全 文 ：天然产物研究与开发 NatProdResDev2008, 20:52-55
文章编号:1001-6880(2008)01-0052-04
　
　
　ReceivedNovember29, 2006;AcceptedMarch6, 2007
＊CorrespondingauthorTel:86-28-85225401;E-mail:zhanggl@cib.ac.
cn
水麻的化学成分研究
肖艳华 1, 2 ,曹　辉 3 ,张国林 1＊
1中国科学院成都生物研究所 , 成都 610041;
2武汉工程大学化工与制药学院 ,武汉 430073;3贵州凯里学院 ,凯里 556000
摘　要:从水麻(DebregeasiaorientalisCJChen)地上部分的 95%乙醇提取物中首次分离到 18个化合物 , 应用波
谱方法或与已知品对照的手段鉴定它们为棕榈酸 (1)、正二十烷酸 (2)、正二十烷酸甲酯 (3)、β-谷甾醇 (4)、
MonogynolA(5)、白桦酸 (6)、Hederagenin(7)、β-胡萝卜甙 (8)、18αH-20(29)-烯-3-酮-乌苏烷 (9)、3, 4-开环-
20(29)-烯-乌苏烷-3-酸 (10)、Pomolicacid(11)、表儿茶素 (12)、儿茶素 (13)、槲皮素 (14)、槲皮素-3-O-β-D-
吡喃葡萄糖苷 (15)、紫丁香苷 (16)、紫丁香酚苷 (17)和山萘酚-3-O-β-D-芦丁糖苷 (18)。
关键词:水麻;儿茶素;槲皮素;乌苏烷;紫丁香苷;
中图分类号:Q949.776.606;R284.1 文献标识码:A
ChemicalConstituentsofDebregeasiaorientalis
XIAOYan-hua1, 2 , CAOHui3 , ZHANGGuo-lin1＊
1ChengduInstituteofBiology, ChineseAcademyofSciences, Chengdu610041 , China;
2SchoolofChemicalEngineeringandPharmacy, WuhanInstituteofTechnology,
Wuhan430073 , China;3KailiInstituteofGuizhou, Kaili556000 , China
Abstract:Eighteencompoundswereisolatedfromthe95% ethanolextractoftheaerialpartsofDebregeasiaorientalisC
JChenforthefirsttime.Onthebasisofspectraldataorcomparisonwithauthenticsamples, theywereidentifiedaspal-
miticacid(1), henicosanoicacid(2), henicosanoicacidmethylester(3), β-sitosterol(4), monogynolA(5), betulin-
icacid(6), hederagenin(7), β-daucosterol(8), 18αH-urs-20(29)-en-3-one(9), 3, 4-seco-urs-20(30)-en-3-oicacid
(10), pomolicacid(11), (-)-epicatechin(12), (+)-catechin(13), quercetin(14), quercetin3-O-β-D-glucopyr-
anoside(15), syringin(16), syringiaresinoldigloside(17)andkaempferol3-O-β-D-rutinose(18).
Keywords:Debregeasiaorientalis;catechin;quercetin;ursane;syringin;
Introduction
ThegenusDebregeasiacomprisesabout6speciesinthe
world.AlofthemwerefoundinChina[ 1] .Flavonoids
andvolatilecomponentsinD.longifoliahavebeen
studied[ 2, 3] .Nortriterpenesandantimicrobialtriterpe-
nesinD.salicifoliahavebeenstudied[ 4, 5] .D.orientalis
ismainlydistributedintropicalandsubtropicalareas
inAsia.Nophytochemicalstudyonthisplanthasbeen
reported.InthisstudyontheaerialpartsofD.oriental-
is, eighteencompoundswereisolatedfromthe95%
ethanolextract.Theywereidentifiedaspalmiticacid
(1), henicosanoicacid(2), henicosanoicacidmethyl
ester(3), β-sitosterol(4), monogynolA(5), betulin-
icacid(6), hederagenin(7), β-daucosterol(8),
18αH-urs-20(29)-en-3-one(9), 3, 4-seco-urs-20
(30)-en-3-oicacid(10), pomolicacid(11), (-)-
epicatechin(12), (+)-catechin (13), quercetin
(14), quercetin3-O-β-D-glucopyranoside(15), syrin-
gin(16), syringiaresinoldigloside(17)andkaempfer-
ol3-O-β-D-rutinose(18)onthebasisofspectralevi-
denceorbycomparisonwithauthenticsamples.
ExperimentalSection
Generalexperimentalprocedures
IRspectrawereobtainedonaPerkinElmerspectrum
oneFT-IRspectrometer.Massspectrawerecariedout
onFinngen-LCQDECA massspectrometer(ESIMS).
DOI :10.16333/j.1001-6880.2008.01.040
NMRspectra(1H:600 MHz;13C:150 MHz)werere-
cordedonBrukerAvance600 spectrometerwithTMS
asinternalstandard.Silicagel(QingdaoHaiyang
ChemicalCo.Ltd., whennotmentioned, silicagelwith
160-200meshwasused.), MCIgel(CHP20P, 75-150
μ, MitsubishiChemicalCorporation, Japan)andRP-18
silicagel(Prepex40-63 μm, Phenomenex)wereused
forcolumnchromatography.SilicagelGF254(0-40μm,
QingdaoHaiyangChemicalCo.Ltd.)wasusedfor
TLCplates, whichwereactivatedat110 ℃ for2 h.
TLCwasvisualizedbysprayingLiebermann-Burchard
orKeddereagents.AKromasil100-10C18 column(10
mm×250 mm, 5 μm)wasusedforsemi-preparative
HPLCelutedwithMeOH-H2Oataflowrateof1 mL/
min.Alsolventsincludingpetroleumether(60-90℃)
weredistiledpriortouse.
Plantmaterial
TheaerialpartsofD.orientaliswerecolectedinMay
2004 fromPanzhihua, SichuanProvinceofChina.The
plantmaterialwasidentifiedbyProf.FUFa-Dingat
ChengduInstituteofBiology, ChineseAcademyofSci-
ences(CAS).Avoucherspecimen(4252)wasdepos-
itedatChengduInstituteofBiology, CAS.
Extractionandisolation
Theair-driedandpowderedaerialpartsofD.orientalis
(4.5 kg)weresoakedwith95% ethanol(25L×3,
each7 d)atroomtemperature.Thesolventsweree-
vaporatedunderreducedpresuretogive260 gresi-
due.Theresiduewasdissolvedinwater(2.0 L)and
extractedsuccessivelywithpetroleumether(2.0 L×
4), ethylacetate(2.0 L×4)andn-butanol(2.0 L
×4)togivecorespondingfractionsA(34g), B(50
g)andC(140g).Theaqueousphasewasconcentrat-
edunderreducedpressuretogivefractionD(35g).
ThechlorophylinfractionA(34 g)wasremovedwith
MCIgelcolumn(ф 4.5 ×L40 cm)elutedwith
methanol-water(90:10, 100:0)andfractionA1 (18
g)wasobtained.FractionA1 wasseparatedoversilica
gelcolumn(ф5 ×L35cm)elutedwithpetroleume-
ther-acetone(10:1)toyieldsubfractionsAA(12.5
g), AB(1.5 g), AC(2.0 g)andAD(1.2g).Com-
pounds1 (25mg), 2(18 mg)and3 (10mg)werei-
solatedfromAB(1.5g)bysilicagelcolumn(ф3 ×
L30 cm)elutedwithpetroleumether-acetone(10:
1).Compounds4 (600 mg), 5 (30 mg)and6 (50
mg)wereseparatedfromAC(2.0g)bysilicagelcol-
umn(ф3.2 ×L30cm)elutedwithpetroleumether-
acetone(10:1).TheseparationofAD(1.2g)onsil-
icagelcolumn(ф3 ×L30cm)elutedwithpetrole-
umether-acetone(10:1)afordedcompound7 (80
mg).SubfractionsBA(5.8g), BB(8.0g), BC(3.5
g), BD(3.0g), BE(4.8g), BF(20.7g)andcom-
pound8(2.5g)wereobtainedfromB(50g)separa-
tedoversilicagelcolumn(ф6.0 ×L40cm)eluted
withchloroform-methanol(10:1).SubfractionBB
(8.0 g)wasseparatedoversilicagelcolumn(ф 3.5
×L30 cm)usingchloroform-methanol(10:1)as
solventstogivesubfractionsBBA(1.7 g), BBB(2.2
g)andBBC(1.0g).TherecrystalizationofBBAand
BBBfromacetoneyieldedrespectivelycompounds9
(650 mg)and10 (800 mg).Compound11 (20 mg)
wasisolatedfromBBC(1.0 g)bysilicagelcolumn
(ф2.5×L20 cm)elutedwithpetroleumether-ace-
tone(3:1).BC(3.5g)wasseparatedoversilicagel
column(ф 3.5 ×L30 cm)usingchloroform-metha-
nol(10:1)assolventstogivesubfractionsBCA(1.0
g)andBCB(1.2 g).BCA(1.0g)wasseparatedby
HPLCforseveraltimestogive12(30mg)and13(30
mg).Compounds14 (20 mg)and15 (420mg)were
isolatedfromBCBbysilicagelcolumn(ф 2.0 ×L
20 cm)elutedwithchloroform-methanol(4:1).Com-
pounds16(320mg)and17 (270 mg)wereobtained
fromBD(3.0g)bysilicagelcolumn(ф3.5 ×L40
cm)elutedwithchloroform-methanol(4:1).Com-
pound18(1200mg)wasisolatedfromBE(4.8g)by
silicagelcolumn(ф 5.0 ×L20 cm)elutedwith
chloroform-methanol(3:1).
Identification
Icosanoicacid(2)　Whitepowder;IRυKBrmax cm-1:
3426, 2929, 2850 , 1665, 1472 , 1059, 719;1H NMR
(CDCl3)δ:2.36 (2H, t, J=7.44 Hz, H-2), 1.65
(2H, m, H-3), 1.26-1.33 (32H, brs, H-(4-19)),
0.89 (3H, t, J=6.9Hz, H-20);13CNMR(CDCl3)δ:
178.2 (C-1), 33.7 (C-2), 31.9 (C-3), 29.1-29.7
(C14 -C17)), 24.7 (C-18), 22.7 (C-19), 14.1 (C-
53Vol.20 XIAOYan-hua, etal:ChemicalConstituentsofDebregeasiaorientalis
20);ESI-MSm/z:311 [ M-H] -(negativemode).The
IRandNMRdatawereinaccordancewiththoserepor-
ted[ 6] .
Icosanoicacidmethylester(3)　Whitepowder;
IRυkBrmax cm-1:3427, 2931, 2850, 1628, 1472, 1059,
719;1HNMR(CDCl3)δ:3.50 (3H, s, CH3O-1),
2.36(2H, t, J=7.44Hz, H-2), 1.65 (2H, m, H-3),
1.26-1.33(32H, brs, H-(4-19)), 0.88 (3H, t, J=
6.9Hz, H-20);ESI-MSm/z:327 [ M+H] +(positive
mode).TheIRandNMRdatawerethesameasthose
reported[ 6] .
MonogynolA(5)　Whitepower;[ α] 20D +34.0°(c
0.10, C5H5N);IRυKBrmaxcm-1:3434, 2943, 2870, 1688,
1453, 1043, 750;1HNMR(C5D5N)δ:3.50 (1H, dd,
J=10.7, 5.4 Hz, H-3), 2.44 (1H, m, H-19), 1.44
(3H, s, H-30), 1.40 (3H, s, H-23), 1.27 (3H, s, H-
29), 1.08 (3H, s, H-28), 1.01 (3H, s, H-26), 1.00
(3H, s, H-25), 0.97 (3H, s, H-24), 0.89 (3H, s, H-
27);13CNMR(C5D5N)δ:79.0 (C-3), 73.4 (C-
20), 56.6 (C-5), 55.6 (C-9), 52.5 (C-19), 51.6
(C-18), 51.2 (C-14), 45.3 (C-17), 43.1 (C-8),
42.9(C-22), 42.7 (C-1), 40.4 (C-4), 40.1 (C-
13), 38.3(C-10), 35.7 (C-10), 34.6 (C-16), 32.4
(C-7), 30.8 (C-30), 29.6 (C-21), 29.2 (C-15),
27.9(C-23), 25.4 (C-2), 23.3 (C-12), 22.3 (C-
29), 19.8 (C-11), 18.2 (C-6), 17.8 (C-26), 17.4
(C-25), 17.3 (C-24), 17.1 (C-27);ESI-MSm/z:
471 [ M-H] - , 495 [ M+Na] +(positivemode).TheIR
andNMRdatawereinagreementwiththoserepor-
ted[ 7] .
Hederagenin(7)　Whitepower;[ α] 20D +18.2°(c
0.25, C5H5N);IRυKBrmaxcm-1:3434, 2926, 2856, 1694,
1634, 1453 , 1033;1HNMR(C5D5N)δ:5.51 (1H, br
s, 12-H), 4.24(1H, dd, J=11.7, 5.0Hz, H-3), 4.21
(1H, d, J=10.5 Hz, H-23), 3.75 (1H, d, J=10.5
Hz, H-23), 1.25 (3H, s, H-29), 1.07(3H, s, H-27),
1.06(3H, s, H-30), 1.01 (3H, s, H-26), 0.98(3H,
s, H-25), 0.94 (3H, s, H-24);13CNMR(C5D5N)δ:
181.0 (C-28), 145.7 (C-13), 123.5 (C-12), 74.3
(C-3), 68.8(C-23), 49.5(C-5), 49.1 (C-9), 47.6
(C-19), 47.4 (C-17), 43.8 (C-4), 43.1 (C-18),
42.9(C-14), 40.7 (C-8), 39.7 (C-1), 38.1 (C-
10), 35.1 (C-21), 34.1 (C-7), 34.1 (C-29), 33.9
(C-22), 31.8 (C-20), 29.2 (C-15), 28.6 (C-2),
27.0 (C-26), 24.8 (C-16), 24.6 (C-11), 24.6 (C-
30), 19.5 (C-6), 18.4 (C-26), 16.8 (C-25)51.6
(C-24);ESI-MSm/z:471 [ M-H] -(negativemode).
TheIRandNMRdatawerethesameasthoserepor-
ted[ 8] .
18αH-Urs-19(29)-en-3-one(9)　 Whitepower;
[ α] 20D +48.2°(c0.25, C5H5N);IRυKBrmaxcm-1:3432,
2940, 2870, 1711, 1641, 1459, 1384, 1110;1HNMR
(CDCl3)δ:4.62 (1H, brs, H-29α), 4.61 (1H, brs,
H-29β), 2.51(1H, m, H-2α), 2.43 (1H, m, H-2β),
1.07 (3H, s, H-27), 1.06 (3H, s, H-26), 1.03 (3H,
d, J=6.8 Hz, H-23), 1.03 (3H, s, H-30), 0.95
(3H, s, H-28), 0.94 (3H, s, H-24), 0.86 (3H, s, H-
25);13CNMR(C5D5N)δ:218.3 (C-3), 154.5 (C-
19), 107.2 (C-29), 54.9 (C-5), 49.8 (C-18), 48.6
(C-9), 47.3 (C-17), 42.1 (C-8), 40.8 (C-20),
39.6 (C-13), 39.3 (C-22), 39.3 (C-1), 38.9 (C-
21), 38.2 (C-4), 36.8 (C-10), 34.5 (C-14), 34.1
(C-7), 33.3 (C-15), 26.7 (C-23), 26.6 (C-16),
26.2 (C-12), 25.6 (C-27), 25.5 (C-11), 22.0 (C-
30), 21.0 (C-6), 19.7 (C-2), 19.5 (C-26), 16.1
(C-28), 15.8 (C-24), 14.7 (C-25);ESI-MSm/z:
425 [ M+H] +, 447 [ M+Na] + , 871 [ 2M+Na] +
(positivemode).TheIRandNMRdatawereconsist-
entwiththosereported[ 9] .
3, 4-Seco-urs-20(30)-en-3-oicacid(10)　White
powder;[ α] 20D +11.2°(c0.40, MeOH);IRυKBrmaxcm-1:
3406, 2918, 2850, 1732, 1463, 1059;1H NMR
(CDCl3)δ:4.62 (2H, brs, H-30), 1.03 (3H, s, H-
26), 1.06 (3H, d, J=6.7 Hz, H-29), 0.92 (3H, s,
H-27), 0.91 (3H, d, J=6.8 Hz, H-24), 0.86 (3H,
s, H-26), 0.83 (3H, s, H-25), 0.80 (3H, d, J=6.7
Hz, H-23);13CNMR(CDCl3)δ:179.2(C-3), 154.6
(C-20), 107.2 (C-30), 48.6 (C-18), 47.3 (C-5),
42.4 (C-13), 40.8 (C-14), 40.7 (C-8), 40.0 (C-
10), 39.3 (C-9), 39.3 (C-19), 38.9 (C-22), 38.3
(C-16), 34.6 (C-17), 32.8 (C-1), 32.8 (C-7),
28.3 (C-2), 26.7 (C-12), 26.2 (C-11), 25.6 (C-
21), 25.4 (C-4), 25.4 (C-29), 24.8 (C-27), 22.1
(C-15), 19.7 (C-25), 19.6 (C-28), 18.4 (C-23),
18.2 (C-6), 15.9 (C-26), 14.6 (C-24);EI-MSm/
z:443 [ M+H] +.TheIRandNMRdatawereinac-
54 NatProdResDev　　　　　　　　　　　　　　　　　　　　　 　Vol.20
cordancewiththosereported[ 10].
Syringin(16)　whitepower;IRυKBrmax cm-1:3431,
2870, 1712, 1647 , 1588, 1130, 1093, 1066, 1028;1H
NMR(DMSO-d6)δ:6.74 (2H, s, H-5, 9), 6.48
(1H, d, J=15.8 Hz, H-3), 6.37 (1H, dt, J=15.8,
4.9Hz, H-2), 5.00 (1H, dd, J=8.5, 3.8 Hz, H-1),
4.92(1H, d, J=7.44Hz, H-1′), 4.92-4.10 (5H, m,
OH), 3.78 (6H, s, OCH3-6, 8), 3.61-3.04 (6H, m,
H-(2′-6′));13CNMR(DMSO-d6)δ:153.8 (C-2,
6), 134.4(C-1), 133.1 (C-4), 130.6 (C-7), 128.9
(C-8), 105.0(C-3, 5), 103.1 (C-1′), 77.7 (C-9),
77.0 (C-3′), 74.7 (C-5′), 70.4 (C-2′), 61.9 (C-
4′), 61.4 (C-6′), 56.8 (OCH3-C-2 , 6);ESI-MSm/
z:395 [ M+Na] +, 411 [ M+K] +(positivemode).
TheIRandNMRdataresembledcloselythosereported
[ 11].
Syringiaresinoldigloside(17)　Whitepower;IRυKBrmax
cm-1:3390, 2936, 1594, 1506, 1131, 1073;1HNMR
(DMSO-d6)δ:6.67 (4H, s, H-2′, H-2″, H-6′, H-6″),
5.00-4.92 (6H, s, OH×6), 4.89 (2H, d, J=7.08
Hz, H-1 , 1 ), 4.32 (2H, m, H-2, 6), 4.21 (2H, m,
H-4 , 8), 3.84(2H, m, H-2, 6), 3.76 (12H, s, CH3O-
3′, 5′, 3″, 5″), 3.60-3.14 (12H, m, H-(2 -6 ), (2 -
6 )), 3.03 (2H, m, H-1 , H-5);13CNMR(DMSO-
d6)δ:153.8 (C-3′, 5′, 3″, 5″), 137.6 (C-1′, 1″),
134.2(C-4′, 4″), 104.7(C-2′, 6′, 2″, 6″), 103.2(C-
1 , 1 ), 85.6 (C-4), 85.5 (C-8), 77.7 (C-5 , 5 ),
77.0(C-3 , 3 ), 74.6 (C-2 , 2 ), 71.8 (C-2, 6),
70.4(C-4 , 4 ), 61.4(C-6 , 6 ), 56.9 (OCH3-3′,
5′, 3″, 5″), 54.1 (C-1, 5);ESI-MS m/z:743
[ M+H] +, 765 [ M+Na] +, 781 [ M+K] +(positive
mode).TheIRandNMRdatawerethesameasthose
reported[ 11] .
Palmiticacid(1), β-sitosterol(4), betulinicacid
(6), β-daucosterol(8), pomolicacid(11), (-)-epi-
catechin(12), (+)-catechin(13), quercetin(14),
quercetin3-O-β-D-glucopyranoside(15)andkaempfer-
ol3-O-β-D-rutinose(18):TheirTLCbehaviorwasthe
sameasthatofauthenticsamples.
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55Vol.20 XIAOYan-hua, etal:ChemicalConstituentsofDebregeasiaorientalis