全 文 ：AnewcompoundfromSeneciocannabifoliusvarintegrilifolius
MAHong-yan1 , YANGLi2 , ZHANGMian1 , WANGChang-hong2 , WANGZheng-tao1, 2＊
(1.DepartmentofPharmacognosy, ChinaPharmaceuticalUniversity, Nanjing210038 , China;2.KeyLaboratoryofStandardization
ofChineseMedicines, MinistryofEducation, ShanghaiUniversityofTraditionalChineseMedicine, Shanghai201203 , China)
Abstract:Seneciocannabifoliusvarintegrilifolius(Compositae), localyknownas“Fanhuncao” in
China, isafolkherbusedforthetreatmentofpneumonia, virusinfluenzaandbronchitis.Toinvestigate
thechemicalconstituentsofthisherb, waterextractoftheaerialpartswassubjectedtovarious
chromatographyonnormal/reversedphasesilicagelandSephadexLH-20 column.Elevencompoundswere
obtainedandidentifiedonthebasisoftheirphysicochemicalpropertiesandspectroscopicanalysisas
senecine(1), p-hydroxy-benzeneaceticacid(2), protocatechuicacid(3), 2, 5-dihydroxy-benzeneacetic
acid(4), 3, 4-dihydroxy-benzeneaceticacid(5), vanilicacid(6), caficacid(7), succinicacid(8),
2-furoicacid(9), 1, 2, 4, 5-tetrahydro-jacaranone(10), and4-(pyrolidin-2-one)-phenylaceticacid
(11).Compound1 wasstructuralyidentifiedtobeanewcompound;theothercompoundswereisolated
fromthisplantforthefirsttime.
Keywords:Seneciocannabifoliusvarintegrilifolius;chemicalconstituent;organicacid
CLCnumber:R284.1　　　Documentcode:A　　　ArticleID:0513-4870(2008)06-0626-04
Received2007-12-06.
ProjectsupportedbyNationalNaturalScienceFoundationofChina
(30530840, 30572222 and 30701104);NationalBasic
ResearchProgramofChina(2006CB504704).
＊ Corespondingauthor　Tel:86-21 -51322507,
Fax:86-21-51322519,
E-mail:wangzht@hotmail.com
单麻叶千里光中的一个新化学成分
马鸿雁 1 , 杨　莉 2 , 张　勉 1 , 王长虹 2 , 王峥涛 1, 2＊
(1.中国药科大学 生药学研究室 , 江苏 南京 210038;2.上海中医药大学 中药标准化教育部重点实验室 , 上海 201203)
摘要:研究菊科千里光属植物单麻叶千里光 Seneciocannabifoliusvarintegrilifolius(Koidz.)Kitam.的化学成分。
用硅胶 、 SephadexLH-20及反相 C
18
等柱色谱方法从其水提取物中分离得到 11个化合物 , 根据理化性质和光谱数据
鉴定其结构 , 分别为 senecine(1), 对羟基苯乙酸(2), 原儿茶酸(3), 2, 5-二羟基苯乙酸(4), 3, 4-二羟基苯乙酸
(5), 香草酸(6), 咖啡酸(7), 丁二酸(8), 2-糠酸(9), 1, 2, 4, 5-四氢-jacaranone(10), 4-(吡咯烷-2-酮基)-苯基乙
酸(11)。其中化合物 1为新化合物 , 2 ～ 11均为首次从该植物中分离得到。
关键词:单麻叶千里光;化学成分;有机酸
　　Morethan1 000 speciesofplantsfromthegenus
Senecio(Compositae)arewidespreadaloverthe
world, andabout63 speciesofthemarerecordedin
theFloraofChina[ 1] .ThelargegenusSeneciohas
beenextensivelystudiedandvariouspyrrolizidine
alkaloids, sesquiterpenes, organicacidsandflavonoids
havebeenfoundinthisgenus[ 2] .Seneciocannabifolius
varintegrilifolius, togetherwith S.cannabifolius,
localyknownas“Fanhuncao”, distributesmainlyin
theNorth-EastofChina, Korea, Japan, andfareastof
Russia[ 3] .Itisused totreatpneumonia, virus
influenzaandbronchitisasafolkmedicine.Many
organicacidsandterpenoidshadbeenisolatedfrom
S.cannabifoliusandtheformerwasfoundtoshow
certainbacteriostaticactivity[ 4] , butlitlephytochemical
researchon S.cannabifoiusvarintegrilifoliuswas
conducted.Inthispaper, wereportedtheisolationand
·626· 药学学报 ActaPharmaceuticaSinica2008, 43(6):626-629
structureelucidationofaneworganicacidandten
knowncompoundsfromthewaterextractoftheaerial
partsofS.cannabifoliusvarintegrilifolius(Koidz.)
Kitam.
Resultsanddiscussion
Compound1, colorlesscrystals(EtOAc-hexane),
itsmolecularformulawasestablishedasC16H15NO4 by
HR-EI-MSatm/z285.101 1 (calcd.285.100 1).
ItsIRspectrumshowedabsorptionbandsat3 397 and
1 697 cm-1 , whichindicatedthepresenceof-NHand
-COOH, respectively.Atthesametimetheabsorption
bandsat1 615 and 1 529 cm-1 , indicated the
presenceofbenzenering.Basedonthedatafromthe
1HNMRand13CNMRspectra, itseemedtherewasa
halfofstructuralinformationinthesespectra.Sothe
compound was presumed to have a symmetrical
structure.The1HNMRspectrumindicatedtwosetsof
1, 4-bisubstitutedaromaticringsignalsatδ:7.18
(4H, d, J=8.5 Hz), 7.07(4H, d, J=8.5 Hz), and
3.50(4H, s).Accordingly, the13CNMRspectrum
showedthepresenceofaromaticcarbonsignalsat
δ:117.9(4CH), 127.3(2C), 130.9 (4CH)and
143.4(2C).Inaddition, acarbonylgroupsignalat
δ 173.0 andsecondarycarbonsignalatδ40.5
(2CH2 )showedthesubstituteofaceticacid.The
1HNMRand13CNMRspectraof1 resembledthose
ofp-hydroxy benzeneacetic acid (2 ) in many
respects, exceptforthediferentchemicalshiftofan
aromaticgroup.In compound 1 , thecarbonat
δ 143.4 insteadofthecarbonatδ157.1 atachedto
thehydroxylgroupofcompound2.Together, thepeak
at3 397 cm-1 inIRspectrumrevealedthepresence
ofamineanditwassimilartodiphenylamine[ 5] .So
thecarbonofδ143.4(CH)canbeconsideredtobe
atachedtoanaminegroup.Onthebasisofabove
evidence, compound1 waselucidatedasdi(p-
carboxymethyl-)phenylamine(figure1), andnamed
assenecine.
Figure1　Structuresofcompounds1 and2
Experimental
MeltingpointsweredeterminedusinganX-4
digitalmicromeltingpointapparatus(uncorected).
1HNMR(500 MHz)and13CNMR (125 MHz)
spectrawererecordedwithBrucherACF-500 NMR
spectrometers.MassspectrawereobtainedonMS
Agilent1100 SeriesLC/MSDTrapMassspectrometer
(ESI-MS), andWatersMicromassGCT(HR-MS).
Alsolventsusedwereofanalyticalgrade.Column
chromatographywasconsistedofthefolowing:silica
gel(100 -200, 200 -300 meshandthin-layerH;
Qingdao Marine ChemicalCo. Ltd., Qingdao,
China), andSephadexLH-20 (PharmaciaFine
ChemicalCo.Ltd.).
Plantmaterials　 Senecio cannabifoliusvar
integrilifoliuswasoferedbyXiuzhengPharmaceutical
Co. Ltd. and identified by Prof. Zhang Mian
(DepartmentofPharmacognosy, ChinaPharmaceutical
University).A voucherspecimen(No.DMYQLG-
2004-12 ) is deposited in the Department of
Pharmacognosy, ChinaPharmaceuticalUniversity.
Extractionandisolation　Driedandcrushed
aerialparts(35 kg)ofS.cannabifoliusvarintegrilifolius
wereextractedthreetimes(3 h, 2 h, 1 h)with
boilingwater.Afterevaporationofthesolventin
vacuo, theconcentratedextractwastreatedwith2%
HClaq.topH2 andthenextractedwithEtOAc.The
EtOAcextract(200 g)wasfractionedbyasilicagel
(100 -200 mesh, 1 000 g)columnusinggradient
systemofCH2Cl2-MeOHaseluenttoafordfractions
A-F.FractionA(50 g)waschromatographedon
silicagel(200 -300 mesh, 500 g)withpetroleum
ether-acetoneto yield 10 fractions(A1 -A10 ).
FractionA2 wassubjectedtosilicagel(200 -300
mesh, 100 g)elutedwithCH2Cl2 -Me2CO-formicacid
(97 ∶3 ∶0.1) toafordcompound 9 (20 mg).
FractionA3 wassubjectedtosilicagel(200 -300
mesh, 120 g)elutedwithpetroleum ether-Me2CO
(90 ∶10 -1 ∶1)togive8 fractions(A3 -1 -A3-8).
Fraction A3-6 was further chromatographed on
SephadexLH-20 columnelutedwithCH2Cl2 -MeOH
(1 ∶1)toyieldcompound6 (10 mg).FractionA4
wassubjectedtosilicagel(200 -300 mesh, 40 g)
elutedwithCH2Cl2-MeOH-formicacid(97 ∶3 ∶0.1)
toafordcompound11 (20 mg)and1 (15 mg).
FractionB (10 g) wassubjected tosilicagel
(200 -300 mesh, 200 g)elutedwithCH2Cl2 -Me2CO
(100 ∶3 -1 ∶1)toyieldcompound2 (100 mg)and
10 (50 mg).FractionC(20 g)wasappliedona
·627·MAHong-yan, etal:AnewcompoundfromSeneciocannabifoliusvarintegrilifolius
reversedphaseC18-ODScolumnwith MeOH-H2O
gradientsystem, and10 subfractionswerecolected
(C1 -C10 ).Compound8 (1 g)wasobtainedby
recrystalization from the subfraction C1 , the
subfractionC2 waschromatographed on Sephadex
LH-20 columnwithCH2Cl2 -MeOH(1 ∶1)toyield
compound3 (25 mg).ThesubfractionC4 was
chromatographedonSephadexLH-20 columneluted
withCH2Cl2 -MeOH(1 ∶1)toyieldcompound7 (30
mg).FractionD(18 g)wassubjectedtosilicagel
(200 -300 mesh, 280 g)elutedwithCH2Cl2 -MeOH-
formicacid(97 ∶3 ∶0.1 -80 ∶20 ∶0.1)togive15
fractions(D1 -D15 ), fractionD2 wassubjectedto
silicagel(200 -300 mesh, 60 g)elutedwithCH2Cl2-
MeOH-formicacid(97 ∶3 ∶0.1 -95 ∶5 ∶0.1)toyield
compound4 (15 mg)and5 (20 mg).
Structureidentification
Senecine (1), colorless crystals (EtOAc-
hexane);mp168 -169 ℃;IR(KBr):3 397(NH),
1 697(COOH), 1 615 , 1 529(benzenering), 1 333,
1 241, 1 181, 1 141, 806 cm-1;1HNMR(500
MHz, acetone-d6)δ:3.50(4H, s, H-7), 7.07(4H,
d, J=8.5 Hz, H-2, 6, 2′, 6′), 7.18(4H, d, J=8.5
Hz, H-3, 5, 3′, 5′);13CNMR(125 MHz, acetone-d6)
δ:143.4(C-1, 1′), 117.9(C-2 , 6, 2′, 6′), 130.9
(C-3, 5, 3′, 5′), 127.3(C-4 , 4′), 40.5(C-7, 7′),
173.0(C-8, 8′).HR-EI-MSm/z:285.101 1 (calcd
forC16H15NO4 , 285.100 1).
p-Hydroxy-benzeneacetic acid (2 ), white
crystal(EtOAc-hexane); 1HNMR (500 MHz,
acetone-d6)δ:3.50(2H, s, H-7), 6.77(2H, d, J=
8.4 Hz, H-3, H-5), 7.13(2H, d, J=8.4 Hz, H-2,
H-6), 8.13 (1H, s, 9-OH), 10.50 (-COOH).
13CNMR(125 MHz, acetone-d6)δ:128.0(C-1),
131.0(C-2, 6), 116.1(C-3, 5), 157.1(C-4), 42.7
(C-7), 173.9(C-8).ESI-MSm/z:153[ M+H] +.
Thesedatawereconsistentwiththoseofreference[ 6] .
Protocatechuicacid(3), whitecrystal(EtOAc-
hexane);1HNMR(500 MHz, acetone-d6)δ:6.77
(1H, d, J=8.0 Hz, H-5), 7.34(1H, dd, J=8.0, 2.0
Hz, H-6), 7.40(1H, d, J=2.0 Hz, H-2).13CNMR
(125 MHz, acetone-d6 )δ:123.0 (C-1), 117.4
(C-2), 145.5(C-3), 150.7(C-4), 115.6(C-5),
123.6(C-6), 169.1(C-7).ESI-MSm/z:155[ M+
H] +.Thesedatawereconsistentwiththoseof
reference[ 7] .
2, 5-Dihydroxy-benzeneaceticacid(4), yelow
crystal(EtOAc-hexane); 1HNMR (500 MHz,
acetone-d6)δ:3.52(2H, s, H-7), 6.63(1H, dd, J=
8.6, 2.0 Hz, H-4), 6.72(1H, d, J=2.0 Hz, H-6),
6.80(1H, d, J=8.6 Hz, H-3), 8.10 (s, -OH).
13CNMR(125 MHz, acetone-d6)δ:125.9(C-1),
148.6(C-2), 112.8 (C-3), 111.3 (C-4), 154.8
(C-5), 115.3(C-6), 33.8(C-7), 175.0(C-8).
ESI-MSm/z:169 [ M +H] +.Thesedatawere
consistentwiththoseofreference[ 6] .
3, 4-Dihydroxy-benzeneaceticacid(5), white
crystal(EtOAc-hexane); 1HNMR (500 MHz,
acetone-d6)δ:3.50(2H, s, H-7), 6.45(1H, dd, J=
8.6, 2.9 Hz, H-6), 6.55(1H, d, J=8.6 Hz, H-5),
6.58(1H, d, J=2.9 Hz, H-2).13CNMR(125 MHz,
acetone-d6)δ:118.4(C-1), 116.5(C-2), 149.0
(C-3), 151.0(C-4), 115.1(C-5), 123.1(C-6),
36.0(C-7), 173.3(C-8).ESI-MSm/z:169[ M+
H] +.Thesedatawereconsistentwiththoseof
reference[ 8] .
Vanilicacid(6), yelow powder(EtOAc-
hexane);1HNMR(500 MHz, acetone-d6)δ:3.90
(3H, s, 4-OCH3), 6.91(1H, d, J=8.2 Hz, H-5),
7.55(1H, d, J=1.9 Hz, H-2), 7.58(1H, dd, J=
8.2, 1.9 Hz, H-6).13CNMR(125 MHz, acetone-d6)
δ:122.8(C-1), 115.4(C-2), 148.0(C-3), 151.9
(C-4), 113.4(C-5), 124.8(C-6), 167.4(C-7),
56.3(4-OCH3).ESI-MSm/z:169[ M+H] +.These
datawereconsistentwiththoseofreference[ 9] .
Cafficacid (7), yelow powder(EtOAc-
methanol);1HNMR(500 MHz, acetone-d6)δ:6.15
(1H, d, J=15.9 Hz, 2-H), 6.74(1H, d, J=8.1 Hz,
8-H), 6.92(1H, dd, J=15.9, 2.0 Hz, 9-H), 7.04
(1H, d, J=2.0 Hz, 5-H), 7.42(1H, d, J=15.9 Hz,
3-H).13CNMR(125 MHz, acetone-d6)δ:168.1
(C-1), 122.4(C-2), 145.9(C-3), 127.7(C-4),
116.3(C-5), 146.2 (C-6), 148.6 (C-7), 115.7
(C-8), 115.1(C-9).ESI-MSm/z:179[ M-H] +.
Thesedatawereconsistentwiththoseofreference[ 10] .
Succinicacid(8), colorlesscrystal(EtOAc-
methanol), 1HNMR(500 MHz, DMSO-d6)δ:2.40
(4H, s, CH2 ), 12.12(2H, s, OH).13CNMR(125
MHz, DMSO-d6)δ:28.8(CH2), 173.6(COOH).
ESI-MSm/z:101 [ M-OH] -.Thesedatawere
consistentwiththoseofreference[ 11] .
2-Furoicacid (9), whitecrystal(EtOAc-
hexane);1HNMR(500 MHz, DMSO-d6 )δ:6.65
(1H, dd, J=3.0 , 1.6 Hz, H-3), 7.20(1H, dd, J=
3.0, 0.7 Hz, H-2), 7.87(1H, dd, J=1.6, 0.7 Hz,
H-4).13CNMR(125 MHz, DMSO-d6)δ:144.9
(C-1), 117.6(C-2), 112.0(C-3), 146.9(C-4),
·628· 药学学报 ActaPharmaceuticaSinica2008, 43(6):626-629
159.2(C-5).EI-MSm/z:112(100%), 95(71%),
84 , 67, 55, 45.Thesedatawereconsistentwiththose
ofreference[ 5] .
1, 2, 4, 5-Tetrahydro-jacaranone(10), colorless
crystal(EtOAc-hexane);1HNMR(500 MHz, DMSO-
d6)δ:1.85(2H, m, H-3a, 5a), 1.95 -2.05(4H, m,
H-2b, 3b, 5b, 6b), 2.45(2H, s, H-7), 2.55(2H, m,
H-2a, 6a).13CNMR (125 MHz, DMSO-d6 )δ:
210.9(C-1), 36.5(C-2 , 6), 36.0(C-3, 5), 67.9
(C-4), 46.2(C-7), 172.3(C-8).ESI-MSm/z:171
[ M-H] -.Thesedatawereconsistentwiththoseof
reference[ 12] .
4-(Pyrrolidin-2-one)-phenylaceticacid(11),
whitecrystal(EtOAc-hexane);1HNMR(500 MHz,
DMSO-d6)δ:2.15(2H, q, J=7.9 Hz, H-4′), 2.48
(2H, t, J=7.9 Hz, H-3′), 3.60(2H, s, H-7), 3.88
(2H, t, J=7.1 Hz, H-5′), 7.28(2H, d, J=8.7 Hz,
H-2 , H-6), 7.56(2H, d, J=8.7 Hz, H-3, H-5).
13CNMR(125 MHz, DMSO-d6 )δ:131.1(C-1),
130.2(C-2, C-6), 120.0(C-3, C-5), 139.8(C-4),
40.6(C-7), 172.7 (C-8), 174.3 (C-2′), 33.1
(C-3′), 18.5(C-4′), 48.9(C-5′).ESI-MSm/z:
220[ M+H] +.Thesedatawereconsistentwiththose
ofreference[ 13] .
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·629·MAHong-yan, etal:AnewcompoundfromSeneciocannabifoliusvarintegrilifolius