全 文 ：天然产物研究与开发 NatProdResDev2011, 23:258-261
文章编号:1001-6880(2011)02-0258-04
　
　
　ReceivedAugust25, 2009;AcceptedOctober21, 2009
　FoundationItem:ThisresearchprojectwassupportedbytheScientific
FoundationofShanghaiChina(08DZ1971302).
＊CorrespondingauthorTel:86-21-34205989;E-mail:wdzhangy@hot-
mail.com
显脉旋覆花化学成分的研究
严　岚1 ,金慧子 1＊ ,聂利月 1 ,覃江江 1 ,付建军 1 ,张卫东1, 2＊
1上海交通大学药学院 , 上海 200240;2上海第二军医大学药学院 , 上海 200433
摘　要:从显脉旋覆花(InulanervosaWall.)地上部分的 75%乙醇提取物中分离到 13个化合物 , 经波谱鉴定为
紫菀酮(1), β-谷甾醇(2), α-菠菜甾醇(3), 熊果酸(4), 胡萝卜苷(5), bigelovin(6), loliolide(7), 24S-乙基-5α-胆
甾-7, 22E-二烯-3α-醇-β-半乳糖苷 (8),菠叶素(9),山萘酚(10), α-菠甾醇-3-O-β-D-葡萄糖苷(11),苄醇-β-D-葡
萄糖苷(12)和 2-苯乙醇-β-D-葡萄糖苷(13)。其中 ,化合物 1 ～ 3和 6 ～ 13为首次从该植物中分离得到。
关键词:显脉旋覆花;菊科;化学成分;分离
中图分类号:R284.2;Q946.91 文献标识码:A
ChemicalConstituentsfromInulanervosaWal.
YANLan1 , JINHui-zi1＊ , NIELi-yue1 , QINJiang-jiang1 , FUJian-jun1 , ZHANGWei-dong1, 2＊
1SchoolofPharmacy, ShanghaiJiaoTongUniversity, Shanghai200240 , China;
2SchoolofPharmacy, SecondMilitaryUniversity, Shanghai200433 , China
Abstract:Thirteencompoundswereisolatedfromthe75%ethanolextractoftheaerialpartsofInulanervosaWal..On
thebasisofspectraldata, theywereidentifiedasshionone(1), β-sitosterol(2), α-spinasterol(3), ursolicacid(4),
daucosterol(5), bigelovin(6), loliolide(7), 24S-ethyl-5α-cholesta-7, 22E-dien-3α-ol-β-galactopyranoside(8), spi-
nacetin(9), kaempferol(10), α-spinasterol-3-O-β-D-glucoside(11), benzyl-β-D-glucopyranoside(12), and2-phenyl-
ethyl-β-D-glucopyranoside(13).Compounds1-3 and6-13 wereisolatedfromthisplantforthefirsttime.
Keywords:InulanervosaWal.;Asteraceae;chemicalconstituents;isolate
Introduction
InulanervosaWal.(Asteraceae)isaperennialtree,
mainlydistributedinsouthwestChina.Therootsofthis
planthavebeenusedasChinesefolkmedicinefortrea-
tingstomachacheandrelievingrheumatism[ 1] .Howev-
er, uptonow, onlyafewchemicalconstituents, suchas
daucosterol[ 2] , oleanolicacid[ 3] , stigmasterol[ 2, 3] , thy-
mol[ 2] , havebeenisolatedfromthisplant.Inthisstudy
ontheaerialpartsofI.nervosa, thirteencompounds
wereisolatedandidentifiedasshionone(1), β-sitos-
terol(2), α-spinasterol(3), ursolicacid(4), dau-
costerol(5), bigelovin(6), loliolide(7), 24S-ethyl-
5α-cholesta-7, 22E-dien-3α-ol-β-galactopyranoside
(8), spinacetin(9), kaempferol(10), α-spinasterol-
3-O-β-D-glucoside(11), benzyl-β-D-glucopyranoside
(12), and2-phenylethyl-β-D-glucopyranoside(13).
Compounds1-3and6-13 wereisolatedfromthisplant
forthefirsttime.
Experimental
Generalprocedures
AlmeltingpointsweredeterminedonanRY-1 mi-
cromeltingpointapparatus(uncorected).TheESIMS
weremeasuredonanAgilent1100 seriesmassspec-
trometer, whereasEIMSweremeasuredonanAuto-
spec-UltimaETOFapparatus.NMRspectraweremeas-
uredonaBrukerDRX-500 spectrometer, operatingat
500 MHzfor1Hand125 MHzfor13CNMR.Chemical
shift(δ)weregiveninppmrelativetoTMSasinternal
standardandcouplingconstantsinHz.Silicagel(200-
300 mesh, Yantai, China)andsephadexLH-20 (GE
HealthcareBio-SciencesAB, Sweden)wereusedfor
columnchromatography, andprecoatedsilicaGF254
plateswereusedforTLC(QingdaoHaiyangChemical
Co., Ltd., China).
Plantmaterial
TheaerialpartsofI.nervosawerecolectedfromYun-
nanProvinceofChinainJuly, 2006 andidentifiedby
Prof.HuangBao-kang, DepartmentofPharmacognosy,
SchoolofPharmacy, SecondMilitaryMedicalUniversi-
ty.AvoucherspecimenwasdepositedatSchoolof
Pharmacy, ShanghaiJiaoTongUniversity.
Extractionandisolation
Theair-driedandpowderedaerialpartsofI.nervosa
(15.0 kg)wereextractedwith75% EtOHforthree
timesatroomtemperature.Thesolventswereconcen-
tratedundervacuumtoyieldaresidue(1361.0 g).
Theresiduewasdissolvedinwater(5.0 L)andex-
tractedsuccessivelywithpetroleumether(5.0 L×
10), ethylacetate(5.0 L×10)andn-butanol(5.0L
×10)togivecorrespondingfractionsA(200.2 g), B
(277.6 g), andC(291.7 g).FractionAwassubjec-
tedtosilicagelcolumnchromatographywithpetroleum
ether:ethylacetate(100∶1-0∶100)togive16fractions
A1-A16.FractionsA5, A8, A9, A12 andA16 werepu-
rifiedbyrecrystalizationfromCH2Cl2 toyieldcom-
pounds1 (63.3 mg), 2(50.5mg), 3 (120.0mg), 4
(8.6mg), and5(141.5mg), respectively.FractionB
wassubjectedtosilicagelcolumnchromatographywith
CH2Cl2∶MeOH(100∶1-0∶100)togive9fractionsB1-
B9.FractionB3wasseparatedonsilicagelcolumnelu-
tedbypetroleumether-ethylacetate(10∶1)toaford6
(8.2 mg)and7 (9.4 mg).FractionB5 waspurified
byrecrystalizationfromMe2COtoyield8 (5.0 mg).
Compounds9 (11.9mg)and10 (3.0 mg)wereob-
tainedfromtheresidueofB5 bycolumnchromatogra-
phyonsephadexLH-20 elutedwithMeOH.Eleven
subfractionsB6a-B6kandcompound11 (551.0 mg)
wereobtainedfromfractionB6separatedoversilicagel
columnelutedwithCH2Cl2∶MeOH(10∶1-1∶1).Sub-
fractionB6cwasseparatedoversilicagelcolumnusing
CH2Cl2 -MeOH(10∶1)togivecompounds12 (18.6
mg)and13 (7.0 mg).
StructureIdentification
Shionone(1)　 C30 H50 O, whiteneedlecrystal
(CH2Cl2 ), mp.159-160 ℃;EI-MSm/z(%):426
[ M] +(80), 411 [ M-CH3 ] + (20), 341(50), 109
(70), 95(70), 69(100);1HNMR(CDCl3)δ:5.10
(1H, m, H-21), 1.69(3H, s, H-29), 1.61(3H, s, H-
30), 1.14(3H, s, H-27), 0.93(3H, s, H-25), 0.91
(3H, s, H-28), 0.90(3H, s, H-26), 0.88(3H, d, J=
6.6 Hz, H-23), 0.72 (3H, s, H-24);13 C NMR
(CDCl3)δ:213.3(C-3), 130.8(C-22), 125.2(C-
21), 59.6(C-10), 58.2(C-4), 49.9(C-8), 44.5(C-
18), 43.6(C-19), 42.2(C-5), 41.4(C-2), 41.1(C-
6), 38.6(C-14), 38.5(C-9), 36.9(C-13), 35.3(C-
11), 34.6(C-16), 32.9(C-28), 32.3(C-12), 31.7
(C-17), 29.2(C-15), 25.7(C-29), 23.2(C-20),
22.3(C-1), 20.6(C-27), 19.6(C-25), 17.9(C-7),
17.6(C-30), 15.2(C-26), 14.6(C-24), 6.8(C-23)
.TheNMRandMSdatawereinaccordancewiththose
reportedintheliterature[ 4] , andidentified1asshion-
one.
β-Sitosterol(2)　 C29 H50 O, whiteneedlecrystal
(CH2Cl2), mp.141-143 ℃.TLCbehaviorwasidenti-
calwiththatofauthenticβ-sitosterol.
α-Spinasterol(3)　C29 H48 O, whiteneedlecrystal
(CH2Cl2), mp.160-162 ℃;ESI-MSm/z:413 [ M+
H] +;1HNMR(CDCl3)δ:5.18(1H, m, H-22), 5.15
(1H, m, H-7), 5.03(1H, m, H-23), 3.60(1H, m, H-
3), 1.03(3H, d, J=7.0 Hz, H-21), 0.86(3H, d, J=
7.0 Hz, H-26), 0.82(3H, m, H-29), 0.81(3H, s, H-
19), 0.80(3H, d, J=7.0 Hz, H-27), 0.57(3H, s, H-
18);13 CNMR(CDCl3 )δ:139.6(C-8), 138.2(C-
22), 129.5(C-23), 117.5(C-7), 71.1(C-3), 55.9
(C-17), 55.1(C-14), 51.3(C-24), 49.5(C-9), 43.3
(C-13), 40.8(C-20), 40.3(C-5), 39.5(C-12), 38.0
(C-4), 37.2(C-1), 34.2(C-10), 31.9(C-25), 31.5
(C-2), 29.6(C-6), 28.5(C-16), 25.4(C-28), 23.0
(C-15), 21.6(C-11), 21.4(C-21), 21.1(C-26),
19.0(C-27), 13.0(C-19), 12.2(C-18), 12.0(C-
29).TheNMRandMSdatawereinaccordancewith
thosereportedintheliterature[ 5] , andidentified3 as
α-spinasterol.
Ursolicacid(4)　C30H48 O3 , whiteamorphouspow-
der, mp.258-259 ℃;TLCbehaviorwasidenticalwith
thatofauthenticursolicacid.
Daucosterol(5)　C35 H60 O6 , whiteamorphouspow-
der, mp.285-287 ℃;TLCbehaviorwasidenticalwith
thatofauthenticdaucosterol.
259Vol.23 　　　　　　YANLan, etal:ChemicalConstituentsfromInulanervosaWall.　
Bigelovin(6)　 C17 H20 O5 , whiteneedlecrystal
(CH2Cl2), mp.180-182 ℃;ESI-MSm/z:327[ M+
Na] +;1HNMR(CDCl3)δ:7.10(1H, dd, J=6.0, 1.5
Hz, H-2), 6.22(1H, d, J=3.0 Hz, H-13a), 6.11
(1H, dd, J=6.0, 3.0 Hz, H-3), 5.92(1H, d, J=3.0
Hz, H-13b), 5.61(1H, d, J=7.5 Hz, H-6), 4.61
(1H, dt, J=12.0, 3.0 Hz, H-8), 3.07(1H, m, H-7),
3.03(1H, m , H-1), 2.57(1H, m, H-9a), 2.06(1H,
m, H-10), 1.97(3H, s, H-17), 1.54(1H, m, H-9b),
1.29(3H, d, J=6.5 Hz, H-14), 1.21(3H, s, H-
15);13 CNMR(CDCl3)δ:209.1(C-4), 169.6(C-
16), 168.9(C-12), 162.5(C-2), 137.1(C-11),
130.8(C-3), 122.1(C-13), 76.1(C-8), 73.1(C-6),
56.2(C-5), 53.9(C-7), 52.2(C-1), 44.4(C-9),
27.2(C-10), 22.6(C-15), 21.0(C-17), 19.7(C-14)
.Theabovedatawereidenticalwiththeliterature s
[ 6] .
Loliolide(7)　 C11 H16 O3 , whiteneedlecrystal
(CH2Cl2), mp.156-158 ℃;ESI-MSm/z:219[ M+
Na] +;1HNMR(CDCl3)δ:5.69(1H, s, H-7), 4.32
(1H, t, J=3.5Hz, H-3), 2.46(1H, dt, J=14.0, 2.5
Hz, H-4a), 1.97(1H, dt, J=14.0 , 2.5 Hz, H-2a),
1.77(1H, m, H-4b), 1.78(3H, s, H-11), 1.52(1H,
dd, J=14.5, 3.5Hz, H-2b), 1.47(3H, s, H-9), 1.29
(3H, s, H-10);13 CNMR(CDCl3 )δ:182.6(C-6),
172.0(C-8), 112.8(C-7), 86.8(C-5), 66.7(C-3),
47.3(C-2), 45.6(C-4), 35.9(C-1), 30.6(C-9),
27.0(C-11), 26.4(C-10).Theabovedatawereiden-
ticalwiththeliterature s[ 7] .
24S-Ethyl-5α-cholesta-7 , 22E-dien-3α-ol-β-galacto-
pyranoside(8)　C35 H58 O6 , whitepowder, mp.290-
291 ℃;ESI-MSm/z:575 [ M +H] +;1H NMR
(C5D5N)δ:5.17(1H, m, H-7), 5.14(1H, m, H-22),
5.03(1H, dd, J=15.0, 4.0Hz, H-23), 3.57(1H, m,
H-3), 1.03(3H, d, J=6.5 Hz, H-21), 0.86(3H, d, J
=6.0 Hz, H-26), 0.85(3H, m, H-29), 0.79(3H, s,
H-19), 0.78(3H, d, J=6.5 Hz, H-27), 0.55(3H, s,
H-18);Galactose:4.49(1H, dd, J=12.0, 4.5 Hz, H-
6′a), 4.39(1H, d, J=8.0 Hz, H-1′), 4.27(1H, dd, J
=12.0, 2.5 Hz, H-6′b), 3.60(2H, m, H-3′, H-4′),
3.45(1H, m, H-5′), 3.36(1H, m, H-2′);13 CNMR
(C5D5N)δ:139.6(C-8), 138.1(C-22), 129.5(C-
23), 117.3(C-7), 78.9(C-3), 55.9(C-17), 55.1(C-
14), 51.3(C-24), 49.4(C-9), 43.2(C-13), 40.8(C-
20), 40.2(C-5), 39.4(C-12), 37.1(C-1), 34.4(C-
10), 34.2(C-4), 31.9(C-25), 29.5(C-2), 29.2(C-
6), 28.5(C-16), 25.4(C-28), 23.0(C-15), 21.5(C-
11), 21.4(C-21), 21.1(C-26), 19.0(C-27), 13.0
(C-19), 12.2(C-29), 12.0(C-18);Galactose:101.1
(C-1′), 76.0(C-3′), 74.0(C-5′), 73.6(C-2′), 70.1
(C-4′), 62.7(C-6′).TheNMRandMSdatawerein
accordancewiththosereportedintheliterature[ 8] , and
identified8 as24S-ethyl-5α-cholesta-7, 22E-dien-3α-
ol-β-galactopyranoside.
Spinacetin(9)　C17 H14 O8 , yelowpowder, mp.122-
124 ℃;ESI-MSm/z:347 [ M +H] +;1H NMR
(CD3OD)δ:7.61(1H, d, J=2.0 Hz, H-2′), 7.51
(1H, dd, J=8.0 , 2.0 Hz, H-6′), 6.89(1H, d, J=8.0
Hz, H-5′), 6.48 (1H, s, H-8), 3.88(3H, s, 3′-
OCH3), 3.78(3H, s, 6-OCH3);13CNMR(CD3OD)δ:
180.3(C-4), 158.7(C-7), 158.1(C-9), 153.8(C-
5), 153.7(C-2), 150(C-4′), 146.5(C-3′), 139.2
(C-3), 132.6(C-6), 123(C-1′), 122.4 (C-6′),
116.5(C-5′), 116.4(C-2′), 106.3(C-10), 94.9(C-
8), 61.0(6-OCH3 ), 60.5(3′-OCH3 ).TheNMRand
MSdatawereinaccordancewiththosereportedinthe
literature[ 9] , andidentified9 asspinacetin.
Kaempferol(10)　C15H10O6 , yelowpowder, mp.276-
278 ℃;ESI-MSm/z:285[ M-H] -;1HNMR(CD3OD)
δ:8.09(2H, d, J=8.5 Hz, H-2′, 6′), 6.91(2H, d, J
=8.5Hz, H-3′, 5′), 6.40(1H, d, J=2.0 Hz, H-8),
6.19(1H, d, J=2.0 Hz, H-6);13CNMR(CD3OD)δ:
177.4(C-4), 165.6(C-7), 162.5(C-9), 160.6(C-
4′), 158.3(C-5), 148.0(C-2), 137.2(C-3), 130.7
(C-2′, 6′), 121.6(C-1′), 116.3(C-3′, 5′), 104.6(C-
10), 99.3(C-6), 94.5(C-8).TheNMRandMSdata
wereinaccordancewiththosereportedinthelitera-
ture[ 10] , andidentified10 askaempferol.
α-Spinasterol-3-O-β -D-glucoside(11)　C35 H58 O6 ,
whitepowder, mp.272-280 ℃;ESI-MSm/z:575[ M+
H] +;1HNMR(C5D5N)δ:5.28(1H, m, H-7), 5.20
(1H, m, H-22), 5.15(1H, dd, J=15.0, 3.5 Hz, H-
23), 3.60(1H, m, H-3), 1.25(3H, d, J=6.5 Hz, H-
21), 0.95(3H, d, J=6.0 Hz, H-26), 0.92(3H, d, J
=6.5Hz, H-27), 0.91(3H, m, H-29), 0.78(3H, s,
H-19), 0.63(3H, s, H-18);Glucose:5.00(1H, d, J=
260 NatProdResDev　　　　　　　　　　　　　　　　　　　　 　Vol.23
8.0Hz, H-1′), 4.52(1H, dd, J=12.5, 2.0 Hz, H-6′
b), 4.37(1H, dd, J=12.5, 5.0 Hz, H-6′a), 4.22
(2H, m, H-3′, H-4′), 3.98(2H, m, H-2′, H-5′);13C
NMR(C5D5N)δ:139.6(C-8), 138.2(C-22), 129.5
(C-23), 117.5(C-7), 77.0(C-3), 55.9(C-17), 55.0
(C-14), 51.1(C-24), 49.4(C-9), 43.2(C-13), 40.6
(C-20), 40.0(C-5), 39.4(C-12), 37.1(C-1), 34.5
(C-4), 34.3(C-10), 31.8(C-25), 29.7(C-2), 29.6
(C-6), 28.4(C-16), 25.2(C-28), 23.0(C-15), 21.4
(C-11), 21.2(C-21), 20.8(C-26), 18.9(C-27),
12.6(C-19), 12.1(C-29), 11.9(C-18);Glucose:
102.0(C-1′), 78.3(C-5′), 77.9(C-3′), 75.0(C-
2′), 71.6(C-4′), 62.7(C-6′).TheNMRandMSdata
wereinaccordancewiththosereportedinthelitera-
ture[ 11] , andidentified11 asα-spinasterol-3-O-β-D-
glucoside.
Benzyl-β-D-glucopyranoside(12)　C13H18O6 , color-
lesgum;ESI-MSm/z:293 [ M +Na] +;1H NMR
(CD3OD)δ:7.42(2H, d, J=7.5 Hz, H-2, 6), 7.33
(2H, m, H-3, 5), 7.27(1H, d, J=7.5Hz, H-4), 4.93
(1H, d, J=12.0 Hz, H-7a), 4.67(1H, d, J=12.0
Hz, H-7b);13CNMR(CD3OD)δ:139.1(C-1), 129.3
(C-3, 5), 129.2(C-2 , 6), 128.7(C-4), 71.8(C-7);
Glucose:103.3(C-1′), 78.1(C-3′), 78.0(C-5′),
75.1(C-2′), 71.7(C-4′), 62.8(C-6′).TheNMRand
MSdatawereinaccordancewiththosereportedinthe
literature[ 12] , andidentified12asbenzyl-β-D-glucopyr-
anoside.
2-Phenylethyl-β-D-glucopyranoside(13)　C14 H20
O6 , colorlessgum;ESI-MSm/z:307 [ M+Na] +;1H
NMR(CD3OD)δ:7.22(5H, m, H-2, 3, 4, 5 , 6), 4.10
(1H, m, H-8a), 3.74(1H, m, H-8b), 2.94(2H, m, H-
7);13CNMR(CD3OD)δ:140.1(C-1), 130.0(C-2,
6), 129.3(C-3, 5), 127.2(C-4), 71.7(C-8), 37.2
(C-7);Glucose:104.4(C-1′), 78.1(C-3′), 78.0(C-
5′), 75.1(C-2′), 71.6(C-4′), 62.7(C-6′).Thea-
bovedatawereidenticalwiththeliterature s[ 13].
References
1　ZhaoL, XinKX, LiYQ.ResearchadvanceofInulanervosa
Wal.inChina.FoodDrug, 2007, 9:53-54.
2　FanDQ, LuoSD, WangHL, etal.Studiesonthechemical
constituentsofVeinedInula(Inulanervosa).ChinTradit
HerbDrugs, 1997, 28 (2):67-69.
3　XuQF, LiuKL.Researchontheanti-inflammatoryconstitu-
entsfromwater-solublepartofInulanervosa.HunanJTradit
ChinMed, 1988, 6:46-47.
4　ZhangB, WangY, LuJ, etal.Isolationandidentificationof
effectiveconstituentsand HPLC-ELSD determination of
shiononeinRadixAsteris.ChinJPharmAnal, 2003, 23:296-
298.
5　ZhuZJ, PanRL, SiJY.Studyonthechemicalconstituentsof
BupleurumbicauleHelm.NatProdResDev(天然产物研究
与开发), 2008, 20:833-835.
6　LeeHT, YangSW, KimKH, etal.Pseudoguaianolidesisola-
tedfromInulabritannicavar, chinenisasinhibitoryconstitu-
entsagainstinduciblenitricoxidesynthase.ArchPharmRes,
2002, 25 (2):151-153.
7　CuiXQ, WangHQ, LiuC, etal.Chemicalcomponentsof
Faecesbombycis.ChinTraditHerbDrugs, 2007, 38:501-503.
8　AlexandraP, CatarinaD, CarlosB, etal.Anew■ 7, 22 sterol
fromthebulbsofAutonoëmadeirensis.Fitoterapia, 2005, 76:
765-767.
9　Lǜ H, LiQ, ZhongJ, etal.StudiesonflavonoidsfromHeli-
chrysumarenarium.ChinPharm, 2008, 43:11-13.
10 RenFZ, LiuGS, ZhangL, etal.Studiesonchemicalconstitu-
entsofHedyotisdifusaWild.ChinPharmJ, 2005, 40:502-
504.
11 JiangY, TuPF.StudyonchemicalconstituentsofPolygala
tenuifoliaⅢ.ChinJNatMed, 2003, 1 :142-145.
12 ZhouYZ, ChenH, QiaoL, etal.Chemicalconstituentsfrom
CarthamustinctoriusL.ChinJMedChem, 2007, 17:380-
382.
13 KimKH, LeeHY, ChoiSU, etal.Terpeneandphenoliccon-
stituentsofLactucaindicaL..ArchPharmRes, 2008, 31:
983-988.
261Vol.23 　　　　　　YANLan, etal:ChemicalConstituentsfromInulanervosaWall.