全 文 ：天然产物研究与开发 NatProdResDev2007, 19:610-613
文章编号:1001-6880(2007)04-0610-04
　
　
　ReceivedSeptember20, 2006;AcceptedDecember7, 2006
　FoundationItem:ThisworkwassupportedbytheFundofYunnan
Province-ChineseAcademyofScienceCooperation(2000YK-01).
＊CorrespondingauthorTel:86-013908775960;E-mail:yxnzymsc@ya-
hoo.com.cn
裂褶菌化学成分研究
毛绍春 1＊ ,李竹英 1 ,李　聪 2
1玉溪农业职业技术学院 ,玉溪 653100;2云南大学应用化学系 , 昆明 650091
摘　要:经硅胶反复柱层析 , 从裂褶菌子实体的醇提物中首次分离得到 8个化合物 ,利用波谱方法及理化性质鉴
定为 5α, 8α-过氧麦角甾-6, 22E-二烯-3β-醇(1)、麦角甾-7, 22-二烯-3β醇(2)、(22E, 24R)-麦角甾-7, 22-二烯-3β,
5α, 6β-三醇(3)、烟酸(4)、苯甲酸(5)、D-阿拉伯糖醇(6)、甘露醇(7)、海藻糖(8)。
关键词:裂褶菌;子实体;麦角甾醇
中图分类号:R284.2 文献标识码:A
ChemicalConstituentsfromSchizophylumcommune
MAOShao-chun1＊ , LIZhu-ying1 , LICong2
1YuxiAgriculturalVocationalTechnologyInstitute, Yuxi653100 , China;
2TheDepartmentofChemistry, YunanUniversity, Kunming650091 , China
Abstract:Bysilicagelcolumnchromatography, eightcompoundswereisolatedfromethanolicextractsofSchizophylum
communfruitingbodiesforthefirsttime.Onthebasisofspectraldateandphysicochemicalproperty, whichoneight
compoundswereidentifiedas5α, 8α-epidioxy-ergosta-6, 22E-dien-3β-ol(1), ergosta-7, 22-dien-3β-ol(2), (22E, 24R)-
ergosta-7, 22-diene-3β, 5α, 6β-triol(3), nicotinicacid(4), benzoicacid(5), D-arabitol(6), D-mannitol(7), D-treha-
lose(8).
Keywords:Schizophylumcommune;fruitingbodies;ergosterol
Introduction
Schizophylum commune, othernamewhiteginseng,
trees-flowers, belongstoEumycophyta, Basidiomycetes,
Agaricales, Schizophylaceae, Schizophylum[ 1] .Three
kindshavealreadybeendiscoveredinSchizophylum.
Schizophylum communewidelydistributesinwhole
world.Schizophylumcommuneisfamousformedicinal
purposesfungusinourcountry, ithasbeenreceived
widespreadatentionbecauseoffunctions[ 2] onnutri-
tiously, calm, resistbacteria, anti-tumor.Theresearches
onpolysaccharidefrom Schizophylum communeare
manyathomeandabroad.GuoMeng-bietal.[ 3] stud-
iedtheingredientofthevolatileoil, theaminoacids
andinorganictraceelementfromSchizophylumcom-
mune.ThechemicalcompositionofSchizophylumcom-
munewasnotreported.Inordertoseektheactivecon-
stituent, whichoneightcompounds(Fig.1)wereisola-
tedfromethanolextractsofSchizophylumcommunein
thisarticle.
InstrumentsandMaterials
XT-4meltingpointapparatus(Thethermometerhasnot
adjusted);AVATARFT-IRspectrometer(KBrdisc);
BrukerAM-500 nuclearmagneticresonanceapparatus;
AgilentLC/MSDTOFmassspectrograph(CDCl3 isthe
solventandTMSisaninternalstandard);VarioELor-
ganicelementanalyzer;BrukerSMARTCCDsingle-
crystaldifractometer;silicagel(HA:100-200 mesh,
HB:200-300 mesh);GF254 -Hsilicagel(0-40 μm).
ThedrynaturalSchizophylumcommune, wasboughtin
theKunmingdry-vegetable-market.
ExtractionandIsolation
ThenaturalSchizophylumcommune(0.5 kg), driedat
60℃ andcrushed, weresoakedwith95% EtOH(1 L
×4, eachtime3h)at50℃.Thecombinedextractwas
evaporatetedunderreducedpressuretogive110 g.
Thenextractivewereextractedbypetroleum ether,
chloroform, ethylacetateandn-butylalcoholtogive
corespondingfractionsA(16 g), B(16 g), C(26 g)
andD(11 g).
Fig.1　CompoundsisolatedfromSchizophylumcommune
FractionsAwassubjectedtoCConsilicageleluted
withpetroleumether-chloroform, petroleumether-ethyl
acetatetogivecompounds1(60mg).FractionsBwas
subjectedtoCConsilicagelelutedwithpetroleume-
ther-chloroform, petroleumether-ethylacetate, chloro-
form-ethylacetateandacetonetogivecompounds2(60
mg)and3(30 mg).FractionsCwassubjectedtoCC
onsilicagelelutedwithpetroleumether-ethylacetate,
chloroform-ethylacetateandchloroform-carbinoltogive
compounds4(10 mg)5, (30 mg)and6(83 mg).
FractionsDwassubjectedtoCConsilicageleluted
withchloroform-carbinolandacetone-carbinol, again
throughmendsthecrystaltogive7(10mg), 5(40mg)
and8(25 mg).
StructureIdentification
Compound1　Whiteacicularcrystal(ethylacetate),
mp.176-178 ℃, [ α] 20D -6.5°(c0.10, CH3OH).
Lieberman-Berchardrespondedassumesthemasculine.
IRυKBrmax cm-1:3401, 3119, 2952, 2874, 1631, 1458,
1395, 1215, 1077, 963;1HNMRδ:6.50(1H, d, J=
8.4Hz, H-7), 6.25(1H, d, J=8.5 Hz, H-6), 5.23
(1H, dd, J=15.2, 7.6 Hz, H-23), 5.151H, dd, J=
15.2, 7.7 Hz, H-22), 3.98(1H, m, H-3), 1.00(3H,
d, J=6.5 Hz, H-21), 0.91(3H, d, J=6.8 Hz, H-
28), 0.89(3H, s, H-19), 0.85(3H, d, J=6.5 Hz, H-
26or27), 0.84(3H, d, J=6.7Hz, H-27or26), 0.82
(3H, s, H-18);13CNMRδ:136.3(d, C-6), 136.1(d,
C-7), 133.3(d, C-22), 131.7(d, C-23), 83.0(s, C-
8), 80.3(s, C-5), 67.4(d, C-3), 57.2(d, C-17),
52.6(d, C-14), 52.1(d, C-9), 45.5(s, C-13), 43.7
(d, C-24), 40.6(d, C-20), 40.3(t, C-12), 37.9(t, C-
4), 36.7(d, C-10), 35.6(t, C-1), 34.0(t, C-25), 31.
1(t, C-2), 29.5(t, C-16), 24.3(q, C-11), 21.8(t, C-
21), 21.5(t, C-15), 20.8(q, C-26), 20.5(q, C-27),
19.0(q, C-19), 18.4(q, C-28), 13.8(q, C-18).EI-
MS(+TOF)m/z:451[ M+Na] +, 429[ M+1] +,
411[ M+1-H2O] + , 395[ M+1-H2-O2 ] +, 377[ M+1-
O2 -H2O-H2 ] +(100).Elementanalysis:C:78.83%,
H:10.05%, O:10.99%.Thiscompoundisconfirmed
as5α, 8α-epidioxy-ergosta-6, 22E-dien-3β-olcompa-
ringwiththeliterature[ 4] date.
Compound2　Colorlescrystal, easytodissolvein
thechloroform andtheacetone, mp.164-166 ℃,
[ α] 20D-8.7°(c0.10, CH3OH).Lieberman-Berchard
reactionassumesthegreen.IRυKBrmax cm-1:3400, 3127,
3009, 2948, 2870, 1641, 1400, 1162, 1030, 969;1H
NMR(C3D6O)δ:5.27(2H, m, H-22 andH-23), 5.20
(1H, s, H-7), 3.52(1H, m, H-3), 1.10(3H, d, J=
6.6 Hz, H-21), 0.96(3H, d, J=6.8 Hz, H-28), 0.89
(6H, d, J=7.4 Hz, H-26 andH-27), 0.84(3H, s, H-
18), 0.86(3H, s, H-19);13 CNMRδ:140.2(C-8),
611Vol.19 MAOShao-chunetal:ChemicalConstituentsfromSchizophylumcommune
136.7(C-22), 132.7(C-23), 118.4(C-7), 70.7(C-
3), 56.9(C-17), 55.9(C-14), 50.5(C-9), 44.1(C-
13), 43.7(C-24), 41.2(C-4andC-1), 40.3(C-20),
38.9(C-5), 38.1(C-12), 35.0(C-10), 33.9(C-25),
32.3(C-11), 30.5(C-2), 28.8(C-6), 23.6(C-16),
22.3(C-15), 21.6(C-21), 20.3(C-26), 20.0(C-
27), 18.0(C-19), 12.6(C-28), 13.8(C-18).This
compoundisconfirmedasergosta-7, 22-dien-3β-ol
comparingwiththeliterature[ 5] dateandthemolecular
formulaisC28H46O.
Compound3　Colorlesscrystal, easytodissolvein
thechloroformandtheacetone, mp.220-221℃, [ α] 20D
+3.5°(c0.10, CH3OH)Lieberman-Berchardreaction
assumesthegreen.IRυKBrmax cm-1:3127, 3009, 2948,
2870, 1628, 1400, 1162, 1030, 969;1HNMRδ:5.36
(1H, brs, H-7), 5.23(1H, dd, J=15.2 , 7.4 Hz, H-
23), 5.15(1H, dd, J=15.3, 8.2 Hz, H-22), 4.09
(1H, m, H-3), 3.64(1H, brs, H-6), 2.15(2H, brt, J
=12.2 Hz, H-9), 1.09(3H, s, H-19), 1.03(3H, d, J
=6.5 Hz, H-21), 0.92(3H, d, J=6.8 Hz, H-28),
0.84-0.83(6H, d, J=7.2 Hz, H-26 andH-27), 0.56
(3H, s, H-18);13CNMRδ:144.9(s, C-8), 136.3(d,
C-23), 133.1(d, C-22), 118.4(d, C-7), 76.9(s, C-
5), 74.6(d, C-6), 68.7(s, C-3), 57.0(d, C-17),
55.7(d, C-14), 44.7(s, C-13), 44.4(d, C-9), 43.7
(d, C-24), 41.2(d, C-20), 40.4(t, C-4), 38.1(s, C-
10), 34.0(d, C-12), 33.9(t, C-1), 32.9(t, C-2),
31.8(t, C-16), 28.8(t, C-15), 23.8(t, C-11), 23.0
(t, C-27), 22.0(q, C-26), 20.8(q, C-19), 20.5(q,
C-21), 19.7(q, C-28), 18.5(q, C-25), 13.8(q, C-
18);EI-MS(+TOF)m/z:453 [ M+Na] + , 413[ M-
OH] +, 377[ M-OH-2H2O] +(100).Thiscompoundis
confirmed(22E, 24R)-ergosta-7, 22-diene-3β, 5α, 6β-
triolcomparingwiththeliterature[ 6] date.
Compound4　Whitepowder, mp.237-239 ℃.IRυKBrmax
cm-1:3500-3000(br), 2400-2600(br), 1715, 1592,
1484, 1403, 1315, 1183, 1121, 1036 , 814, 748 , 691;1H
NMR(C5D5N)δ:9.65(1H, s), 8.82(1H, s), 8.49
(1H, d), 7.31(1H, d);13CNMRδ:170.1(s), 155.5
(d), 153.8(d), 139.5(d), 130.1(s), 125.6(d);EI-
MS(+TOF)m/z:124[ M+1] +(100), 107[ M+H-
H2O] +, 96 [ M+H-CO] +, 80 [ M+H-CO2 ] +.This
compoundisidentifiedasnicotinicacidcomparingwith
theliteraturedata[ 7] andthemolecularformulais
C6H5O2N.
Compound5 　Whitepowder, mp.120-122℃.IRυKBrmax
cm-1:3121(br), 3005, 2557, 1686, 1599, 1452 , 1400,
1326, 1292, 1183, 1126, 1069, 1020 , 934, 808, 708,
664, 557;1HNMRδ:11.9(1H, brs), 8.14(2H, dd, J
=7.5Hz), 7.64(1H, dd), 7.49(1H, dd);13CNMR
δ:173.4(s), 134.8(d), 131.2(d), 130.2(s), 129.4
(d);EI-MS(+TOF)m/z:121[ M-1] + , 105[ M+1-
H2O] +(100).Thiscompoundisidentifiedasbenzoic
acidcomparingwiththeliteraturedata[ 7] andthemo-
lecularformulaisC7H6O2.
Compound6　Whitepowder, mp.99-100 ℃, [ α] 20D
+11.0°(c0.10, pyridine).IRυKBrmaxcm-1:3168, 3147,
3115, 1399, 1084, 1050, 1024, 905, 865;1H NMR
(DMSO)δ:3.90(1H, t), 3.83(1H, d), 3.80(1H,
d), 3.70(1H, t), 3.65(2H, d), 3.55(1H, d);13 C
NMRδ:72.6(d), 72.0(d), 71.5(d), 64.5(t), 64.3
(t);EI-MS(+TOF)m/z:175[ M+Na] +.Thiscom-
poundisidentifiedasD-arabitolcomparingwiththelit-
eraturedata[ 7] andthemolecularformulaisC5H12O5.
Compound7　Colorlessacicularcrystal, mp.165-166
℃, [ α] 20D +23.5°(c0.10, pyridine).IRυKBrmax cm-1:
3270, 2945, 2936, 1462, 1086 , 1025, 932, 718;1H
NMR(DMSO)δ:4.43(brs), 4.39(1H, brs), 4.36
(1H, brs), 4.16(1H, s), 3.61(1H, d), 3.54(1H,
s), 3.45(2H, s), 3.38(1H, m);13CNMRδ:71.7,
70.1, 64.2.ThiscompoundisidentifiedasD-mannitol
comparingwiththeliteraturedata[ 8] andthemolecular
formulaisC6H14O6.
Compound8　Colorlesscrystal(carbinol), mp.165-
166 ℃, [ α] +178°(c0.01, H2O).IRυKBrmax cm-1:
3494, 3400-3100(br), 2940, 1687, 1632, 1400, 1243,
1134, 1094, 1001, 913, 853, 799 , 657;1H NMR
(C5D5N)δ:5.89(1H, s), 5.55(brs), 4.88(1H, d),
4.74(1H, t), 4.42(1H, d), 4.35(1H, m), 4.22(2H,
m);13CNMRδ:96.2(d), 75.6(d), 74.9(d), 74.2
(d), 73.1(d), 63.5(t);EI-MS(+TOF)m/z:365[ M
+Na] +.Itispossiblytheglucosebythehydrogen
spectrumandthecarbonspectrumanalysis, butthe
massspectrumanalyzesitsmolecularweighttobebig-
gerthanmolecularweightofthesingleglucose.Ac-
612 NatProdResDev　　　　　　　　　　　　　　　　　　　　　 　Vol.19
cordingtothecomputedresultispossiblytwosugars.
Thiscompoundturnsthemonocrystalincarbinolsolu-
tion, thenthiscompoundisidentifiedD-trehalose, the
molecularformulaisC12H22O11.
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