全 文 ：天然产物研究与开发 NatProdResDev2008, 20:644-646
文章编号:1001-6880(2008)04-0644-03
　
　
　ReceivedMay25, 2007;AcceptedOctober29, 2007
＊CorrespondingauthorTel:86-531-82605925;E-mail:gaoyongchao2002@
163.com
中华光萼苔的化学成分研究
高永超 1＊ ,孔　学 1 ,邱维忠 1 ,王加宁 1 ,张树军 2 ,沙　伟2
1山东省科学院生物研究所 ,济南 250014;2齐齐哈尔大学 ,齐齐哈尔 161006
摘　要:首次对中华光萼苔(Porelachinensis(Steph.)Hat.)的化学成分进行了研究 , 从中分离得到四种倍半萜
类化合物。通过波谱学数据并与已知化合物的数据比较 ,它们分别鉴定为环色烯酮(cyclocolorenone, 1)、辛辣木
醇(drimenol, 2)、辛辣木素(drimenin, 3)及 α-古巴烯(α-copaene, 4)。通过 NOESY确定了化合物 1的相对构型。
化合物 2和 4首次从该植物的配子体中分离得到。
关键词:中华光萼苔;光萼苔科;苔类;倍半萜
中图分类号:Q946.91;R284.2 文献标识码:A
ChemicalConstituentsinChineseLiverwort
Porelachinensis(Steph.)Hat
GAOYong-chao1＊ , KONGXue1 , QIUWei-zhong1 , WANGJia-ning1 , ZHANGShu-jun2 , SHAWei2
1InstituteofBiology, ShandongAcademyofScience, Jinan250014 , China;
2SchoolofLifeScienceandTechnology, QiqiharUniversity, Qiqihar161006 , China
Abstract:FoursesquiterpenoidswereisolatedfromPorelachinensis(Steph.)Hat.Theyweredeterminedascyclocolor-
enone(1), drimenol(2), drimenin(3), andα-copaene(4)bycomparisonwiththeirspectraldatawiththosereported.
Therelativeconfigurationofcompound1 wasestablishedonthebasisofNOESYexperiment.Drimenolandα-copaene
wereisolatedforthefirsttimefromthegametrophytesofliverwortP.chinensis.
Keywords:Porelachinensis;Porelaceae;Hepaticae;sesquiterpenoid
Introduction
Thereareabout100 speciesofPorelaceaedistributed
intheworld, especialyinAsiaandtropicAmerica[ 1] .
FiftyvarietiesorsubspecieswerediscoveredinChina
[ 1, 2] .MostofthePorelaspecies, belongingtothe
Jungermanniales(Hepaticae), arerichsourcesofses-
qui-andditerpenoids[ 3] .ThePorelaspeciesareclas-
sifiedintotwotypes.Onetypecontainsthepungent
sesquiterpenedialdehyde, andtheothercontainsnon-
pungentsubstancessuchaspinguisane-, aromaden-
drane-, drimane-, africane-typesesquiterpenoidsand
sacculatane-andkaurane-typediterpenoids[ 4, 5] .The
constituentsofmanyspeciesofthePorelaceaehave
beenstudied[ 3, 6-10] .P.chinensis(Steph.)Hatisdis-
tributedmainlyinChinaandHimalayanarea, atanal-
titudefrom2300 to4100 m[ 11] .Thereisnoreporta-
boutthechemicalconstituentsofthisspecies.
ResultsandDiscussion
Theair-driedplantmaterialwasextractedwithEtOH.
TheEtOHextractwassubjectedtosilicagelcolumn
chromatography.Fourcompoundswereobtainedbypre-
parativeTLC.Theyweredeterminedascyclocolorenone
[ 4, 5, 12] , drimenol[ 13, 14] , drimenin[ 15] , andα-copaene
[ 16] .Compound1 showedamolecularionpeakatm/z
218 (M+), andthe13CNMRspectrumshowed15sig-
nals.The13 CNMR(DEPT)datademonstrated4
methyls, 3 methylenesand4 methines.The1H-1H-
gCOSY, gHMBC, gHMQCindicatedaaromadendrane-
typesesquiterpene.ThestructureandmainHMBCcor-
relationsofcompound1wereshowedinFig.1.Therela-
tiveconfigurationwasdeterminedbyNOESYexperiment
(Fig.2).
Compound2 wasfirstidentifiedinBzaaaniatrilobata
DOI :10.16333/j .1001 -6880.2008.04.026
usingGC-MS[ 17] .Itwasfoundfromthesuspension
culturedcelsofPorelavernicosain1996 [ 18] , andiso-
latedfromtheliverwortB.trilobataandB.decrescens
subsequently[ 19, 20] .Butthereisnoreportaboutthei-
solationofdrimenolfromthegametrophytesofPorel-
laceae.Compound3 hasbeenisolatedfrom Porela
cordeanaandP.gracilima[ 15] .Compound3 wasal-
waysfoundinhigherplant, rarelyinliverwort.Itwasi-
solatedfromtheliverwortPreisiaquadrata[ 16] .Nore-
portabouttheisolationofα-copaenefromPorelaceae
hasbeenfound.
Experimental
MeltingpointsweremeasuredusingSWG X-4 mi-
cromelting-pointaparatus(uncorected).NMRspectra
wererecordedinCDCl3 onVarianInova-600.Themass
spectrawerecariedoutonanAgilent1100 LC/MSD.
TLCwasvisualizedunderUV(254, 302, 365 nm)ir-
radiation.Silicagel60-100 μm (QingdaoHaiyang
Chemicalplant)wasusedforcolumnchromatography
andsilicagelGF254 plateswasusedforTLC.
Plantmaterial
ThegametophyteoftheliverwortP.chinensiswascol-
lectedinYichunCity, HeilongjiangProvinceofChina,
inOctober2005.Theplantsamplewasidentifiedby
Prof.You-FangWangofeastChinaNormalUniversity.
AvoucherspecimenwasdepositedattheBiochemical
LaboratoryinInstituteofBiology, ShandongAcademy
ofSciences, China.
Extractionandisolation
Air-driedandpowderedplantmaterial(200 g)was
percolatedwith95% EtOHatroomtemperaturefor24
h.Thentheplantmaterialwasdistiledwithsoxhlot
distilerat80 ℃ for6 h, andtheextractwasconcen-
tratedunderreducedpressure.Thecrudeextract(16.5
g)wassuspendedinhotwaterandthenextractedwith
petroleumether(boilingrangefrom60 to90 ℃)for3
times.Thepetroleumetherextract(5.2 g)wasfirst
subjectedtosilicagelcolumnelutedgradientlywith
petroleumether/ethylacetatetoafordsevenfractions.
Eachfractionwassubjectedtosilicagelcolumneluted
withtolueneandmethanol(40∶1)andfinalypurified
bypreparativeTLC.Fourcompoundswereobtained.
Theyweredeterminedascyclocolorenone(1, 5.2
mg), drimenol(2 , 2.7 mg), drimenin(3, 4.5 mg),
andα-copaene(4, 1.9 mg).
Cyclocolorenone(1)　[ α] D+404°(1% inCHCl3
26℃), yelowoil.GC-MSm/z:218(100), 175(64),
161(63), 147(83), 133(72), 119(83), 105(84), 91
(74), 77(40), 55(37), 41(56), 29(14);1HNMR
(600 MHz, CDCl3)δ:2.85(1H, d, J=6.6 Hz, H-1),
2.50 (1H, dd, J=18.0, 6.6 Hz, H-2), 2.08 (1H, d,
J=18.0 Hz, H-2), 2.08 (1H, d, J=7.8 Hz, H-6),
1.98 (2H, m, H-8, H-10), 1.73 (3H, s, H-15), 1.60
(1H, m, H-8), 1.48 (1H, brd, J=7.8 Hz, H-7),
1.43 (1H, m, H-9), 1.27 (1H, m, H-9), 1.25 (3H,
s, H-13), 1.03 (3H, s, H-12), 0.81 (3H, d, J=6.6
Hz, H-14);13CNMR(150 MHz, CDCl3)δ:42.5 (C-
1), 40.2 (C-2), 208.5 (C-3), 140.3 (C-4), 176.7
(C-5), 28.5 (C-6), 32.4 (C-7), 21.1 (C-8), 32.3
(C-9), 31.6 (C-10), 26.0 (C-11), 16.5 (C-12),
29.5 (C-5), 17.5 (C-14), 8.2 (C-15).TheGC-MS
andNMRdatawereingoodagreementwiththosere-
ported[ 4, 5, 12] .
Drimenol(2)　Yelowcrystal(methanol), mp.97-98
℃;GC-MSm/z:222(10), 124(48), 109(100), 105
(19), 91(24), 81(22), 55(29), 41(45);1HNMR
(600 MHz, CDCl3)δ:1.93-0.95(8H, m, H-1, H-2 , H-
3, H-5), 4.95(1H, s, H-6), 3.65(2H, m, H-9), 0.86-
0.73(12H, m, H-10, H-11, H-12, H-13);13 CNMR
(150 MHz, CDCl3)δ:40.3(C-1), 17.5(C-2), 49.8
(C-3), 37.9(C-4), 67.2(C-5), 24.0(C-6), 106.3
(C-7), 148.3(C-8), 58.3(C-9), 41.9(C-10), 16.2
(C-11), 21.1(C-12), 25.9(C-13), 29.7(C-14),
18.3(C-15).Themp, GC-MS, andNMRdatawerein
645Vol.20 GAOYong-chao, etal:ChemicalConstituentsinChineseLiverwortPorelachinensis(Steph.)Hat
accordancewiththosereported[ 13, 14] .
Drimenin(3)　 Colorlessneedles(methanol),
mp.127-129 ℃.GC-MSm/z:234(5), 124(70), 109
(100), 105(18), 91(28), 77(12), 69(33), 41(27);
1HNMR(600 MHz, CDCl3)δ:0.87 (3H, s), 0.89
(3H, s), 0.91 (3H, s), 1.19 (2H, m), 1.36 (1H,
dd, J=11.5, 5 Hz), 1.51(3H, m), 1.98 (1H, m),
2.17(1H, m), 2.50 (1H, ddd, J=13.5, 5, 3.5 Hz),
2.78(1H, brs), 4.65(2H, m), 5.73 (1H, brs);13C
NMR(150 MHz, CDCl3)δ:38.4(C-1), 18.2(C-2),
42.4(C-3), 34.3(C-4), 49.6(C-5), 23.3(C-6),
121.2 (C-7), 129.8(C-8), 53.6(C-9), 33.1 (C-
10), 175.3(C-11), 69.8(C-12), 21.4(C-13), 33.0
(C-14), 13.9(C-15).TheGC-MSandNMRdatawere
inconsistentwiththosereported[ 15] .
α-Copaene(4)　Oil, GC-MSm/z:204(20), 161
(100), 119(97), 105(88), 93(59), 81(29), 79
(16), 68(14), 55(24), 41(38);1HNMR(600
MHz, CDCl3)δ:2.39(1H, d, J=2.5 Hz, H-2), 5.40
(1H, s, H-4), 1.68 (4H, m, H-6, H-7, H-8, H-13),
1.55(3H, s, H-12), 1.26(6H, m, H-3, H-9, H-10),
0.87-0.82(9H, m, H-11, H-14 , H-15);13 CNMR
(150 MHz, CDCl3 )δ:54.5 (C-1), 144.2 (C-2),
116.3 (C-3), 23.2 (C-4), 30.3(C-5), 36.9(C-6),
39.5(C-7), 44.5 (C-8), 19.5(C-9), 36.2(C-10),
21.9(C-11), 44.8(C-12), 33.3(C-13), 20.1 (C-
14), 19.7(C-15).TheGC-MSandNMRdatawerere-
semblecloselytothosereported[ 16] .
Acknowledgements　 TheauthorsthankProf.You-
FangWangfrom EastChinaNormalUniversityfor
plantidentification.
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