全 文 ：天然产物研究与开发 NatProdResDev2010, 22:419-421
文章编号:1001-6880(2010)03-0419-03
　
　
　ReceivedAugust12, 2008;AcceptedFebruary26, 2009
＊CorrespondingauthorTel:86-851-3809439;E-mail:wangye.cn@
gmail.com
秃叶黄皮树叶子的化学成分研究
王楠楠 1, 2 ,汪　冶 2＊ ,杨建琼 2
1贵州大学 ,贵阳 550022;2贵州省 、中国科学院天然产物化学重点实验室 ,贵阳 550002
摘　要:从秃叶黄皮树叶子(Phelodendronchinensevar.glabriusculumSchneid)分离到 7个化合物 , 经波谱解析鉴
定为 6 -O-乙酰基黄柏苷(1), 6 -O-乙酰基二氢黄柏苷(2), (2R)-4′, 5-二羟基-7-O-β-D-吡喃葡萄糖基-8-异戊烯
基 -二氢黄酮(3),黄柏苷(4), 2-O-β-D-吡喃葡萄糖基-6-羟基-苯甲酸苄酯(5), 柑橘素 C(6), 3-羰基齐墩果烷
(7), 其中化合物 1 ～ 3, 5 ～ 7为首次从秃叶黄皮树叶子中分离得到。
关键词:秃叶黄皮树;叶子;化学成分
中图分类号:Q946.91;R284.2 文献标识码:A
ChemicalConstituentsfromtheLeavesofPhelodendron
chinenseSchneidvar.glabriusculumSchneid
WANGNan-nan1, 2 , WANGYe2＊ , YANGJian-qiong2
1GuizhouUniversity, Guiyang5500222;2TheKeyLab.ofChemistryforNaturalProductsof
GuizhouProvinceandChineseAcademyofSciences, Guiyang550002
Abstract:SevencompoundswereisolatedfromtheleavesofPhellodendronchinenseSchneidvar.glabriusculum.Based
onspectroscopicanalysis, theirstructurewereelucidatedas6 -O-acetylamurensin(1), 6 -O-acetylphelamurin(2),
(2R)-phelodensin-F(3), amurensin(4), benzyl-2-O-β-D-glucopyranosyl-2, 6-dihydroxy-benzoate(5), citrusinC
(6), 3-ketooleanane(7)respectively, compounds1-3, 5-7wereisolatedfromtheplantforthefirsttime.
Keywords:PhellodendronchinenseSchneidvar.glabriusculum;leaves;chemicalconstituents
Introduction
PhelodendronchinenseSchneidvar.glabriusculumbe-
longingtothefamilyofRutaceaeandthegenusof
Phelodendron, itsstembarkhasbeenusedforanti-
bacterialandanti-inflammationbythefolksofMiao
Nationality.ourpreviousresearchhadledtotheisola-
tionofTirucalane-typetriterpenoidsfromthefruitsof
thisplant[ 1, 2] , asacontinuationofourinvestigationon
chemicalconstituentsofnon-alkaloidsfromtheleaves
ofthisplant, sevencompounds6 -O-acetylamurensin
(1), 6 -O-acetylphelamurin(2), (2R)-pheloden-
sin-F(3), amurensin(4), benzyl2-O-β-D-glucopyr-
anosyl-2, 6-dihydroxy-benzoate(5), citrusinC(6), 3-
ketooleanane(7)wereobtained, Compounds1-3, 5-7
areisolatedfromthisplantforthefirsttime.
Experimental
General
MeltingpointswereobtainedonanX-4 micromeling
pointapparatusandareuncorrected.IRspectrawere
recordedusingaVector22 spectrophotometer.NMR
spectrawererunonaINOVA-400 MHzspectrometer
withTMSasinternalstandard.EI-MSexperimentswere
cariedoutonanHP-5973 massspectrometer.Column
chromatographywasperformedonsilicagel(200-300
mesh, H-60)andTLCwasperformedonGF254 plates
(QingdaoHaiyangChemicalCompany, Qingdao, Chi-
na), SephadexLH-20(25-100 μm, PharmaciaCompa-
ny).SpotsofTLCweredetectedbysprayingwith5%
H2SO4 folowedbyheating.
Plantmaterial
TheleavesofP.chinensevar.glabriusculumSchneid.
werecolectedinGuiyangCity, GuizhouProvince, Peo-
ple sRepublicofChina, inSeptember, 2005andiden-
DOI :10.16333/j.1001-6880.2010.03.004
tifiedbyProf.De-YuanChenatGuiyangColegeof
TraditionalChineseMedicine.A voucherspecimen
(No.070822)isdepositedinTheKeyLaboratoryof
ChemistryforNaturalProductsofGuizhouProvinceand
ChineseAcademyofSciences.
ExtractionandIsolation
Thedryleaves(28 kg)ofP.chinensevar.glabriuscu-
lum Schneid.wereextractedthreetimeswith95%
EtOHunderreflux.Theextractswerecondensedin
vacuotogivecruderesiduewhichwasdissolvedand
suspenedinH2O.Theaqueoussuspensionwaspartition
successivelywithpetroleumetherandethylacetate,
EtOAcfraction(3 kg)waschromatographedonasili-
cagelcolumn, elutinggradualywithCHCl3-MeOH
(60∶1-1∶1)toyield6 sub-fractionsbasedonTLCa-
nalysis.Sub-fraction1 wasfurtherseparatedonasilica
gelcolumn, elutingwithpetroleumether-EtOAc(20∶
1)toyieldcompound1 (30 mg), Sub-fraction3 was
furtherpurifiedbyrepeatedcolumnchromatographyo-
versilicagelHelutingwithpetroleumether-Me2CO
(from20∶1 to10∶1)andSephadexLH-20(CHCl3:
MeOH, 1=1)toprovidecompounds1(17mg), 2(40
mg), 3(18 mg), 4(23 mg), 5(51 mg)and6(21
mg).
Identification
6 -O-acetylamurensin(1)　Yelowpowder, C28H30
O12 , ESI-MSm/z:581[ M+H] +, 1HNMR(400 MHz,
DMSO-d6)δ:1.60(3H, s, 4″-CH3), 1.74(3H, s, 5″-
CH3), 2.03(3H, s, 8 -CH3), 5.03(1H, d, J=7.2
Hz, H-1 ), 6.57(1H, s, H-6), 6.93(2H, J=8.8 Hz,
H-3′, 5′), 8.04(2H, J=8.8 Hz, H-2′, 6′), 12.47
(1H, s, 5-OH);13CNMR(100 MHz, DMSO-d6)δ:17.
9(C-5″), 20.7(C-8′), 21.5(C-1″), 25.5(C-4″), 63.
5(C-6 ), 70.0(C-4 ), 73.3(C-2 ), 73.8(C-5 ),
76.4(C-3 ), 97.6(C-6), 100.2(C-1 ), 104.6(C-
10), 108.1(C-8), 115.6(C-3′, C-5′), 121.9(C-1′),
122.4(C-2″), 129.7(C-2′, C-6′), 131.2(C-3″),
135.9(C-3), 147.6(C-2), 152.7(C-9), 158.5(C-
5), 159.4(C-4′), 159.8(C-7), 170.3(C-7′), 176.4
(C-4).Itwasidentifiedas6 -O-acetylamurensinby
comparisonwiththedataofthereportedliterature[ 3] .
6 -O-acetylphelamurin(2)　Awhiteamorphous
powder, C28H32O12 , ESI-MSm/z:583[ M+H] +, 1H
NMR(400 MHz, DMSO-d6)δ:1.48(3H, s, 4″-CH3),
1.56(3H, s, 5″-CH3), 2.02(3H, s, 8 -CH3), 4.95
(1H, d, J=7.2 Hz, H-1 ), 6.26(1H, s, H-6), 6.78
(2H, J=8.8Hz, H-3′, 5′), 7.30(2H, J=8.8 Hz, H-
2′, 6′), 11.82(1H, s, 5-OH);13CNMR(100 MHz,
DMSO-d6)δ:17.6(C-5″), 20.6(C-8 ), 21.3(C-1″),
25.6(C-4″), 63.5(C-6 ), 71.9(C-3), 73.2(C-2 ),
73.8(C-5 ), 76.4(C-3 ), 82.9(C-2), 95.5(C-6),
99.9(C-1 ), 101.9(C-10), 108.9(C-8), 114.9(C-
3′, C-5′), 122.3(C-2″), 127.7(C-1′), 129.3(C-2′,
C-6′), 130.5(C-3″), 157.7(C-4′), 158.7(C-9),
160.9(C-5), 162.9(C-7), 170.3(C-7 ), 199.3(C-
4).Itwasidentifiedas6 -O-acetylphelamurinby
comparisonwiththedataofthereportedliterature[ 3] 。
(2R)-phelodensin-F(3)　Awhiteamorphouspow-
der, C26H30O10 , ESI-MSm/z:525[ M+H] + , 1HNMR
(400 MHz, Acetone-d6)δ:1.60(6H, s, 4″, 5″-CH3),
5.03(1H, d, J=7.2 Hz, H-1 ), 6.28(1H, s, H-6),
6.89(2H, J=8.8 Hz, H-3′, 5′), 7.39(2H, J=8.8
Hz, H-2′, 6′), 12.08(1H, s, 5-OH);13CNMR(100
MHz, Acetone-d6)δ:17.9(C-5″), 22.4(C-1″), 25.9
(C-4″), 43.5(C-3), 62.4(C-6 ), 71.1(C-4 ), 74.6
(C-2 ), 77.9(C-3 ), 77.9(C-5 ), 79.7(C-2), 96.1
(C-6), 101.3(C-1 ), 104.3(C-10), 110.2(C-8),
116.1(C-3′, C-5′), 123.7(C-2″), 128.8(C-2′, C-
6′), 130.7(C-1′), 131.2(C-3″), 158.6(C-4′),
160.2(C-9), 162.9(C-5), 164.3(C-7), 198.3(C-
4).Itwasidentifiedas(2R)-phelodensin-Fbycom-
parisonwiththedataofthereportedliterature[ 3] .
Amurensin(4)　Yelowpowder, C26H28O11 , ESI-MS:
m/z:581[ M+H] +, 1HNMR(400 MHz, DMSO-d6)δ:
1.60(3H, s, 4″-CH3), 1.75(3H, s, 5″-CH3), 4.99
(1H, d, J=7.2Hz, H-1 ), 6.58(1H, s, H-6), 6.93
(2H, J=8.8Hz, H-3′, 5′), 8.04(2H, J=8.8 Hz, H-
2′, 6′), 12.47(1H, s, 5-OH);13CNMR(100 MHz,
DMSO-d6)δ:18.0(C-5″), 21.5(C-1″), 25.5(C-4″),
60.6(C-6 ), 69.7(C-4 ), 73.4(C-2 ), 76.6(C-
3 ), 77.2(C-5 ), 97.4(C-6), 100.4(C-1 ), 104.5
(C-10), 108.0(C-8), 115.5(C-3′, C-5′), 121.9(C-
1′), 122.4(C-2″), 129.6(C-2′, C-6′), 131.1(C-3″),
135.9(C-3), 147.5(C-2), 152.7(C-4′), 158.6(C-
9), 159.4(C-5), 160.1(C-7), 176.4(C-4).Itwasi-
420 NatProdResDev　　　　　　　　　　　　　　　　　　　　 　Vol.22
dentifiedasamurensinbycomparisonwiththedataof
thereportedliterature[ 4] .
Benzyl-2-O-β-D-glucopyranosyl-2, 6-dihy-droxy-benzo-
ate(5)　Awhiteamorphouspowder, C20H22O9 , ESI-
MS:m/z:517[ M+H] + , 1HNMR(400 MHz, DMSO-
d6)δ:4.83(1H, d, J=7.2Hz, H-1 ), 5.35(2H, s, H-
1′), 6.66(1H, d, J=8.4 Hz, H-6), 6.61(1H, d, J=
8.0Hz, H-4), 7.29(1H, t, J=8.4, 8.0 Hz, H-5),
7.45-7.32(5H, m, H-3′-H-7′);13CNMR(100 MHz,
DMSO-d6)δ:61.4(C-6), 67.5(C-1′), 69.3(C-4 ),
73.3(C-2 ), 75.5(C-3 ), 76.1(C-5 ), 101.6(C-
1 ), 104.7(C-2′), 106.5(C-4), 111.9(C-6), 128.5
(C-3′, C-5′, C-7′), 128.7(C-4′, C-6′), 134.8(C-2),
135.1(C-5), 158.0(C-7), 161.8(C-3), 169.2(C-1)
.Itwasidentifiedasbenzyl-2-O-β -D-glucopyranosyl-
2, 6-dihy-droxy-benzoatebycomparisonwiththedata
ofthereportedliterature[ 5] .
CitrusinC(6)　Awhiteamorphouspowder, C16H22
O7 , ESI-MS:m/z:429[ M+H] + , 1HNMR(400 MHz,
DMSO-d6)δ:3.722(3H, s, 2-OMe), 4.83(1H, d, J=
7.2Hz, H-1′), 5.92(1H, m, H-8), 6.65(1H, d, J=
8.4Hz), 6.78(1H, d, J=0.8 Hz), 6.98(1H, d, J=
8.4Hz);13CNMR(100 MHz, DMSO-d6)δ:39.1(C-
7), 55.6(C-10), 60.7(C-6′), 69.7(C-4′), 73.3(C-
2′), 76.9(C-5′), 77.0(C-3′), 100.2(C-1′), 112.9
(C-6), 115.4(C-3), 115.6(C-9), 120.3(C-5),
133.5(C-4), 138.0(C-8), 144.9(C-1), 148.9(C-2)
.ItwasidentifiedascitrusinCbycomparisonwiththe
dataofthereportedliterature[ 6] .
3-Ketooleanane(7)　Whitesolid, C30H50O, mp.233-
235℃, 1HNMR(400 MHz, CDCl3)δ:0.72(3H, s, H-
26), 0.83(3H, s, H-25), 0.93(3H, s, H-28), 0.95
(3H, s, H-30), 1.00(3H, s, H-29), 1.05(3H, s, H-
27), 1.18(3H, s, H-24), 1.23(3H, s, H-23);13 C
NMR(100MHz, CDCl3)δ:14.6(C-26), 17.9(C-7),
18.2(C-25), 18.7(C-27), 20.2(C-28), 22.3(C-
24), 28.2(C-2), 3 0.0(C-23), 30.5(C-20), 30.9
(C-16), 31.8(C-12), 32.1(C-15), 32.4(C-21),
32.7(C-17), 35.0(C-30), 35.3(C-11), 35.6(C-
29), 36.0(C-19), 37.4(C-22), 38.3(C-1), 39.2(C-
4), 39.7(C-10), 41.3(C-13), 41.5(C-14), 42.1(C-
18), 42.8(C-8), 53.1(C-6), 58.2(C-9), 59.5(C-
5), 213.3(C-3).Itwasidentifiedas3-ketooleanane
bycomparisonwiththedataofthereportedlitera-
ture[ 7] .
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421Vol.22　　　　　　WANGNan-nan, etal:ChemicalConstituentsfromtheLeavesofPhelodendronchinenseSchneidvar.glabriusculumSchneid