全 文 ：天然产物研究与开发 NatProdResDev2008, 20:56-59
文章编号:1001-6880(2008)01-0056-04
　
　
　ReceivedSeptember20, 2006;AcceptedOctober31, 2006
　FoundationItem:ThisprojectwassupportedbythegrantoftheNatural
ScienceFoundationofShanghaiMunicipality(No.036505003).
＊CorrespondingauthorTel:86-21-50806726;E-mail:yye@mail.shc-
nc.ac.cn
直立百部的非生物碱化学成分研究
杨新洲 ,林理根 ,唐春萍 ,柯昌强 ,叶　阳＊
中国科学院上海药物研究所新药研究国家重点实验室 , 上海 201203
摘　要:从直立百部(Stemonasessilifolia)根中首次分离到十四个非生物碱成分。依据波谱数据 , 它们鉴定为豆
甾醇(1)、4-甲氧基苯甲酸(2)、苯甲酸(3)、3, 4-二甲氧基苯酚 (4)、4-甲氧基苯甲酸(5)、4-羟基苯甲酸(6)、 4-羟
基-3-甲氧基苯甲酸(7)、4-羟基-3, 5-二甲氧基苯甲酸(8)、3, 3′-bis(3, 4-dihydro-4-hydroxy-6-methoxy)-2H-1-benzo-
pyran(9)、4-羟基-3-甲氧基苯甲醛(10)、羽扇豆烷-3-酮 (11)、绿原酸(12)、胡萝卜苷(13), 3-feruoyl-chinasueure
(14)。化合物 5 ～ 14为首次从百部属植物中分离得到。
关键词:直立百部;百部属;非生物碱;苯甲酸;苯并吡喃
中图分类号:R284.1;Q946.91 文献标识码:A
Non-alkaloidConstituentsfromStemonasessilifolia
YANGXin-zhou, LINLi-gen, TANGChun-ping, KEChang-qiang, YEYang＊
StateKeyLaboratoryofDrugResearch, ShanghaiInstituteofMateriaMedica, Chinese
AcademyofSciences, Shanghai201203 , China
Abstract:Fourteennon-alkaloidconstituentswerefirstlyisolatedfromtherootsofStemonasessilifolia.Onthebasisof
thespectraldata, theyweredeterminedasstigmasterol(1), 4-methoxybenzoicacid(2), benzoicacid(3), 3, 4-dime-
thoxyphenol(4), 4-methylbenzoicacid(5), 4-hydroxybenzoicacid(6), 4-hydroxy-3-methoxybenzoicacid(7), 4-hy-
droxy-3, 5-dimethoxybenzoicacid(8), 3, 3′-bis(3, 4-dihydro-4-hydroxy-6-methoxy)-2H-1-benzopyran(9), 4-hydroxy-
3-methoxybenzaldehyde(10), lupan-3-one(11), chlorogenicacid(12), daucosterol(13)and3-feruoyl-chinasueure
(14).Compounds5-14 wereisolatedfromthegenusStemonaforthefirsttime.
Keywords:Stemonasessilifolia;Stemona;non-alkaloid;benzoicacid;benzopyran
Introduction
ThegenusStemonacontainsabout25 species, among
whichS.sesilifolia, S.japonicaandS.tuberosahave
longbeenprescribedinthetraditionalChinesemedi-
cinesasinsecticidesandantitussiveagents[ 1, 2] .Upto
now, extractsfromrootsofthesethreespeciesarestil
usedtotreatrespiratorydisorders, includingpulmonary
tuberculosisandbronchitis, andexternalyusedagainst
diferentinsectpests[ 2] .Thepreviouschemicalinvesti-
gationonS.sesilifoliarevealedtheexistenceofalka-
loids, stilbenoids, alignan, asterolandtwoglycerinmo-
noesters[ 3] .Inourfurtherstudiesonthechemical
componentsfrom S.sesilifolia, fourteencompounds
wereisolatedandidentifiedasstigmasterol(1), 4-me-
thoxybenzoicacid(2), benzoicacid(3), 3, 4-dime-
thoxyphenol(4), 4-methylbenzoicacid(5), 4-hy-
droxybenzoicacid(6), 4-hydroxy-3-methoxybenzoic
acid(7), 4-hydroxy-3, 5-dimethoxybenzoicacid(8),
3, 3′-bis(3, 4-dihydro-4-hydroxy-6-methoxy)-2H-1-
benzopyran(9), 4-hydroxy-3-methoxybezaldehyde
(10), lupan-3-one(11), chlorogenicacid(12), dau-
costerol(13)and3-feruoyl-chinasueure(14), respec-
tively.Alcompoundswerefirstlyisolatedfromthetitle
plantandcompound5-14wereisolatedfromthegenus
Stemonaforthefirsttime.
Experimental
General
NMRspectrawererecordedonaBrukerAM-400 in-
strumentwithTMSasinternalstandard, thechemical
shiftvaluesarereportedinunit(δ)andcouplingcon-
stant(J)aregiveninHz.AlMSdatawereobtained
withMAT-95massspectrometer.IRspectrawererecor-
dedonaNicoletMagna750 FTIR(KBr)spectropho-
tometer.MeltingpointsweredeterminedonaFisher-
Johnsmeltingpointapparatusandareuncorrected.Sili-
cagel(100-200, 200-300 mesh) andsilicagel
(GF254 )forprecoatedplateswereusedforcolumn
chromatography(CC)andforpreparativeTLC, respec-
tively.
Plantmaterial
ThefreshrootsofStemonasessilifoliawerecolectedin
TuzhouCounty, AnhuiProvince, P.R.China, inSep-
tember, 2002, andidentifiedbyProf.Jin-guiShenof
ShanghaiInstituteofMateriaMedica, ChineseAcademy
ofSciences.Avoucherspecimen(20020014B)was
depositedintheHerbariumoftheinstitute.
Extractionandisolation
Air-driedrootsofS.sessilifolia(10 kg)wereground
andthenpercolatedwith95% EtOH.Theconcentrated
extractwassuspendedinH2Oandpartitionedsucces-
sivelywithPe(petroleumether), CHCl3 , EtOAcand
n-BuOH.TheCHCl3-solublefraction(55 g)wassub-
jectedtosilicagelcolumnelutedgradientlywithPe-ac-
etone(4:1-1:2).TheevaporatedresiduefromPe-ace-
tone(4:1)elutionwassubjectedtorepeatedcolumn
chromatographyoversilicagelelutedwithhexane-EtO-
Ac(8:2)toafordsuccessivelycompounds1 (100
mg), 2(55mg), 3(37 mg), 4 (45mg), 5(15mg),
6 (90 mg), 7(10mg)and8(14mg).Theevaporat-
edresiduefromPe-acetone(2:1)elutionwassepara-
tedoversilicagelcolumnwithhexane-EtOAc-formic
acid(100:40:1, 2 L)assolventstoyieldcompounds
9 (8 mg), 10(15mg)and11(9mg).Theevaporat-
edresiduefromacetoneelution(10 g)wassubjected
tothecolumnchromatographyoverRP-18elutedgradi-
entlywithH2O-MeOH(3:1-1:2)togivecompounds
12 (110mg), 13 (21 mg)and14 (120mg).
Identification
Stigmasterol(1)　Colorlessneedles(MeOH);mp.
152-154℃;EI-MSm/z:412 [ M] + , 394, 327, 301,
273, 255;1HNMR(CDCl3)δ:5.32 (1H, d, J=5.2
Hz, H-6), 5.12 (1H, dd, J=15.2, 8.8 Hz, H-22),
5.00 (1H, dd, J=15.2, 8.8 Hz, H-23), 3.50 (1H,
m, H-3), 1.02 (3H, s, H-19), 0.99 (3H, d, J=8.1
Hz, H-21), 0.84 (3H, t, J=7.7 Hz, H-29), 0.82
(3H, d, J=8.7 Hz, H-27), 0.80 (3H, d, J=8.7 Hz,
H-26), 0.66 (3H, s, 18-Me).TheabovedataandRf
valuesonTLCareconsistentwiththoseofauthentic
sample.
4-Methoxybenzoicacid(2)　 Colorlessneedles
(EtOH);mp.183-185 ℃;EI-MSm/z:152 [ M] +,
135, 122, 109, 92, 84, 56;1HNMR(CDCl3)δ:8.42
(2H, dd, J=8.6 , 2.0 Hz, H-2, H-6), 7.06 (2H, dd, J
=8.6, 2.0 Hz, H-3, H-5), 3.68 (3H, s, OMe);13 C
NMR(CDCl3)δ:125.1 (C-1), 132.3 (C-2, C-6),
114.1 (C-3, C-5), 163.6 (C-4), 168.8 (C-7), 55.4
(OMe).TheabovedataandRfvaluesonTLCarecon-
sistentwiththoseofauthenticsample.
Benzoicacid(3)　 Colorles needles(CHCl3 );
mp.121-123 ℃;EI-MSm/z:122 [ M] +, 105, 94, 77,
51;1HNMR(CDCl3)δ:8.05 (2H, br.d, J=7.3 Hz,
H-2, H-6), 7.14 (1H, m, H-4), 7.52 (2H, dd, J=
7.8, 7.3Hz, H-3, H-5).TheabovedataandRfvalues
onTLCareconsistentwiththoseofauthenticsample.
3, 4-Dimethoxyphenol(4)　Colorlesspowder;EI-MS
m/z:154 [ M] +, 136 , 108, 97, 80 , 69, 55;1HNMR
(CDCl3)δ:7.24 (1H, d, J=3.0 Hz, H-2), 6.77
(1H, d, J=8.0 Hz, H-5), 6.93 (1H, dd, J=8.0 , 3.0
Hz, H-6), 3.31and3.28 (each3H, s, OMe).Thea-
bovedatawasidenticalwiththosereported[ 4] .
4-Methylbenzoicacid(5)　Colorlesspowder;EI-MS
m/z:136 [ M] +, 121 , 107, 93, 77 , 65, 53;1HNMR
(CDCl3)δ:12.67(1H, br.s, COOH), 8.08 (2H, m,
H-2, H-6), 7.18 (2H, m, H-3, H-5), 2.51 (3H, s, 4-
Me).TheabovedataandRfvaluesonTLCareconsist-
entwiththoseofauthenticsample.
4-Hydroxybenzoicacid(6)　 Colorlessneedles
(CHCl3);mp.214-216 ℃;EI-MSm/z:138 [ M] +,
122, 121, 93, 65;1HNMR(CDCl3)δ:12.37 (1H,
br.s, COOH), 10.22(1H, br.s, OH), 7.77 (2H, d, J
=8.6Hz, H-3, H-5), 6.83 (2H, d, J=8.6 Hz, H-2,
H-6);13CNMR(CDCl3):167.2(C=O), 161.6(C-
1), 131.7 (C-2, C-6), 115.3 (C-3, C-5), 121.3 (C-
4).TheabovedataandRfvaluesonTLCareconsistent
withthoseofauthenticsample.
57Vol.20 YANGXin-zhou, etal:Non-alkaloidConstituentsfromStemonasesilifolia
4-Hydroxy-3-methoxybenzoicacid(7)　Colorless
powder;EI-MSm/z:168 [ M] +, 153, 125, 97 , 45;1H
NMR(CDCl3)δ:7.45 (1H, br.d, J=8.8 Hz, H-6),
6.85(1H, d, J=8.8 Hz, H-5), 7.44 (1H, br.s, H-
2), 3.81 (3H, s, OMe);13 CNMR(CDCl3)δ:168.1
(C=O), 151.0(C-3), 147.5 (C-4), 142.0 (C-1),
123.8 (C-2), 115.3 (C-5), 113.3 (C-6), 56.0
(OMe).TheabovedataandRfvaluesonTLCarecon-
sistentwiththoseofauthenticsample.
4-Hydroxy-3 , 5-dimethoxybenzoicacid(8)　Light
yelowpowder;EI-MSm/z:198 [ M] + , 183, 127,
109, 43;1HNMR(CDCl3 )δ:7.21 (2H, s, H-2, H-
6), 3.80(6H, s, 3-OMe, 5-OMe);13CNMR(CDCl3)δ:
168.1 (C=O), 147.8 (C-3, C-5), 140.3 (C-4),
121.7 (C-1), 107.3 (C-2, C-6), 56.4 (3-OMe, 5-
OMe).Theabovedatawasidenticalwiththoserepor-
ted[ 5] .
3, 3′-Bis(3, 4-dihydro-4-hydroxy-6-methoxy)-2H-1-
benzopyran(9)　Colorlesscubiccrystals(MeOH);
[ α] 20D -128°(MeOH, c0.14);EI-MSm/z:358
[ M] +, 343, 340, 327, 270, 258, 205, 180, 166, 152,
137, 131;1HNMR(CDCl3)δ:4.22 (4H, dd, J=
9.1, 6.8 Hz, H-2a, H-2a′), 3.85 (2H, dd, J=7.4,
3.8 Hz, H-2e, H-2e′), 3.09 (2H, m, H-3, H-3′),
4.73(2H, d, J=4.1 Hz, H-4, H-4′), 6.87 (2H, d, J
=1.8 Hz, H-5, H-5′), 6.80 (2H, dd, J=8.1, 1.8
Hz, H-7 , H-7′), 6.88 (2H, d, J=8.1 Hz, H-8, H-
8′), 3.88 (6H, s, OMe);13CNMR(CDCl3)δ:71.7
(C-2, C-2′), 54.2 (C-3, C-3′), 85.2 (C-4, C-4′),
114.4 (C-5, C-5′), 46.8 (C-6, C-6′), 118.9 (C-7,
C-7′), 108.8 (C-8, C-8′), 145.4 (C-9, C-9′), 132.9
(C-10, C-10′), 56.0 (OMe).Theabovedatawasi-
denticalwiththosereported[ 6] .
4-Hydroxy-3-methoxybezaldehyde(10)　Colorless
power;EI-MSm/z:152 [ M] + , 151, 137, 123 , 109,
92 , 81, 77, 65, 53, 39;1H NMR(CDCl3 )δ:9.82
(1H, s, CHO), 6.39(1H, br.s, H-2), 7.42(1H, dd,
J=8.0, 1.8 Hz, H-6), 7.04 (1H, d, J=8.0 Hz, H-
5), 3.93 (3H, s, OMe);13CNMR(CDCl3)δ:191.0
(C=O), 151.8(C-3), 147.2 (C-4), 129.8 (C-1),
127.5 (C-2), 114.5 (C-5), 108.9 (C-6), 56.1
(OMe).Theabovedatawasidenticalwiththoserepor-
ted[ 7] .
Lupan-3-one(11)　Whitepowder;EI-MSm/z:426
[ M] + , 411, 341, 302 , 287, 273, 257, 246, 233, 218,
205, 191, 179, 163, 149, 137, 123, 109 , 95, 81 , 69,
55;1HNMR(CDCl3)δ:0.72 (3H, s), 0.86 (3H,
s), 0.94 (3H, s), 0.99 (6H, d, J=5.0 Hz), 0.98
(3H, s), 1.04 (3H, s), 1.18 (3H, s), 2.39 (1H,
m), 2.31 (1H, m), 2.25 (1H, m), 1.95 (1H, m),
1.6-1.8 (3H, m), 1.2-1.6 (16H, m).Theabovedata
wasidenticalwiththosereported[ 8] .
Chlorogenicacid (12)　 Colorlesspower;UV
(MeOH)λmaxnm:327, 300, 235, 216;EI-MSm/z:354
[ M] + , 163;1HNMR(CD3OD)δ:6.24 (1H, d, J=
15.9 Hz, H-2′), 7.54 (1H, d, J=15.9 Hz, H-3′),
6.76 (1H, d, J=8.2 Hz, H-5″, 6.94 (1H, dd, J=
8.2, 2.0Hz, H-6″, 7.04 (1H, d, J=2.0 Hz, H-2″),
2.01-2.62 (4H, m, H-2, H-6), 3.70 (1H, dd, J=
8.2, 3.0 Hz, H-4).TheabovedataandtR inHPLC
wereconsistentwiththoseofauthenticsample.
Daucosterol(13)　Colorlesspowder;ES-MSm/z:
599 [ M+Na] + , 576 [ M] + , 413 [ M-glu-1] +;EI-MS
m/z:414 [ M] +, 396, 381, 354, 329, 303, 273, 255,
231, 213;1HNMR(DMSO-d6)δ:5.34 (1H, m, H-
6), 4.92 (1H, d, J=8.0 Hz, Glu, H-1′), 3.50 (1H,
m, H-3), 0.99 (3H, s, H-19), 0.92 (3H, d, J=8.1
Hz, H-21), 0.84 (3H, t, J=7.7 Hz, H-29), 0.82
(3H, d, J=8.7 Hz, H-27), 0.80 (3H, d, J=8.7 Hz,
H-26), 0.66 (3H, s, 18-Me);13CNMR(DMSO-d6):
36.7 (C-1), 29.3 (C-2), 76.8 (C-3), 38.2 (C-4),
140.3 (C-5), 120.1 (C-6), 31.3 (C-7, C-8), 50.5
(C-9), 36.1 (C-10), 22.5 (C-11), 41.7 (C-12),
45.0 (C-13), 56.1 (C-14), 24.8 (C-15), 27.7 (C-
16), 55.3 (C-17), 11.6 (C-18), 19.0 (C-19), 35.4
(C-20), 18.8 (C-21), 33.0 (C-22), 25.3 (C-23),
49.5 (C-24), 28.5 (C-25), 19.6 (C-26), 12.9 (C-
27), 23.8(C-28), 12.0(C-29), 100.6(Glu, C-1′),
73.3 (C-2′), 76.8 (C-3′), 69.9 (C-4′), 76.6 (C-
5′), 60.9 (C-6′).TheabovedataandtR inHPLC
wereconsistentwiththoseofauthenticsample.
3-Feruoyl-chinasueure(14)　Colorlespowder;EI-
MSm/z:368 [ M] +, 350, 194, 177, 150, 145, 134,
117, 105, 91, 89, 77 , 63, 51;1HNMR(CD3OD)δ:
6.44 (1H, d, J=16.0 Hz, H-2′), 7.69 (1H, d, J=
16.0 Hz, H-3′), 6.91 (1H, d, J=8.1 Hz, H-5″),
58 NatProdResDev　　　　　　　　　　　　　　　　　　　　　 　Vol.20
7.12(1H, dd, J=8.1, 2.0Hz, H-6″), 7.23(1H, d, J
=2.0 Hz, H-2″), 1.98-2.62 (4H, m, H-2, 6), 3.70
(1H, dd, J=8.2, 3.0Hz, H-4), 3.87 (3H, s, OMe).
Theabovedatawasidenticalwiththosereported[ 9] .
Acknowledgement　Thisprojectwassupportedbya
grantoftheNaturalScienceFoundationofShanghai
Municipality(No.036505003).
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59Vol.20 YANGXin-zhou, etal:Non-alkaloidConstituentsfromStemonasesilifolia