacidbutylester(13), 4, 5-di-O-caffeoylquinicacidbutylester(14), 28-O-β-D-glucopyr-
anosylrotundioicacid(16)andthreehemiterpenederivatives:4, 5-dihydroxyprenylcafeate(15), 4-(6-O-cafeoyl-β-D-
glucopyranosyloxy)-5-hydroxyprenylcafeate(aohada-glycosideC, 17), 4-β-D-glucopyranosyloxy-5-hydroxyprenylcaf-
feate(aohada-glycosideA, 18).
Keywords:Osmanthusyunnanensis;steroid;triterpene;caffeoylquinicacidbutylester;hemiterpene
Introduction
PreviousphytochemicalstudiesonOsmanthusgenusre-
vealedthepresenceofsecoiridoidglycosides, lignans,
phenylpropanoidglycosidesandp-coumaroylglyco-
sides[ 1, 2, 18] .Chinaisthecenterofgeographicaldistri-
butionofOsmanthusspeciesintheworld.Researchof
OsmanthusspeciesmainlyfocusesontheOsmanthus
fragrans, atraditionalChinesemedicinalplantandfa-
mousornamentalplant.Studiesaboutgermplasmre-
sources, cultivarclassification, cultivatingandpropaga-
tionwerereported[ 3] .O.yunnanensis(Fr.)P.S.Green
ismainlydistributedinYunnan, SichuanandTibet
provincesofChina[ 4] .Itsflowersareusedinfolkmedi-
cineasexpectorantandanti-coughagent;Itsrootsare
usedforthetreatmentofgastralgia, odontalgia, expel-
lingwindandforremovingdampness[ 17] .Untilnow, no
chemicalinvestigationswerecarriedoutonthisplant.
Inthisstudyeighteencompoundswereisolatedfrom
the95% ethanolextractofaerialpartsofthisplant.On
thebasisofspectralevidenceorcomparisonofthem
withauthenticsamples, theywereidentifiedasfolows:
E-ferulicacideicosylester(1), β-sitosterol(2), lupe-
DOI :10.16333/j.1001-6880.2009.04.031
nol(3), oleanolicacid(4), 7-oxo-β-sitosterol(5),
acetyloleanolicacid(6), (6′-O-palmitoyl)-sitosterol-3-
O-β-D-glucoside(7), rotundioicacid(8), ziyuglyco-
sideⅡ(9), 3β-hydroxy-27-p-(E)-coumaroyloxyolean-
12-en-28-oicacid(10), 3β-hydroxy-27-p-(Z)-cou-
maroyloxyolean-12-en-28-oicacid(11), hycandinic
acidester(12), chlorogenicacidbutylester(13), 4, 5-
di-O-cafeoylquinicacidbutylester(14), 28-O-β-D-
glucopyranosylrotundioicacid(16), 4, 5-dihydroxypre-
nylcafeate(15), 4-(6-O-cafeoyl-β-D-glucopyranosy-
loxy)-5-hydroxyprenylcafeate(aohada-glycosideC,
17)and4-β-D-glucopyranosyloxy-5-hydroxyprenylcaf-
feate(aohada-glycosideA, 18).
图 1　CompoundsfromOsmanthusyunnanensis
ResultsandDiscussion
Compounds12-14 wereidentifiedasbutylesters.Com-
pound14 wasfirstisolatedfromEtOAcsolublefraction
ofthemethanolextractfromthestembarkofIsertiapit-
tieri[ 14] .Itwasreportedthat12 and13 werefirstob-
tainedfromn-butanolsolubleextractofHydrastiscana-
densisandSpondiasmombin, respectively[ 12, 13] .Inthis
studyn-butanolwasextensivelyusedforextraction.It
isnotclearthattheoriginalformofthesecompoundsin
thisplantisbutylesteroracid.Thus, thefractionFof
EtOAcfraction, obtainedbeforetheuseofn-butanol,
wassubjectedtoESI-MSanalysis, andthequasimolec-
ularionpeaksatm/z463 [ M+K] + , 433 [ M+
Na] +, 595 [ M+Na] +, correspondingtothoseofcom-
pounds12, 13 and14 werefound.Therefore, itcould
beconcludedthatcompounds12-14 maynotbearti-
factsandcouldpresentinbutylesterformintheplant.
Experimental
Materialsandmethods
MeltingpointsweremeasuredonanX-6 meltingpoint
apparatusandareuncorected.Opticalrotationswere
measuredonaPerkin-Elmer341 automaticpolarime-
ter.UVandIRspectrawererecordedrespectivelyona
Lambda35spectrometerandaPerkinElmerspectrum
oneFT-IRspectrometer(KBrdisc).Massspectrawere
carriedoutonaFinnigan-LCQDECA massspectrometer
(ESI-MS), andNMRspectra(1H:600 MHz;13C:150
MHz)onaBrukerAvance600 spectrometerwithTMS
asinternalstandard.SilicagelH(200-300 mesh;Qing-
daoHaiyangChemicalGroupCo.ofChina), MCIgel
(75-150 μm, Mitsubishi)andSephadexLH-20(Phar-
maciaBiotech, Sweden)wereusedforcolumnchroma-
tography(CC).Theplatesforthinlayerchromatogra-
phy(TLC)wereprecoatedwithSilicagelGF254 (0-40
μm)andactivatedat110 ℃ for2 h.SpotsonTLC
plateswerevisualizedbyspraying10% EtOHsolution
ofphosphomolybdicacidfolowedbyheating.
Plantmaterial
TheaerialpartsofO.yunnanensiswerecolectedinA-
pril2004 fromYanbianCounty, SichuanProvinceof
China, andidentifiedbyProf.FUFadingatChengdu
InstituteofBiology, ChineseAcademyofSciences
(CAS).Avoucherspecimen(No.A170)wasdeposited
intheDepartmentforNaturalProductsResearchat
ChengduInstituteofBiology, CAS.
Extractionandisolation
Theair-driedandpowderedaerialpartsofO.yun-
nanensis(3.5 kg)werepercolatedwith95% ethanol
(30 L×3, each10 days)atroomtemperature.After
evaporatingthesolventsunderreducedpresureat50
℃, aresidue(280 g)wasobtained.Theresiduewas
suspendedinH2Oandfractionatedsuccessivelywith
petroleumether(1.5 L×2), EtOAc(1.5L×5)and
n-BuOH(1.5L×3)toafordpetroleumetherfraction
594 NatProdResDev　　　　　　　　　　　　　　　　　　　　 　Vol.21
(4g), EtOAcfraction(92 g)andn-BuOHfraction(98
g).
TheEtOAcfractionwasdividedintofractionsA(26
g), B(10g), C(19 g), D(15 g), E(3 g)andF(2.8
g)oversilicagelcolumn(Υ8.7 ×L40cm, 1kg)elu-
tedgradientlywithpetroleumether-acetone(15∶1※ 2
∶1).FractionsBandCtogetherwassubjectedtoMCI
gelcolumn(Υ5.5 ×L13cm), elutedwithmethanol-
water(9∶1)toyieldBC1 (960 mg), BC2 (10 g)and
BC3(1.6 g).BC1 wasdissolvedinMeOHandthe
methanolsolutionwasextractedwithpetroleumether.
Thepetroleumetherlayer(618mg)wasseparatedover
silicagelcolumn(Υ2×L20 cm), elutedwithn-hex-
ane-ethylacetate(20∶1)toprovide1(40 mg).Recrys-
talizationofBC2 fromMeOHaforded2(830 mg).The
motherliquidofBC2 wassubjectedtosilicagelcolumn
elutedwithpetroleumether-acetone(10∶1)togive3(20
mg)and4(2g).Usingpetroleumether-acetone(4∶1)
assolvents, fractionBC3 wasseparatedoversilicagel
column(Υ5 ×L14cm)togive5(10mg)and6(130
mg).FractionDwasseparatedoversilicagelcolumn
(Υ8.4 ×L18 cm)elutedgradientlywithCHCl3-
CH3COCH3(30∶1※5∶1)toyieldD4(1 g)andD6(2.1
g).Compound7(30 mg)wasprecipitatedfromD4 in
MeOH.D6 wasfurtherseparatedoversilicagelcolumn
(Υ3 ×L14 cm), usingCHCl3 -MeOH(15∶1)assol-
ventstogive8(17mg)and9(13 mg).FractionEwas
dividedintofourfractionsE1-E4 bysilicagelcolumn
(Υ5 ×L20 cm).E4 (1.1g)wasseparatedover
SephadexLH-20 column(Υ3 ×L53cm)elutedwith
MeOHandtheE4-2(100mg)wassubjectedtosilicagel
column(Υ1.8 ×L50cm)withCHCl3 -MeOH(50∶1)
assolventstoyield10(10 mg)and11(15 mg).
Then-BuOH fractionwassubjectedtomacroporous
resinD101 column(Υ3.9 ×L50 cm), elutedwith
H2OandthenwithMeOH.TheMeOHfractionBu(28
g)wasdividedinto9 fractionsBu1 -Bu9 , oversilicagel
column(Υ 9.2 ×L30 cm)elutedgradientlywith
CHCl3-MeOH(8∶1※2∶1).Bu1(800 mg)wassubjec-
tedtoSephadexLH-20 column(Υ3 ×L55 cm)and
theBu1-1(45 mg)waspurifiedbyHPLCtoyield12(6
mg).Bu2(1.1 g)wasseparatedoverSephadexLH-20
column(Υ3 ×L55cm)withMeOHassolventsand
theBu2-5(27 mg)waspurifiedbyTLCtogive13(10
mg).14(20 mg)and15(30 mg)wereobtainedfrom
theseparationofBu3(1.7g)overSephadexLH-20col-
umn(Υ3 ×L55 cm)withMeOH.Bu4(1.2 g)was
separatedrepeatedlyoverSephadexLH-20 column(Υ
3 ×L55 cm)withMeOHtoprovide16(80 mg).Bu5
(3.2g)wasfirstsubjectedtosilicagelcolumn(Υ3.4
×L23 cm), usingCHCl3 -MeOH-H2O(7∶1∶0.1)as
solventsandtheBu5-1(300mg)waspurifiedbySepha-
dexLH-20 column(Υ 3 ×L55cm)withMeOHto
give17(110 mg).UsingMeOHassolvent, Bu6 was
separatedoverSephadexLH-20 column(Υ 3 ×L55
cm)toyield18(70mg).
Identification
Compounds2, 3, 4 and6 wereidentifiedsuccessively
asβ-sitosterol, lupenol, oleanolicacidandacetylolean-
olicacidbycomparingthemwithauthenticsampleson
TLCandco-mp..
E-Ferulicacideicosylester(1)　Whitepowder;ESI-
MS(positivemode)m/z:497 [ M +Na] + , 475 [ M
+H ] +, 513 [ M +K] +;1HNMR(600 MHz,
CDCl3)δ:7.60(1H, d, J=15.9 Hz, H-β), 7.07(1H,
dd, J=8.2, 1.6 Hz, H-6), 7.03(1H, d, J=1.6 Hz,
H-2), 6.92(1H, d, J=8.2 Hz, H-5), 6.28(1H, d, J
=15.9 Hz, H-α), 5.83(1H, s, -OH), 4.18(2H, t, J
=6.8Hz, H-1′), 3.92(3H, s, -OCH3), 1.69(2H, m,
H-2′), 0.87(3H, t, J=6.9 Hz, H-20′).TheESI-MS
andNMRdatawereinaccordancewiththoserepor-
ted[ 5] .
7-Oxo-β-sitosterol(5)　Whitepowder, mp.120-123
℃;UVλMeOHmax (logε)nm:237(3.99);IRυKBrmax cm-1:
3450, 1674;ESI-MS(positivemode)m/z:451 [ M +
Na] +, 429[ M +H] +;1HNMR(600MHz, CDCl3)
δ:5.68(1H, brs, H-6), 3.67(1H, t, J=11.0 , 5.0
Hz, H-3), 2.50(1H, ddd, J=13.0 , 5.0, 1.8 Hz, H-
4α), 2.40(1H, ddt, J=13.0, 11.0, 1.8 Hz, H-4β),
2.23(1H, t, J=11.8 Hz, H-8), 2.03(1H, dt, J=
12.7, 4.0 Hz, H-12β), 1.19(3H, s, H-19), 0.93
(3H, d, J=6.5 Hz, H-21), 0.85(3H, d, J=6.8 Hz,
H-27), 0.81(3H, t, J=6.8 Hz, H-29), 0.66(3H, s,
H-18);13CNMR(150 MHz, CDCl3)δ:202.3(C-7),
165.0(C-5), 126.1(C-6), 70.0(C-3), 54.7(C-17),
49.9(C-9, 14), 45.8(C-24), 45.4(C-8), 43.1(C-
595Vol.21 　　　　　　MAXiao-li, etal:ChemicalConstituentsofOsmanthusyunnanensis　
13), 41.8(C-4), 38.7(C-12), 38.3(C-10), 36.4(C-
1), 36.1(C-20), 33.9(C-22), 31.2(C-2), 29.1(C-
25), 28.5(C-16), 26.3(C-15), 26.1(C-23), 23.0
(C-28), 21.2(C-11), 19.8(C-27), 19.0(C-26),
18.9(C-21), 17.3(C-19), 11.9(C-18, 29).The
mp., UV, IR, ESI-MSandNMRdatawereidenticalto
thosereported[ 6].
(6′-O-Palmitoyl)-sitosterol-3-O-β-D-glucoside(7)
　Colourlesswax, mp.163-165 ℃;[ α] 20D -47.4 °(c
0.21, CHCl3);ESI-MS(positivemode)m/z:837 [ M
+Na] +;1HNMR(600 MHz, CDCl3)δ:5.35(1H, br
s, H-6), 4.37(1H, m, H-6′α), 4.36(1H, d, J=7.7
Hz, H-1′), 4.31(1H, d, J=11.5 Hz, H-6′β), 3.55
(1H, m, H-3′), 3.53(1H, m, H-3), 3.45(1H, m, H-
5′), 3.38(1H, t, J=9.5 Hz, H-4′), 3.35(1H, t, J=
7.7Hz, H-2′), 2.32(2H, t, J=7.5 Hz, H-2″), 1.01
(3H, s, -CH3), 0.92(3H, d, J=6.5 Hz, -CH3), 0.89
(3H, t, J=7.0 Hz, H-29), 0.85(3H, t, J=7.5 Hz,
H-16″), 0.84(3H, d, J=7.0 Hz, -CH3), 0.81(3H,
d, J=6.5 Hz, -CH3), 0.68(3H, s, -CH3);13 CNMR
(150 MHz, CDCl3 )δ:174.3(C-1″), 140.3(C-5),
122.1(C-6), 101.2(C-1′), 79.6(C-3), 76.1(C-
3′), 73.9(C-5′), 73.4(C-2′), 70.3(C-4′), 63.4(C-
6′), 56.7(C-14), 56.1(C-17), 50.1(C-9), 45.8(C-
24), 42.3(C-13), 39.7(C-12), 38.9(C-4), 37.2(C-
1), 36.7(C-10), 36.1(C-20), 34.2(C-2″), 33.9(C-
22), 31.9(C-7), 31.8(C-8), 29.7(C-2), 29.7-29.2
(11 ×CH2), 29.3(C-25), 28.2(C-16), 26.1(C-
23), 24.9(CH2 ), 24.3(C-15), 23.0(C-28), 22.7
(CH2), 21.0(C-11), 19.8(C-26), 19.3(C-19),
19.0(C-21), 18.7(C-27), 14.1(C-16″), 11.9(C-
29), 11.8(C-18).Themp., [ α] D, ESI-MSandNMR
datawereidenticaltothosereported[ 7 ] .
Rotundioicacid(8)　 Whiteamorphouspowder,
mp.295-298 ℃;UVλMeOHmax (logε)nm:210(3.65);
IRυKBrmaxcm-1:3600-3200, 1690, 1635;ESI-MS(negative
mode)m/z:501 [ M-H ] -;1HNMR(600 MHz, pyri-
dine-d5)δ:5.57(1H, brs), 4.96(1H, s, -OH), 4.64
(1H, dd, J=10.1, 6.0 Hz), 3.04(1H, m), 3.01
(1H, s), 1.08(3H, d, J=6.5 Hz), 0.95, 1.07, 1.41,
1.60, 1.65(each3H, s);13 CNMR(150 MHz, pyri-
dine-d5)δ:180.4(C-23, 28), 139.7(C-13), 127.6
(C-12), 75.3(C-3), 72.4(C-19), 54.4(C-18), 54.2
(C-4), 51.7(C-5), 48.0(C-9), 47.8(C-17), 42.1
(C-14), 41.8(C-8, 20), 40.5(C-1), 38.9(C-10),
38.2(C-22), 36.5(C-7), 33.1(C-15), 29.0(C-2,
29), 27.5(C-16), 26.8(C-21), 26.6(C-27), 26.1
(C-11), 21.5(C-6), 16.8(C-30), 16.5(C-26), 15.7
(C-25), 11.9(C-24).Themp., UV, IR, ESI-MSand
NMRdatawereequaltothosereported[ 8] .
ZiyuglycosideⅡ(9)　Crystalinepowder, mp.243-
245 ℃;[ α] 20D +38.0 °(c2.2, DMSO);IRυKBrmaxcm-1:
3430, 1689, 1620, 1459, 1385;ESI-MS(negative
mode)m/z:603 [ M-H] +;1HNMR(600 MHz, pyri-
dine-d5)δ:5.59(1H, brs, H-12), 4.75(1H, d, J=
7.0 Hz, Ara-H-1), 4.41(1H, dd, J=8.8, 7.0 Hz,
Ara-H-2), 4.31(1H, m, Ara-H-4), 4.29(1H, m, Ara-
H-5α), 4.14(1H, dd, J=8.8, 2.8 Hz, Ara-H-3),
3.82(1H, d, J=11.0 Hz, Ara-H-5β), 3.33(1H, dd, J
=12.1, 4.3 Hz, H-3), 3.05(1H, brs, H-18), 1.75
(3H, s, H-29), 1.11(1H, d, J=6.6 Hz, H-30),
1.43, 1.32, 1.08, 0.94, 0.87(each3H, s);13CNMR
(150 MHz, pyridine-d5)δ:181.5(C-28), 140.8(C-
13), 128.9(C-12), 108.3(C-1′), 89.7(C-3), 75.5
(C-3′), 73.8(C-2′), 73.6(C-19), 70.4(C-4′), 67.6
(C-5′), 56.8(C-5), 55.5(C-18), 49.2(C-17), 48.6
(C-9), 43.2(C-20), 43.0(C-14), 41.2(C-8), 40.5
(C-4), 39.7(C-1), 39.4(C-22), 37.9(C-10), 34.4
(C-7), 30.2(C-15), 29.1(C-23), 28.0(C-29), 27.8
(C-21), 27.5(C-2), 27.3(C-16), 25.6(C-27), 24.9
(C-11), 19.5(C-6), 18.1(C-24), 17.8(C-26), 17.6
(C-30), 16.4(C-25).Themp., [ α] D, IR, ESI-MS
andNMRdatawereinaccordancewiththoseofziyu
glycosideⅡ [ 9] .
3β-Hydroxy-27-p-(E)-coumaroyloxyolean-12-en-
28-oicacid(10)　Whiteamorphouspowder;[ α] 20D -
2.56°(c0.5 , iPrOH);UVλiPrOHmax (logε)nm:206
(4.17), 229(4.05), 315(4.37);IRυKBrmaxcm-1 3447,
1685, 1640, 1509, 1168;ESI-MS(positivemode)m/z:
641 [ M + Na] +, 657 [ M + K] +, 455 [ M-
C9H6O3 ] +;1HNMR(600MHz, pyridine-d5)δ:8.01
(1H, d, J=15.9Hz, H-3′), 7.62(2H, d, J=6.9 Hz,
H-5′, 9′), 7.16(2H, d, J=6.9 Hz, H-6′, 8′), 6.69
(1H, d, J=15.9 Hz, H-2′), 5.86(1H, brs, H-12),
4.73(1H, d, J=12.6 Hz, H-27α), 4.58(1H, d, J=
12.6 Hz, H-27β), 3.42(1H, brs, H-3), 1.21, 1.07,
596 NatProdResDev　　　　　　　　　　　　　　　　　　　　 　Vol.21
1.02, 1.00, 0.93, 0.92(each, 3H, s);13CNMR(150
MHz, pyridine-d5 )δ:181.4(C-28), 168.5(C-1′),
162.7(C-7′), 146.4(C-3′), 140.1(C-13), 131.9(C-
5′, 9′), 128.3(C-12), 127.3(C-4′), 118.1(C-6′,
8′), 116.8(C-2′), 79.2(C-3), 67.4(C-27), 57.0
(C-5), 50.4(C-9), 47.7(C-17), 47.3(C-14), 46.7
(C-19), 43.1(C-18), 41.7(C-8), 40.6(C-1), 40.3
(C-4), 38.8(C-10), 35.3(C-21), 34.9(C-7), 34.4
(C-22, 29), 32.1(C-20), 29.9(C-23), 29.2(C-2),
25.6(C-11), 25.3(C-15), 25.0(C-30), 24.9(C-
16), 20.1(C-6), 19.8(C-26), 17.8(C-25), 17.0(C-
24).The[ α] D, UV, IR, ESI-MSandNMRdatawere
identicaltothosereported[ 10] .
3β -Hydroxy-27-p-(Z)-coumaroyloxyolean-12-en-
28-oicacid(11)　Whiteamorphouspowder, mp.240-
242℃;ESI-MS(positivemode)m/z:641 [ M +Na
] +;1HNMR(600 MHz, pyridine-d5)δ:8.05(2H, d, J
=6.9 Hz, H-5′, 9′), 7.15(2H, d, J=6.9 Hz, H-6′,
8′), 7.00(1H, d, J=12.9 Hz, H-3′), 6.02(1H, d, J
=12.9 Hz, H-2′), 5.78(1H, brs, H-12), 4.63(1H,
d, J=12.7Hz, H-27α), 4.51(1H, d, J=12.7 Hz, H-
27β), 3.42(1H, dd, J=11.0, 4.8 HzH-3), 1.20,
1.02, 1.00, 0.99 , 0.90, 0.89(each, 3H, s);13CNMR
(150 MHz, pyridine-d5 )δ:179.9(C-28), 166.4(C-
1′), 160.4(C-7′), 143.9(C-3′), 138.4(C-13),
133.4(C-5′, 9′), 126.9(C-12), 126.2(C-4′), 116.1
(C-2′), 115.7(C-6′, 8′), 77.7(C-3), 65.9(C-27),
55.5(C-5), 48.8(C-9), 46.2(C-17), 45.6(C-14),
45.2(C-19), 41.5(C-18), 40.2(C-8), 39.1(C-1),
38.5(C-4), 37.3(C-10), 33.8(C-21), 33.3(C-22),
34.9(C-7), 32.9(C-29), 30.6(C-20), 28.4(C-23),
27.8(C-2), 24.1(C-11), 24.0(C-15), 23.6(C-30),
23.4(C-16), 18.6(C-6), 18.3(C-26), 16.2(C-25),
15.5(C-24).Themp., ESI-MSandNMRdatawerein
accordancewiththosereported[ 10, 11].
Hycandinicacidester(12)　Colorlessoil;[ α] 24D
-38.6°(c0.145, CHCl3 );UVλEtOHmax 223(4.96), 298
(5.00), 340(5.02);IRυKBrmaxcm-1:3420, 2980, 2920,
2860, 1710, 1620, 1590, 1510, 1450, 1420, 1270,
1160, 1120, 1080 , 1050, 1030, 980, 910, 850, 810,
730;ESI-MS(positivemode)m/z:447 [ M +Na] + ,
463 [ M +K] +;1HNMR(600MHz, CDCl3)δ:7.64
(1H, d, J=15.9 Hz, H-3′), 7.06(1H, d, J=7.9 Hz,
H-9′), 7.02(1H, s, H-5′), 6.91(1H, d, J=7.9 Hz,
H-8′), 6.31(1H, d, J=15.9 Hz, H-2′), 5.39(1H,
ddd, J=11.0 , 9.8, 3.2 Hz, H-5), 4.21(1H, m, H-
3), 4.20(2H, t, J=6.2 Hz, H-8), 3.91(3H, s, 6′-
OCH3), 3.68(1H, d, J=9.8 Hz, H-4), 2.31(1H, br
d, J=12.8 Hz, H-6α), 2.21(1H, d, J=14.5 Hz, H-
2α), 2.08(1H, d, J=14.5 Hz, H-2β), 1.93(1H, dd,
J=12.8, 11.0 Hz, H-6β), 1.64(2H, m, H-9), 1.38
(2H, sext, J=7.3 Hz, H-10), 0.94(3H, t, J=7.3
Hz, H-11);13CNMR(150 MHz, CDCl3)δ:174.1(C-
7), 167.4(C-1′), 148.1(C-7′), 146.8(C-6′), 145.7
(C-3′), 126.8(C-4′), 123.2(C-9′), 115.0(C-2′),
114.7(C-8′), 109.4(C-5′), 75.6(C-1), 74.0(C-
4), 70.7 (C-5), 70.6(C-3), 66.4(C-8), 55.9
(OCH3), 38.7(C-6), 37.0(C-2), 30.5(C-9), 18.9
(C-10), 13.6(C-11).The[ α] D, UV, IR, ESI-MSand
NMRdatawereinaccordancewiththosereported[ 12] .
Chlorogenicacidbutylester(13)　Apaleyelow
needles(MeOH), mp.151-152 ℃;ESI-MSm/z:433
[ M +Na] +, 449 [ M +K] +;1HNMR(600 MHz,
CDCl3)δ:7.52(1H, d, J=15.9Hz, H-3′), 7.03(1H,
d, J=7.9 Hz, H-9′), 6.94(1H, s, H-5′), 6.77(1H,
d, J=7.9 Hz, H-8′), 6.20(1H, d, J=15.9Hz, H-
2′), 5.27(1H, ddd, J=10.8, 9.0, 3.5 Hz, H-5),
4.15(1H, m, H-3), 4.14(2H, t, J=7.0 Hz, H-8),
3.72(1H, dd, J=10.8, 2.9 Hz, H-4), 2.22(1H, d, J
=13.8Hz, H-6α), 2.15(1H, d, J=14.5 Hz, H-2α),
2.13(1H, d, J=14.5 Hz, H-2β), 1.93(1H, d, J=
13.8 Hz, H-6β), 1.61(2H, m, H-9), 1.34(2H, sext, J
=7.5 Hz, H-10), 0.89(3H, t, J=7.5 Hz, H-11).
Themp., ESI-MSandNMRdatawereinconsistent
withthosereported[ 13] .
4, 5-di-O-Caffeoylquinicacidbutylester(14)　Yel-
lowishgum;UVλMeOHmax (logε)nm :242(4.29), 300
(4.39), 331(4.52);ESI-MS(positivemode)m/z:595
[ M +Na] +, 611 [ M +K] +;1HNMR(600 MHz,
CD3OD)δ:7.60(1H, d, J=15.8 Hz, H-3′), 7.50
(1H, d, J=15.8Hz, H-3″), 7.02(1H, d, J=1.8 Hz,
H-5′), 7.00(1H, d, J=1.8 Hz, H-5″), 6.91(1H, dd,
J=8.4 , 1.8 Hz, H-9′), 6.90(1H, dd, J=8.4, 1.8
Hz, H-9″), 6.76(each1H, d, J=8.4 Hz, H-8′, 8″),
6.28(1H, d, J=15.8 Hz, H-2′), 6.16(1H, d, J=
15.8 Hz, H-2″), 5.54(1H, ddd, J=9.1, 8.8, 3.0 Hz,
597Vol.21 　　　　　　MAXiao-li, etal:ChemicalConstituentsofOsmanthusyunnanensis　
H-5), 5.11(1H, dd, J=8.8, 3.0 Hz, H-4), 4.35
(1H, m, H-3), 4.09(1H, m, H-8), 2.32(1H, dd, J=
13.8, 3.0Hz, H-6α), 2.26(1H, brd, J=11.1Hz, H-
2α), 2.21(1H, brd, J=11.1 Hz, H-2β), 2.06(1H,
brd, J=13.8 Hz, H-6β), 1.62(2H, m, H-9), 1.35
(2H, sext, J=7.5 Hz, H-10), 0.90(3H, t, J=7.5
Hz, H-11);13CNMR(150 MHz, CD3OD)δ:173.4(C-
7), 167.1(C-1′), 166.5(C-1″), 148.3(C-7′), 148.2
(C-7″), 146.3(C-3′), 146.2(C-3″), 145.4(C-6′),
145.3(C-6″), 126.3(C-4′), 126.1(C-4″), 121.7(C-
9′, 9″), 115.1(C-8′, 8″), 113.7(C-5′, 5″), 113.3(C-
2′), 113.1(C-2″), 74.3(C-1), 73.4(C-4), 67.7(C-
5), 67.1(C-3), 65.1(C-8), 37.0(C-2, 6), 30.0 (C-
9), 18.6(C-10), 12.5(C-11).TheUV, ESI-MSandNMR
datawereinaccordancewiththosereported[ 14].
4, 5-Dihydroxyprenylcafeate(15)　 Amorphous
powder;[ α] 24D-1.2 °(c0.1, MeOH);ESI-MS(positive
mode)m/z:303 [ M +Na] +, 319 [ M +K] +;
NMRdataseeTable1.The[ α] D, ESI-MSandNMR
datawereinconsistentwiththosereported[ 15] .
Table1　NMRdataofcompounds15, 17 and18 inCD3OD
15 17 18
No. δH(J=Hz) δC δH(J=Hz) δC δH(J=Hz) δC
1 4.84, d, 6.6 59.9 4.73, d, 6.6 59.8 4.73, d, 6.6 59.8
2 5.76, t, 6.6 121.5 5.73, t, 6.6 121.6 5.74, t, 6.6 124.5
3 - 143.3 - 139.7 - 140.1
4 4.22, s 63.1 4.40, d, 12.1
4.13, d, 12.1 70.5
4.34, d, 12.1
4.13, d, 12.1 70.3
5 4.14, s 57.1 4.16, s 57.1 4.16, s 57.1
Caf-1 - 167.7 - 167.7 - 167.6
167.6
Caf-2 6.24, d, 15.9 113.6 6.20, d, 15.9 113.5 6.15, d, 15.9 113.5
6.13, d, 15.9 113.4
Caf-3 7.53, d, 15.9 145.6 7.48, d, 15.9 145.8 7.45, d, 15.9 145.4
7.43, d, 15.9 145.4
Caf-4 - 126.3 - 126.3 - 126.3
124.9
Caf-5 7.02, d, 1.9 113.7 6.95, d, 1.9 113.8 6.94, d, 1.5 113.7
6.92, d, 1.9 113.8
Caf-6 - 148.2 - 148.2 - 148.2
148.2
Caf-7 - 145.4 - 145.7 - 145.7
145.7
Caf-8 6.77, d, 8.2 115.1 6.67, d, 8.1 115.1 6.68, d, 8.1 115.1
6.67, d, 8.1 115.1
Caf-9 6.93, dd, 8.2, 1.9 121.1 6.83, dd, 8.1, 1.9
6.81, dd, 8.1, 1.9
121.5
121.5 6.84, dd, 8.1, 1.5 121.5
Glu-1 - - 4.23, d, 7.9 101.7 4.22, d, 7.7 101.9
Glu-2 - - 73.6 73.6
Glu-3 - - 76.5 76.7
Glu-4 - - 69.1 70.5
Glu-5 - - 74.1 76.5
Glu-6 - - 4.28, d, 12.6
4.19, dd, 12.6, 5.9 63.2
3.77, d, 11.5
3.56, dd, 11.5, 4.9 61.3
28-O-β-D-Glucopyranosylrotundioicacid(16)　
Colorlessneedles(EtOH), mp.214-215 ℃;[ α] 24D +
26.9 °(c3.2, MeOH);ESI-MS(positivemode)m/z:
687 [ M +Na] + , 703 [ M +K] +;1HNMR(600
MHz, pyridine-d5)δ:6.29(1H, d, J=8.1 Hz, Glu-H-
1), 5.58(1H, brs, H-12), 4.67(1H, dd, J=10.9,
5.3 Hz, H-3), 2.94(1H, brs, H-18), 1.07(1H, d, J
598 NatProdResDev　　　　　　　　　　　　　　　　　　　　 　Vol.21
=6.5 Hz, H-30), 1.66, 1.65 , 1.41, 1.22, 1.05(each
3H, s, 5 ×CH3);13 CNMR(150 MHz, CD3OD)δ:
180.1(C-23)177.1(C-28), 138.1(C-13), 128.0(C-
12), 94.3(Glu-C-1), 77.1(Glu-C-3), 76.9(Glu-C-
5), 75.0(C-3), 72.4(Glu-C-2), 72.2(C-19), 69.7
(Glu-C-4), 61.0(Glu-C-6), 53.5(C-18), 53.3(C-
4), 51.1(C-5), 48.0(C-9), 47.8(C-17), 41.5(C-
14), 41.2(C-8, 20), 40.1(C-1), 38.4(C-10), 36.8
(C-22), 36.0(C-7), 32.3(C-15), 28.2(C-2, 29),
26.0(C-16), 25.8(C-21), 25.6(C-27), 25.1(C-
11), 20.8(C-6), 16.0(C-30), 15.1(C-26), 14.8(C-
25), 10.1(C-24).Themp., [ α] D, ESI-MSandNMR
datawereequaltothosereported[ 8, 16] .
4-(6-O-Cafeoyl-β-D-glucopyranosyloxy)-5-hydroxy-
prenylcafeate(17)　Apaleyelowamorphouspow-
der;UVλMeOHmax (logε)nm:329(4.6), 300(4.47), 245
(4.35), 216(4.49);ESI-MS(positivemode)m/z:627
[ M +Na] +, 643 [ M +K] +;NMRdataseeTable
1.TheUV, ESI-MSandNMRdatawereinconsistent
withthosereported[ 15] .
4-β-D-Glucopyranosyloxy-5-hydroxyprenylcaffeate
(18)　Apaleyelowamorphouspowder;UVλMeOHmax
(logε)nm:329(4.31), 300(4.18), 245(4.07), 216
(4.24);ESI-MS(positivemode)m/z:465 [ M +Na
] + , 481 [ M +K] +;NMRdataseeTable1.The
UV, ESI-MSandNMRdatawereequaltothoserepor-
ted[ 15] .
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