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Phenolic components from Dendrobium nobile

金钗石斛中的酚性成分(英文)



全 文 :·652· 中草药ChineseTraditionalandHerbalDrugs第37卷第5期2006年5月
化学成分
PhenoliccomponentsfromDendrobiumnobile
ZHANGXuel’2,GAOHa01“,WANGNai—li3,YAOXin—shen91·2’
(1.SchoolofTraditionalChineseMateriaMedica,ShenyangPharmaceuticalUniversity,Shenyang110016,China;
2.KeylaboratoryforResearchandDevelopmentofNewDrugsinShenzhen,Shenzhen518055,China;3.Life
ScienceDivision。GraduateSchoolatShenzhen,TsinghuaUniversity,Shenzhen518055,China)
Abstract:ObjectiveTostudythechemicalconstituentsfromthetemsofDendrobiumnobile.Meth—
odsCompoundswerei olatedthroughvariouschromatographictechniquesandidentifiedbyspectralda—
ta.ResultsTwelveph noliccompoundswereobtained.Theirstructureswerecharacterizedasdihydro—
coniferyldihydro—P—coumarate(I),vanillin(Ⅱ),apocynin(11I),P—hydroxybenzaldehyde(1V),sy—
ringaldehyde(V),syringicacid(VI),syringylethanone(Ⅶ),a—hydroxypropiosyringone(Ⅶ),eoniferyl
aldehyde(IX),dihydroconiferylalcoh l(X),2一hydroxyphenylpropanol(XI),and3-hyd xy一4一methoxy—
phenylethanol(Ⅻ),respectively.ConclusionAllabovecompoundsarereportedfromthisplantforthe
firsttime.CompoundsI andⅢ一ⅫarereportedforthefirsttimefromtheplantsofDendrobiumSw.
Keywords:DendrobiumnobileLindl.;0rchidaceae;phenolicconstituents
金钗石斛中的酚性成分
张 雪1‘2,高 昊1’2,王乃利3,姚新生1’p
(1.沈阳药科大学中药学院,辽宁沈阳 110016;2.深圳市创新药物研究重点实验室,广东深期l518055;
3.清华大学深圳研究生院生命学部,广东深圳 518055)
摘要:目的对金钗石斛茎的化学成分进行研究。方法运用多种色谱学技术对金钗石斛的化学成分进行分离,
并根据光谱数据鉴定化合物的结构。结果从该植物中分离得到12个酚性化合物,其结构分别为二氢松柏醇二氢
对羟基桂皮酸酯(I),香草醛(Ⅱ),罗布麻宁(Ⅲ),对羟基苯甲醛(IV),丁香醛(V),丁香酸(Ⅵ),丁香乙酮(Ⅶ),a一
羟基丁香丙酮(Ⅷ),松柏醛(IX),二氢松柏醇(x),2-羟基苯丙醇(Ⅺ)和3一羟基一4一甲氧基苯乙醇(Ⅻ)。结论上述
化合物均为首次报道从金钗石斛中分离得到,化合物I,Ⅲ~Ⅻ为首次报道从石斛属植物中分离得到。
关键词:金钗石斛;兰科;酚性成分
中图分类号:R284.1 文献标识码:A 文章编号:0253—2670(2006)05—0652—04
SeveralspeciesofDendrobiumSw.(Orchi—
daceae)arewidelyusedintraditionalChinese
medicineasaYintonicc⋯.Dendrobiumnobile
Lindl.iSoneofthemostfamousmedicalplants
andhasbeenrecordedintheChinesePharma—
copoeia(2005ed.)asoneoftheoriginalm terials
of“ShiHu”.Severalcomponentsincludingalka—
loids,bibenzyls,phenanthrenes,sesquiterpenes
andsesquiterpeneglycosideshavebeenidentified
fromthisplantinthearlierwork[2~引,andsome
ofwhichwerefoundtOpossessantitumor,antimU-
tagenicandimmunomodulatoryactivities[3~5|.In
oursystematicalstudyonthechemicalconstituents
ofD.nobile,twelveph noliccompoundswereob—
rained.Theirstructureswerecharacterizedasd —
hydroconiferyldihydro—P—coumarate(I),vanillin
( Ⅱ ), apocynin(Ⅲ),P—hydroxybenzaldehyde
(Ⅳ),syringaldehyde(V),syringicacid(V1),sy—
ringylethanone(Ⅶ),o【一hydroxypropiosyringone
(Ⅷ),coniferylaldehyde(IX),dihydroconiferylal一
收稿日期:2005—07—01
作者简介:张雪(1979一),女,辽宁省沈阳市人,在读博士研究生,主要从事天然产物活性成分研究。
Tel:(0755)26036133Fax:(0755)26036131E—mail:zxalice@sohu.tom
*通汛作者姚新生Tel:86—755—26036137Fax:86-755—26036131E—mail:yaoxs@SZ.tsinghua.edu.cn
万方数据
中草芮ChineseTraditionalandHerbalDrugs第37卷第5期2006年5月·653·
cohol(X),2一hydroxyphenylpropanol(Ⅺ),and
3-hydroxy一4一methoxyphenylethanol(Ⅻ). A l
abovecompoundsarereportedfromthisplantfor
thefirsttime.andcompoundsI andⅢ~Ⅻare
reportedforthefirsttimefromtheplantsofDen—
drobiumSw.
1 Experiment
1.1 General:Meltingpointsweredeterminedon
aYANACOapparatusndwereuncorrected.ESI—
MSspectrawereperformedona BrukerEsquire
2000MassSpectrometerandHR—ESI—MSspectra
wereobtainedonaMicromassQ——TOFMassSpec—-
trometer.NMRspectrawererunona BrukerA—
VANCE400NMRSpectrometer(400MHzfor
1H—NMR,100MHzfor13C—NMR)withTMSas
internalstandard.Theanalyticalandpreparative
HPLCwereperformedonaShimadzuPakwithRI
detectorusinga Shim—packVP—ODScolumn(250
mm×4.6mm)andaShim—packPREP—ODScol—
umn(250mm×10mm),respectively.Column
chromatographywascarriedoutonsilicagelH60
(QingdaoHaiyangChemicalGroupCorporation,
Qingdao,China),SephadexLH一20(Amersham
BiosciencesAB)andODS(60—80pm,Merck)as
packingmaterials.SilicagelGwasusedforanaly—
ticalTLC.
1.2 Plantmaterial:ThefreshtemsofD.nobile
werecollectedinYunnanProvinceandidentified
byMs.XiaoLi—pingofHongkongKadoorieFarm
&BotanicGarden.Avoucherspecimenisdeposit—
edatResearchCenterofTraditionalChinese
M:edicinea dNaturalProducts,Shenzhen,China.
1.3 Extractionandisolation:Thepowd redair—
driedstemsofD.nobile(5kg)wererefluxedwith
60%Et0Hforthreetimes.Afterevaporationof
EtOHinvacuo,theaqueousresiduewasextracted
withEtOAcandn-BuOHsuccessively.TheEtOAc
extractwasfirstubjectedtocolumnchromatogra—
phyonsilicagelelutedwithCHCl3一MeOH(100:
O·0:100)toaff rd12fractions.Fraction5w s
furtherchromatographedonsilicagelMPLCby
gradientelutionwithcyclohexane—EtOAc(95:5÷
0:1)togive13fractions.Subfractions7,9,10
werepassedoverSephadexLH一20 columnwith
CHCl3一MeOH(1:1)aseluentandthenappliedto
ODScolumnelutedwithMeOH—H20(4:6·8:
2)respectively.CompoundsⅡ(12.1g),Ⅲ
(8.1mg),V(30.9mg),Ⅶ(23.0mg),andlX
(12.2mg)werefinallyobtainedfromrespective
eluentof40%MeOHbypurificationwithprepara—
tiveHPLC(125%MeOH).Throughthesame
chromatographicmet ods,compoundsI (5.6
mg),Ⅳ(3.8mg),Ⅷ(1.9mg),X(2·7mg),
andⅫ(3.3mg)wereisolatedfromfraction6,and
compoundsVI(28.4mg)andⅪ(4.8mg)were
isolatedfromfraction7.
2 Structureidentification
CompoundI ( ihydroconiferyldihydro—P—
coumarate)‘6|:C19H2205,lightyellowoil.+HR—
ESI—Q—TOF—MSm/z331.1528,EM—卜H3—卜.ESI—
MSm/z353.0,[M+Na]十;m/z:329.0,[M—
H3一.1H—NMR(400MHz,CDCl。)d:7.06(2H,
d,J一8.4Hz,H一27,6’),6.82(1H,d。J一
8.6Hz,H一5),6.74(2H,d,J=8.4Hz,H一37,
57),6.65(1H,brs,H一2),6.64(1H,dd,J一
8.8,1.8Hz,H一6),5.46(1H,H一4一OH),4.08
(2H,t,J一6.5Hz,H一9),3.87(3H,s,H一3一
OCH。),2.88(2H,t,J一7.6Hz,H一7’),2.59
(2H,t,J=7.6Hz,H一87),2.56(2H,t,J=
7.4Hz,H一7),1.89(2H,m,H一8).13C—NMR
(100MHz,CDCl。)艿:173.1(C一97), 54.0(C一
4’),146.4(C一3),143.8(C一4),133.1(C一1),
132.7(C一17),129.4(C一27,67),121.0(C一6),
115.3(C一37,57),114.3(C一5),111.0(C一2),63.8
(C一9),55.9(C一3一OCH,),36.2(C一8’),31.8(C一
7),30.5(C一8),30.2(C一77).
CompoundⅡ (vanillin)[川:C8H803,white
needles(MeOH),mp170—172C.ESI—MSm/z
153.1,[M+H]+;优/z151.1,[M—H3一.1H—NMR
(400MHz,CDCl3)艿:9.83(1H,s,CHO),7.43
(1H,dd,J一8.5,1.7Hz,H一6),7.42(1H,d,
J一1.7Hz,H一2),7.04(1H,d,J一8.5Hz,H一5),
6.16(1H,s,H一4一OH),3.97(3H,s,H一3一
OCH。).13C—NMR(100MHz,CDCl3)艿:190.8
(CHO),151.7(C一4),147.2(C一3),129.9(C一1),
127.5(C一6),114.3(C一5),108.8(C一2),56.2
(C一3一oCH,).
万方数据
·654· 中草芮ChineseTraditionalandHerbalDrugs第37卷第5期2006年5月
CompoundⅢ(apocynin)[引:C9H1003,white
solid.ESI—MSm/z167.1,rM+H]+,m/z189.1,
EM+Na]+;m/z165.1,EM—H]。.1H—NMR(400
MHz,CDCl3)艿:7.54(1H,d,,=1.8Hz,H一2),
7.53(1H,dd,J=8.6,1。9Hz,H一6),6.95(1H,
d,J=8.7Hz,H一5),6.13(1H,s,H一4一OH),
3.95(3H,s,H一3一OCH3),2.56(3H,s,COCH3).
13C—NMR(100MHz,CDCl3)d:196.8(COCH3),
150.4(C一4),146.6(C一3),130.3(C一1),124.0
(C一6),113.8(C一5),109.8(C一2),56.1(C一3一
OCH3),26.2(COCH3).
CompoundIV (P—hydroxybenzaldehyde)[91:
C7H602,whitesolid.ESI—MSm/z123.1,rM+
H3+,m/z145.0,CM+Na]+;m/z121.0,EM—
H]。.1H—NMR(400MHz,CDCl3)艿:9.87(1H,
s,CHO),7.81(2H,d,J=8.4Hz,H一2,6),
6.96(2H,d,J一8.4Hz,H一3,5),5.91(1H,s,
H一4—0H).13C—NMR(100MHz,CDCl3)d:190.9
(CHO),161.3(C一4),132.4(C一2,6),130.1(C一
1),116.0(C一3,5).
CompoundV(syringaldehyde)[1叫:C9H1004,
colorlesscubits(MeOH),mp254—255℃.ESI—
Msm/z183.1,EM+H]+;m/z181.0,EM—H3’.
1H—NMR(400MHz,CDCl3)艿:9.82(1H,s,
CHO),7.15(2H,s,H一2,6),6.15(1H,s,H一4一
OH),3.97(6H,s,H一3,5-OCH3).13C—NMR
(100MHz,CDCl。)艿:190.7(CHO),147.3(C一3,
5),140.8(C一4),128.4(C一1),106.7(C一2,6),
56.4(C一3,5一OCH,).
CompoundⅥ(syringicacid)[11]:C9Hl005,
colorlessn edles(MeOH),mp213—215℃.ESI—
Msm/z199.1,EM+H3+,m/z221.1,EM+
Na3+;m/z197.0,EM—H3‘.1H—NMR(400MHz,
CD。OD)艿:7.32(2H,s,H一2,6),3.87(6H,s,
H一3,5一OCH3).13C—NMR(100MHz,CD3 D)艿:
170.0(C00H),148.8(C一3,5),141,7(C一4),
122。0(C一1),108.4(C一2,6),56.8(C一3,5一
OCH。).
CompoundⅦ(syringylethanone):CloHl204,
colorlesscubics(MeOH),mp241—242℃.ESI—
Msm/z197.0,EM+H3+,m/z219.0,EM+
NaJ+;m/z195.0,f-M—H-]’.1H—NMR(400MHz,
CDCl。)艿:7.25(2H,s,H一2,6),6.06(1H,s,
H一4一OH),3.95(6H,s,H一3,5一OCH3),2.57
(3H,s,COCH。).13C—NMR(100MHz,CDCl3)
艿:196.5(COCH。),146.7(C一3,5),139.7(C一
4),128.8(C一1),105.8(C一2,6),56.4(C一3,5一
oCH3),26.2(COCH3).
CompoundW(a—hydroxypropiosyringone):
C11H1405,lightyellowil.ESI—MS优/z227.1,
rM+Hq+,m/z249.0,EM+Na]+;m/z225.0,
[M—H]’.1H—NMR(400Hz,CDCl3)艿:7.21
(2H,s,H一2,6),6.03(1H,s,H一4一OH),5.11
(1H,m,COCH(OH)CH3),3.96(6H,s,H一3,5一
OCH。),3.77(1H,d,J一6.4Hz,COCH(oH)
CH。),1.46(3H,d,J一7.0Hz,COCH(OH)
CH3).13C—NMR(100MHz,CDCl3)艿:200.7
(COCH(OH)CH,),147.0(C一3,5),140.6(C一4),
124.7(C一1),106.2(C一2,6),68.9(COCH(OH)
CH3),56.6(C一3,5一OCH3),22.9(COCH(OH)
CH3)
CompoundIX(coniferylaldehyde):CloHl003,
yellowsolid.ESI—MSm/z179.1,EM+H]+,m/z
201.1,[M+Na]+;m/z177.1,[M—H]-.
1H—NMR(400MHz,CDCl3)艿:9.64(1H,d,J=
7.7Hz,CH—CHCHO),7.40(1H,d,J一
15.8Hz,CH—CHCHO),7.12(1H,dd,J一8.2,
1.9Hz,H一6),7.07(1H,d,J一1.8Hz,H一2),
6.96(1H,d,J=8.2Hz,H一5),6.59(1H,dd,
J=16.1,7.7Hz,CH—CHCHO),3.94(3H,s,
H一3一OCH3).13C—NMR(100MHz,CDCl3)占:
193.6(CH—CHCHO),153.1(CH=CHCHO),
148.9(C一4),146.9(C一3),126.6(C一1),126.4
(CH—CHCHO),124.O(C一6),114.9(C一5),
109.5(C一2),55.9(C一3一OCH。).
CompoundX (dihydroconiferylalcoh01):
CloHl403,lightyellowil.ESI—MSm/z205.0,
EM+Na]+;m/z181.0,EM—HI一.1H—NMR(400
MHz CD l3 艿:6.83(1H,m,H一5),6.70(1H,
m,H一2),6.68(1H,m,H一6),5.46(1H,s,H一4一
OH),3.88(3H,s,H一3一OCH3),3.68(2H,t,
,一6.4 z,CH2CH2CH20H),2.64(2H,m,
CH2CH2CH20H),1.87 (2H, m,
CH2CH2CH20H).13C—NMR(100MHz,CDCl3)艿:
146.4(C一3),143.8(C一4),133.7(C一1),121.O
(C一6),114.3(C一5),111.O(C一2),62.3
万方数据
中草药ChineseTraditionalandHerbalDrugs第37卷第5期2006年5月·655·
(CH2CH2CH20H),55.9(C一3一OCH3),34.5
(CH2CH2CH20H),31.8(CH2CH2CH20H).
CompoundⅪ (2一hydroxyphenylpropan01):
C9Hl202,lightyellowil.ESI—MSm/z175.2,
[M+Na]+;m/z151.3,[M—H]-.1H—NMR(400
MHz,CDCl3)d:7.11(2H,m,H一4,6),6.86
(2H,m,H一3,5),3,65(2H,t,J=5.8Hz,
CH2CH2CH20H),.78(2H,t,t厂一6.8Hz,
CH2CH2CH20H),1.89(2H,m, CH2CH2一
CH20H).13C—NMR(i00MHz,CDCl3)艿:154.6
(C一2),130.6(C一6),127.6(C一4),127.1(C一1),
120.8(C一5),116.2(C一3),60.8(CH2CH2一
CH20H),32.2(CH2CH2CH20H),25.2(CH2CH2一
CH,OH).
CompoundⅫ (3一hydroxy一4一methoxyphenyl—
ethan01):C9H1203,lightyellowoil.ESI—MSm/z
191.0,[M+Na]+.1H—NMR(400MHz,CDCl3)
d:6.80(1H,brs,H一2),6.79(1H,d,J=
8.2Hz,H一5),6.70(1H,dd,J一8.1,2.1Hz,H一
6),5.78(1H,s,H一3一OH),3.87(3H,s,H一4一
OCH3),3.82(2H,t,,一6.5Hz,CH2CH20H),
2.78(2H,t,J一6.5Hz,CH2CH20H).13C—NMR
(100MHz,CDCl3)艿:145.8(C一3),145.3(C一4),
131.7(C一1),120.5(C一6),115.1(C一2),110.8
(C一5),63.7(CH2CH20H),56.0(C一4一OCH3),
38.6(CH2CH20H).
Acknowledgements:TheauthorsthankMs.
XiaoLi—ping,HongkongKadoorieFarm&Botanic
Garden,foridentificationoftheplantmaterials.
WearegratefultoShanghaiInstituteofMateria
MedicaofChineseAcademyofScienceformea—
suringtheHR—ESI—Q—ToF—MS.Thanksarealso
giventoChenBinandLuoQun-huiforUV
spectraldata.
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茯苓化学成分研究
胡 斌,杨益平。,叶 阳
(中国科学院上海生命科学研究院上海药物研究所新药研究国家重点实验室,上海201203)
摘 要:目的 研究茯苓PoriaCOCOS的化学成分,从中寻找有重要生物活性及药用前景的天然产物。方法采用正
相硅胶,反相RP一18,SephadexLH一20及MCI等柱色谱分离化合物,运用波谱技术分析确定化学结构。结果从茯
苓的提取物中共分离并鉴定了13个化合物,经波谱分析确定分别为:麦角甾一7,22一二烯一3p醇(I)、胡萝b苷
(Ⅱ)、茯苓酸(Ⅲ)、36一乙酰基一16a一羟基一羊毛甾一7,9(11),24(31)一三烯一21一酸(Ⅳ)、3B,16a一二羟基一羊毛甾一7,9(11),
收稿日期;2005—08—15
作者简介:胡斌(1978一),男,安徽淮南人,中国科学院上海药物研究所有机化学专业2001级硕士生。
*通讯作者杨益平Tel:(021)50806600Fax:(021)50807088E—mail:ypyang@mail.shone.ac.ca
万方数据
金钗石斛中的酚性成分
作者: 张雪, 高昊, 王乃利, 姚新生, ZHANG Xue, GAO Hao, WANG Nai-li, YAO Xin-
sheng
作者单位: 张雪,高昊,姚新生,ZHANG Xue,GAO Hao,YAO Xin-sheng(沈阳药科大学中药学院,辽宁,沈阳
,110016;深圳市创新药物研究重点实验室,广东,深圳,518055), 王乃利,WANG Nai-li(清华
大学深圳研究生院生命学部,广东,深圳,518055)
刊名: 中草药
英文刊名: CHINESE TRADITIONAL AND HERBAL DRUGS
年,卷(期): 2006,37(5)
被引用次数: 21次

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3.Lee Y H;Park J D;Baek N I In vitro and vivo antitumoral phenanthrenes from the aerial parts of
Dendrobium nobile[外文期刊] 1995(02)
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5.Ye Q H;Qin G W;Zhao W M Immunomodulatory sesquiterpene glycosides from Dendrobium nobile[外文期刊]
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9.Wang S J;Pei Y H Studies on the chemical constituents of the leaves of Betula platyphylla Suk[期刊
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10.Guo H L;Zhou J Y Study on the chemical constituents of Periploca calophylla[期刊论文]-中国药学杂
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11.Zhang W D;Chen W S;Kong D Y Studies on the chemical constituents of Erigeron breviscapus 2000(08)

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