全 文 ：天然产物研究与开发 NatProdResDev2010, 22:422-424
文章编号:1001-6880(2010)03-0422-03
　
　
　ReceivedOctober13, 2008;December10, 2008
　FoundationItem:ThisworkwasfinantialysupportedbytheQuality-
controlingStandardofChineseMedicinalMaterialsandPreparation
TechniqueofStandSampleofChineseMedicinal(2006GG1109078).
＊CorrespondingauthorTel:86-531-89628085;E-mail:zyq622003@
126.com
茶藨子叶孔菌子实体(忍冬)的化学成分研究
李　聪 ,张永清＊ ,李　佳 ,邱丽丽
山东中医药大学 , 济南 250355
摘　要:从茶藨子叶孔菌(忍冬)中分离了 8个化合物 ,通过波谱法和理化性质分别鉴定为豆甾醇(1), 二十八酸
(2), β-谷甾醇(3),麦角甾醇(4),麦角甾醇过氧化物(5), 壬二酸(6), 烟酸(7), 原儿茶酸(8)。化合物 1, 3, 6
均为首次从该属真菌中分到。
关键词:茶藨子叶孔菌(忍冬);子实体;化学成分
中图分类号:R284.1;Q946.91 文献标识码:A
ChemicalConstituentsfromFruitingBodiesof
Phyloporiaribis(LonicerajaponicaThunb.)
LICong, ZHANGYong-qing＊ , LIJia, QIULi-li
ShandongUniversityofTraditionalChineseMedicine, Jinan250355 , China
Abstract:EightcompoundswereisolatedfromthefruitingbodiesofPhylloporiaribis(LonicerajaponicaThunb.).On
thebasisofspectradataandphysicochemicalproperties, theywereidentifiedasstigmasterol(1), n-octacosanoicacid
(2), β-sterol(3), ergosterol(4), ergosterol-5, 8-peroxide(5), azelaicacid(6), niacin(7), protocatechuicacid(8).
Compounds1, 3, 6 wereobtainedfromthisgenusforthefirsttime.
Keywords:Phyloporiaribis(LonicerajaponicaThunb.);fruitingbodies;chemicalconstituents
Introduction
Phyloporiaribis(LonicerajaponicaThunb.), afungi
ofthegenusPhyloporiainthefamilyHymenochaet-
ales, hasbeenusedasatraditionalmedicineforthe
treatmentofpharyngitis, laryngitisandtonsilitis.The
fruitingbodiesofPhyloporiaribis(Lonicerajaponica
Thunb.)revealedvariousbiologicalactivitiesincluding
antitumor, immune-enhancing, anti-inflammatoryactivi-
tyandsoon[ 1] .Inthecourseofaphytochemicalstudy
onthefruitingbodiesofPhyloporiaribis(Loniceraja-
ponicaThunb.), eightcompoundswereisolatedandi-
dentifiedasstigmasterol(1), n-octacosanoicacid
(2), β -sitosterol(3), ergosterol(4), ergosterol-5, 8-
peroxide(5), azelaicacid(6), niacin(7)andproto-
catechuicacid(8).Compounds1, 3, 6 wereobtained
fromthisgenusforthefirsttime.
Experimental
General
NMRspectrawererecordedonBrukerDRX-500 spec-
trometerswithTMSasinternalstandard.MSdatawere
obtainedonaFinniganTracemassspectrometer.Melt-
ingpointsweremeasuredonanX-4 digitalmelting
pointapparatusandthetemperaturewasuncorrected.
Silicagel(100-200 mesh, 200-300 mesh, Qingdao
MarineChemicalFactory), SephadexLH-20 (Amer-
shamPharmaciaBiotech), andODS(50 μm, YMC
Co.)wereusedforcolumnchromatography.Althe
chemicalsusedinthisstudywereanalyticalgrade.
PlantMaterial
Phyloporiaribis(LonicerajaponicaThunb.)wascol-
lectedfrom Pingyi, ShandongProvince, in August
2007, andwasidentifiedbyProfZhangXiao-Qing(In-
stituteofMicrobiology, ChinaAcademyofScience).A
voucherspecimenwasdepositedinShandongUniversi-
tyofTraditionalChineseMedicine.
ExtractionandIsolation
ThefruitingbodiesofPhyloporiaribis(Lonicerajapon-
icaThunb.)(13kg)wasextractedthreetimes(3h/
each)with95% EtOH, andabout305 gofaresidue
wasobtainedafterevaporatingthesolventsinvacuo.
Theresiduewassuspendedinwaterandpartitioned
withpetroleumether, EtOAc, andn-BuOH, successive-
ly, toafordapetroleumetherextract(84 g), aEtOAc
extract(47g)andan-BuOHextract(30 g).Thepe-
troleumetherfractionwassubjectedtosilicagelcol-
umnchromatography, andelutedwithgradientofpetro-
leumetherandEtOAc(from100:0 to0:100, v/v)to
yield7 fractions(A-G).FractionAwasseparatedby
columnchromatographyonsilicagelwithpetroleume-
therandMe2CO(100:1 to1:100, v/v)andtoaford
Compound1 (20 mg).Compound2(15 mg)wasob-
tainedfromfractionBbycolumnchromatographyon
silicagel(petroleumether-Me2CO100:1 to1:100, v/
v).FractionCwasseparatedbycolumnchromatogra-
phyonsilicagel(petroleumether-Me2CO100:1 to1:
100, v/v)andcompound3(30mg)wascrystalized.
FractionDwasseparatedbycolumnchromatographyon
silicagel(petroleumether-Me2CO100:1 to1:100, v/
v)toafordcompound4 (10 mg).Compound5 (27
mg)wasobtainedbycolumnchromatographyonsilica
gel(petroleumether-Me2CO100:1 to1:100, v/v)
andwascrystalizedfrom(petroleumether-Me2CO7:
1)fractionandSephadexLH-20 (CHCl3 -MeOH1:1,
v/v)toafordCompound6 (7 mg)fromfractionE.
TheEtOAcfractionwassubjectedtosilicagelcolumn
chromatography, and eluted withpetroleum ether-
Me2CO(5:1to1:1)andCHCl3 -MeOH(20:1 to1:
1, v/v)toyield8 fractions(H-0)andCompound7
(200 mg)wasobtainfromfractionI.FractionLwas
separatedbycolumnchromatographyonsilicagel
(CHCl3 -MeOH 10:1 to1:1, v/v), SephadexLH-20
(MeOH)andODS(MeOH-H2O1:1, v/v)toaford
compounds8(7 mg).
Identification
Stigmasterol(1)　Colorlessneedles(CHCl3), mp.
152-154℃.EI-MSm/s:412 (M+), 394 , 369, 351,
327, 301, 273, 255, 199, 145, 95 , 69, 55.Theaboveda-
taandRfvaluesonTLCareconsistentwiththoseof
authenticsample.
N-octacosanoicacid(2)　Whitepowder(Me2CO),
mp.78-80 ℃.EI-MSm/s:424 (M+), 396, 368, 73,
57, 43;1HNMR(CDCl3 , 500 MHZ)δ:0.85(3H, t, J
=6.8 Hz), 1.25 (brs, CH2 ×n), 1.65 (2H, m),
2.30 (2H, t, J=6.6 Hz).13 CNMR(CDCl3 , 125
MHz)δ:14.1, 22.7, 24.7, 31.9, 33.7, 29.4 (CH2 ×
n), 179.7.Thesedatawereinagreementwiththoseof
n-octacosanoicacid[ 2] .
β-sterol(3)　Colorlessneedles(CHCl3), mp.139-
140 ℃.EI-MSm/s:414(M+), 396, 381, 329, 303,
145.ItshowedapositiveLibermann-Burchardreac-
tion.Itwasidentifiedasβ-sitosterolbycomparisionof
theTLCbehaviorandthemeltingpointwiththeau-
thenticcompound.
Ergosterol(4)　Colorlessneedles(CHCl3 ), mp.
153-155 ℃.EI-MSm/s:396(M+), 383, 363, 337,
271, 253, 227, 171, 105.1HNMR(CDCl3 , 500 MHz)
δ:5.54 (1H, bs, C6-H), 5.36 (1H, bs, C7 -H), 5.17
(2H, m, C22 -H, C23 -H), 3.61 (1H, m, C3-H), 1.01
(3H, d, J=6.59Hz, C21 -Me), 0.92(3H, s, C19 -Me),
0.89 (3H, d, J=6.87Hz, C28-Me), 0.82(3H, d, J=
6.32 Hz, C26-Me), 0.78 (3H, d, J=8.52 Hz, C27 -
Me), 0.60 (3H, s, C18-Me).13 CNMR(CDCl3 , 125
MHz)δ:38.8(C-1), 31.4(C-2), 69.8(C-3), 41.3
(C-4), 140.9 (C-5), 119.5 (C-6), 116.9 (C-7),
141.1(C-8), 46.7 (C-9), 37.4 (C-10), 22.2 (C-
11), 39.4 (C-12), 43.1 (C-13), 54.8 (C-14), 31.4
(C-15), 19.0 (C-16), 56.0 (C-17), 40.9 (C-18),
136.2 (C-19), 132.2 (C-20), 43.3 (C-21), 33.4
(C-22), 16.2 (C-23), 11.9 (C-24), 21.1 (C-25),
17.6(C-26), 19.5 (C-27), 19.9 (C-28).Thesedata
wereinagreementwiththoseofergosterol[ 3] .
Ergosterol-5, 8-peroxide (5)　 White needles
(CHCl3), mp.169-173 ℃.EI-MSm/s:428 (M+),
396, 271;1HNMR(CDCl3 , 500 MHz)δ:0.81 (3H,
s, C18 -Me), 0.81(6H, d, J=7.0Hz, C26, 27 -Me), 0.88
(3H, s, C19 -Me), 0.90 (3H, d, J=7.0 Hz, C28-Me),
1.00 (3H, d, J=7.0 Hz, C21-Me), 3.96 (1H, m, H-
3), 5.12 (1H, dd, J=15.5, 8.0 Hz, C23 -Me), 5.24
(1H, dd, J=15.5, 8.0 Hz, C22-Me), 6.23 (1H, d, J
423Vol.22　　　　　　LICong, etal:ChemicalconstituentsfromfruitingbodiesofPhyloporiaribis(LonicerajaponicaThunb.)　
=8.5 Hz, H-6), 6.49 (1H, d, J=8.5 Hz, H-7).13C
NMR(CDCl3 , 125 MHz)δ:36.9 (C-1), 30.1 (C-
2), 66.4 (C-3), 34.7 (C-4), 79.4 (C-5), 130.7
(C-6), 135.4(C-7), 82.1(C-8), 51.1 (C-9), 36.9
(C-10), 20.9 (C-11), 39.3 (C-12), 44.5 (C-13),
51.7(C-14), 28.6(C-15), 23.4 (C-16), 56.2 (C-
17), 12.9(C-18), 18.2(C-19), 39.7 (C-20), 19.6
(C-21), 132.3 (C-22), 135.2 (C-23), 42.8 (C-
24), 33.1(C-25), 19.9(C-26), 20.6 (C-27), 17.6
(C-28).Thesedatawereinagreementwiththoseofer-
gosterol-5, 8-peroxide[ 4] .
Azelaicacid(6)　Whiteneedles(CHCl3), mp.107
℃.EI-MSm/s:188 (M+), 171, 152, 124, 83, 41.1H
NMR(CDCl3 , 500MHz)δ:2.36 (4H, t, J=7.2 Hz,
H-2 , 8), 1.64 (4H, m, H-3, 7), 1.35 (6H, m, H-4 , 5,
6).13CNMR(CDCl3 , 125 MHz)δ:179.5 (C-1 , 9),
33.7 (C-2, 8), 24.3 (C-3, 7), 28.4 (C-4, 5, 6).
Thesedatawereidenticaltothoseofazelaicacidrepor-
tedintheliterature[ 5] .
Niacin(7)　Whitepowders(CHCl3), mp.233-234
℃.1HNMR(DMSO-d6 , 500MHZ)δ:7.54(1H, dd,
J=7.9, 4.8 Hz, 5-H), 8.26 (1H, dd, J=7.9, 1.9
Hz, 4-H), 8.78 (1H, dd, J=4.8, 1.9 Hz, 6-H), 9.06
(1H, d, J=1.2 Hz, 2-H), 13.41 (1-H).13 CNMR
(DMSO-d6 , 125 MHz)δ:166.2 (-COOH), 153.4
(C-2), 126.7(C-3), 137.0(C-4), 123.9(C-5),
150.3(C-6).Thesespectraldatawereinconsistent
withthoseofniacin[ 6] .
Protocatechuicacid(8)　Whiteneedles(CHCl3),
mp.197-198 ℃.EI-MSm/s:154(M+), 137, 109,
81 , 63.1HNMR(DMSO-d6 , 500 MHz)δ:7.53(1H,
d, J=2.0 Hz, H-2), 7.47 (1H, dd, J=8.5, 2.0 Hz,
H-6), 6.90 (1H, d, J=8.5 Hz, H-5).13 CNMR
(DMSO-d6 , 125 MHz)δ:123.0 (C-1), 117.2 (C-
2), 145.2 (C-3), 150.3 (C-4), 115.4 (C-5), 123.3
(C-6), 167.3 (-COOH).Thesedatawereinagree-
mentwiththoseofprotocatechuicacid[ 7] .
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