全 文 ：天然产物研究与开发 NatProdResDev2007, 19:978-981
文章编号:1001-6880(2007)06-0978-04
　
　
　ReceivedApril14, 2006;AcceptedMay15, 2006
＊CorrespondingauthorTel:86-28-85225401;E-mail:zhanggl@cib.ac.
cn
尼泊尔水东哥的化学成分研究
肖艳华 1, 2 ,张爱莲 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浙江林学院食品与药学院 , 临安 311300
摘　要:从尼泊尔水东哥树皮的 95%乙醇提取物中首次分离到 12个化合物 , 应用波谱方法或与已知品对照的
手段鉴定为 auranamide(1)、aurantiamidebenzoate(2)、齐墩果酸(3)、β-谷甾醇(4)、β-胡萝卜甙(5)、乌苏酸
(6)、 2α, 3α-二羟基-12-烯-28-乌苏酸(7)、 2α, 3β, 24-三羟基-12-烯-28-乌苏酸(8)、(2S, 3S, 4R, 10E)-2-[ (2′R)-
2′-hydroxytetracosanoylamino] -10-octadecene-1, 3, 4-triol(9)、 2α, 3α, 24-三羟基-12-烯-28-齐墩果酸(10)、2α, 3β-
二羟基-12-烯-28-乌苏酸(11)和 2α, 3α, 24-三羟基-12-烯-28-乌苏酸(12)。
关键词:尼泊尔水东哥;二羟基乌苏酸;auranamide;aurantiamidebenzoate
中图分类号:R284.1 文献标识码:A
ChemicalStudyonSaurauianapaulensis
XIAOYan-hua1, 2 , ZHANGAi-lian3 , ZHANGGuo-lin1＊
1ChengduInstituteofBiology, ChineseAcademyofSciences, Chengdu610041 , China;
2SchoolofChemicalEngineeringandPharmacy, WuhanInstituteofTechnology, Wuhan430073 , China;
3SchoolofFoodandPharmaceuticalScience, ZhejiangForestryColegy, Linan311300 , China
Abstract:Twelvecompoundswereisolatedfromthe95% ethanolextractofthebarkofSaurauianapaulensisforthefirst
time.Onthebasisofspectralevidenceorbycomparisonwithauthenticsamplestheywereidentifiedasauranamide(1),
aurantiamidebenzoate(2), oleanolicacid(3), β-sitosterol(4), β-daucosterol(5), ursolicacid(6), 2α, 3α-di-
hydroxyurs-12-en-28-oicacid(7), 2α, 3β, 24-trihydroxyurs-12-en-28-oicacid(8), (2S, 3S, 4R, 10E)-2-[ (2′R)-2′-
hydroxytetracosanoylamino] -10-octadecene-1, 3, 4-triol(9), 2α, 3α, 24 -trihydroxyolean-12-en-28-oicacid(10), 2α,
3β-dihydroxyurs-12-en-28-oicacid(11), and2α, 3α, 24-trihydroxyurs-12-ene-28-oicacid(12).
Keywords:Saurauianapaulensis;dihydroxyursolicacid;auranamide;aurantiamidebenzoate
Introduction
ThegenusSaurauiacomprisesofabout300 speciesin
theworld.ThirteenofthemwerefoundinChina.[ 1] N-
tricosylalcohol, β-sitosterolandanabasinehavebeeni-
solatedfromS.excels.[ 2] S.napaulensisismainlydistrib-
utedintropicalandsubtropicalareainAsia.Thebark
wasusedinfolkmedicineforlumbago, nostalgia, hurt
andothersymptoms.[ 3] Thereisnoreportonthephyto-
chemicalstudyofthisplant.Inthisstudy, twelvecom-
poundswereisolatedfromthe95% ethanolextractof
thebarkofS.napaulensisss.Onthebasisofspectralevi-
denceorcomparisonwithauthenticsamples, theywere
identifiedasauranamide(1), aurantiamidebenzoate
(2), oleanolicacid(3), β-sitosterol(4), β-daucosterol
(5), ursolicacid(6), 2α, 3α-dihydroxyurs-12-ene-28-
oicacid(7), 2α, 3β, 24-trihydroxyurs-12-ene-28-oic
acid(8), (2S, 3S, 4R, 10E)-2-[ (2′R)-2′-hydroxytetra-
cosanoylamino] -10-octadecene-1, 3, 4-triol(9), 2α,
3α, 24-trihydroxyolean-12-ene-28-oicacid(10), 2α, 3β-
dihydroxyurs-12-ene-28-oicacid(11), and2α, 3α, 24-
trihydroxyurs-12-ene-28-oicacid(12).
Experimental
Generalexperimentalprocedures
IRspectrawereobtainedonaPerkinElmerspectrum
oneFT-IRspectrometer(KBrdisc).Massspectrawere
cariedoutonaFinngen-LCQDECAmassspectrometer
DOI :10.16333/j.1001-6880.2007.06.022
Fig.1　CompoundsisolatedfromS.napaulensis
(ESIMS).NMRspectra(1H:600 MHz, 13 C:150
MHz)wererecordedonaBrukerAvance600spectrom-
eterwithTMSasinternalstandard.SilicagelH(160-
200mesh, QingdaoHaiyangChemicalCo., Ltd.), MCI
Gel(CHP20P, 75-150 μm, MitsubishiChemicalCor-
poration, Japan)andRP-18 silicagel(Prepex40-63
μm, Phenomenex)wereusedforcolumnchromatogra-
phy.SilicagelGF254 (0-40 μm, QingdaoHaiyang
ChemicalCo., Ltd.)wasusedforTLCplates, which
wereactivatedat110°Cfor2h.TLCplateswerevisu-
alizedbysprayingLiebermann-BurchardorKedderea-
gents.Alsolventsincludingpetroleumether(60-90
℃)weredistiledpriortouse.
Plantmaterial
ThebarkofS.napaulensiswascolectedinNovember
1999fromXishuangbanna, YunnanProvinceofChina.
TheplantsamplewasidentifiedbyProf.Jing-YunCui
atXishangbannaTropicalBotanicalGarden, Chinese
AcademyofSciences(CAS).Avoucherspecimen
(GF-37)wasdepositedatChengduInstituteofBiolo-
gy, CAS.
Extractionandseparation
Theair-driedandpowderedbarkofS.napaulensis
(4.0 kg)wassoakedwith95% ethanol(25 L×3,
each7 d)atroomtemperature.Thesolventsweree-
vaporatedunderreducedpresuretogive173 gresi-
due.Theresiduewasdissolvedinwater(1.0 L)and
extractedsuccessivelywithpetroleumether(1.0 L×
4), ethylacetate(1.0 L×4)andn-butanol(1.0 L
×4)togivecorespondingfractionsA(48 g), B(15
g)andC(50g).Theaqueousphasewasconcentrated
invacuotogivefractionD(60g).
ThechlorophylinfractionA(48g)wasremovedwith
MCIGelcolumnelutedwithmethanol-water(90:10,
100:0)andfractionA1 wasobtained.FractionsA1
(18 g)wasseparatedonsilicagelcolumnelutedwith
petroleumether-acetone(10:1)toyieldsubfractions
A1A(2.6 g), A1B(7.5 g), A1C(4.0 g)andA1D
(3.0 g).Compounds1(5 mg), 2(18 mg)and3(7
mg)wereseparatedfromA1C(4.0 g)bysilicagel
columnelutedwithpetroleumether-acetone-ethylace-
tate(10:1:0.04).
FractionBwasdividedintosubfractionsB1(3.0g), B2
(3.5g), B3(4.5g), B4(1.0g)andB5(3g)bysil-
icagelcolumnelutedwithchloroform-methanol(10:
1).Compounds4(1.9g)and5(2.4 g)wereobtained
byrecrystalizingB1andB5frommethanol.B2(3.5g)
wasseparatedonsilicagelcolumnusingchloroform-
methanol(10:1)assolventstogivesubfractionsB2A
(0.5g), B2B(1.2 g), B2C(1.0 g)andB2D(0.5
g).Compounds6(5 mg)and7(8 mg)wereobtained
fromB2B(1.2 g)bysilicagelcolumnelutedwithpe-
troleumether-acetone(15:1).Compound8(12 mg)
wasisotaedfromB2C(1.0g)bysilicagelcolumnelu-
tedwithpetroleumether-acetone(10:1).Compound9
(11mg)wasisolatedfromB2D(0.5 g)bysilicagel
columnelutedwithpetroleum ether-acetone(5:1).
Compounds10(7 mg)and11(8 mg)wereobtained
fromB3(4.5g)bysilicagelcolumnelutedwithpetro-
leumether-acetone(5:1).Compound12(17mg)wasi-
solatedfromB4 (1.0 g)bysilicagelcolumneluted
withchloroform-methanol(10:1).
Identification
Auranamide(1)　Whitepowder, [ α] -24.8°(c
0.4, CHCl3);IRυmaxcm-1:3434 , 1753, 1639 , 1580,
1534, 1034, 695;1H NMR(CDCl3)δ:7.65-7.71
(4H, m, H-3″, 7″, 3 , 7 ), 7.20-7.52 (16H, m, aro-
maticprotons), 6.69 (1H, d, J=8.4 Hz, H-a), 6.60
(1H, d, J=6.6 Hz, H-b), 4.94 (1H, dd, J=12.8,
6.6 Hz, H-2), 4.64 (1H, m, H-2′), 4.56 (1H, dd, J
=14.4, 3.0 Hz, H-1′α), 4.05(1H, dd, J=14.4 , 4.2
979Vol.19 XIAOYan-huaetal:ChemicalStudyonSaurauianapaulensis
Hz, H-1′β), 3.31 (1H, dd, J=13.8, 6.4 Hz, H-3α),
3.23(1H, dd, J=13.8, 6.9 Hz, H-3β), 3.01 (1H,
dd, J=13.7, 6.4 Hz, H-3′α), 2.91(1H, dd, J=
13.7, 8.4 Hz, H-3′β);13CNMR(CDCl3)δ:172.1
(C-1), 167.6 (C-1″), 167.4 (C-1 ), 128.6-137.4
(24 aromaticcarbons), 65.6 (C-1′), 54.6 (C-3),
50.5 (C-3′), 37.8 (C-2), 37.5 (C-2′);ESI-MSm/
z:507[ M+H] +(positivemode), 505[ M-H] -(nega-
tivemode).TheIRandNMRdatawereinaccordance
withthoseofauranamide[ 4] .
Aurantiamidebenzoate(2)　Whitepowder, [ α] -
27.0°(c0.4, CHCl3);IRυmaxcm-1:3435, 2924, 1751,
1639, 1580, 1534, 1491 , 1455, 1034, 695;1H NMR
(DMSO-d6)δ:8.87 (1H, d, J=7.2 Hz, H-a), 8.34
(1H, d, J=7.2 Hz, H-b), 7.73-7.78 (4H, m, H-3′,
7′, 3″, 7″), 7.50 (2H, m, H-5′, 5″), 7.42 (4H, m, H-
4′, 6′, 4″, 6″), 7.15-7.26 (10H, m, aromaticpro-
tons), 4.66 (1H, m, H-2), 4.40 (1H, m, H-2 ),
4.18 (2H, m, H-1 ), 3.18 (1H, dd, J=14.4, 4.2
Hz, H-3α), 3.05 (1H, dd, J=13.8, 6.4 Hz, H-3β),
2.88(1H, dd, J=13.8, 6.9 Hz, H-3 α), 2.83(1H,
dd, J=13.7, 6.4 Hz, H-3 β);13CNMR(CDCl3)δ:
172.0 (C-1″), 167.1 (C-1′), 166.7 (C-1), 138.8
(C-4), 138.3(C-5), 135.0 (C-2′), 134.1 (C-5′),
131.9 (C-2″), 131.6 (C-5″), 127.6-129.5, 126.9,
126.6(18aromaticcarbons), 66.0(C-1 ), 54.9(C-
2), 50.3 (C-2 ), 36.8(C-3), 36.4(C-3 );ESI-MS
m/z:541.1[ M+Cl] -(negativemode), 529.2[ M+
Na] +(positivemode).TheIRandNMRdatawerein
agreementwiththoseofauranamidebenzoate.[ 5]
Oleanoicacid(3), β-sitosterol(4), β -daucosterol
(5)andursolicacid(6)　TheirTLCbehaviorswere
thesameasthoseofauthenticsamples.
2α, 3α-Dihydroxyurs-12-ene-28-oicacid (7)　
Whitepowder, [ α] 20D +50.2°(c0.24, C5H5N);
IRυmaxcm-1:3435, 2926, 1693, 1456, 1379, 1035;1H
NMR(C5D5N)δ:5.45(1H, brs, H-12), 4.28 (1H,
td, J=11.6, 2.6 Hz, H-2), 3.75 (1H, s, H-3), 2.60
(1H, d, J=11.4 Hz, H-18), 1.29 (3H, s, H-23),
1.15(3H, s, H-27), 1.05 (3H, s, H-24), 0.95(3H,
s, H-25), 0.94 (3H, d, J=6.0 Hz, H-29), 0.92
(3H, d, J=6.0 Hz, H-30), 0.88 (3H, s, H-26);13C
NMRseeTable1;ESI-MSm/z:473[ M+H] +(posi-
tivemode), 471[ M-H] -(negativemode).TheIRand
NMRdatawereinconsistentwiththosereported[ 6] .
2α, 3β, 24-Trihydroxyurs-12-ene-28-oicacid(8)　
Whitepowder, [ α] 20D +38.2°(c0.20, C5H5N);
IRυmax cm-1:3430 , 2927, 2871, 1693, 1455, 1378,
1241, 1050;1HNMR(C5D5N)δ:5.44 (1H, s, H-
12), 4.29 (1H, m, H-2), 3.55 and4.44 (each1H,
d, J=10.9 Hz, H-24), 3.70 (1H, d, J=11.0 Hz, H-
3), 2.60(1H, d, J=11.4Hz, H-18)1.58 (3H, s, H-
23), 1.18 (3H, s, H-26), 1.00 (3H, s, H-27), 0.96
(3H, s, H-25), 0.96(3H, d, J=4.2 Hz, H-29), 0.93
(3H, d, J=6.1 Hz, H-30);13CNMRdataseeTable
1;ESI-MSm/z:489 [ M+H] +(positivemode), 487
[ M-H] -(negativemode).TheIRandNMRdatawere
resemblecloselywiththosereported[ 7].
(2S, 3S, 4R, 10E)-2-[ (2′R)-2′-Hydroxytetraco-
sanoylamino] -10-octa-decene-1, 3, 4-triol(9)　
Whitepowder, [ α] 20D +11.3°(c0.20, CHCl3);IRυmax
cm-1:3335, 2919, 2850 , 1622, 1544, 1467;1H NMR
(C5D5N)δ:4.43 (1H, dd, J=10.4, 4.8 Hz, H-1),
4.51 (1H, dd, J=10.4, 4.8 Hz, H-1), 5.12 (1H,
dd, J=8.1, 4.0 Hz, H-2), 4.35 (1H, m, H-3), 4.29
(1H, m, H-4), 2.21 (2H, m, H-5), 1.95 (2H, m, H-
9), 2.03(2H, m, H-12), 1.2-1.5(10H, H-(13-17),
0.85 (3H, t, J=6.4 Hz, H-18), 8.59(1H, d, J=9.1
Hz, N-H), 4.62 (1H, dd, J=7.8, 4.2 Hz, H-2′),
2.22 (2H, m, H-3′), 1.78 (2H, m, H-4′), 1.2-1.5
(38H, H-(5′-23′)), 0.85 (3H, t, J=6.4 Hz, H-
24′);13CNMR(C5D5N)δ:62.1 (C-1), 53.0 (C-
2), 76.9(C-3), 72.9(C-4), 34.2 (C-5), 26.6 (C-
6), 32.9(C-9), 130.7 (C-10), 130.8 (C-11), 33.2
(C-12), 29.5-30.1 (C-(13-16)), 22.9 (C-17),
14.2 (C-18), 175.3 (C-1′), 72.6 (C-2′), 35.7 (C-
3′), 25.8 (C-4′), 29.5-30.1 (C-5′-22′), 22.9 (C-
23′), 14.2 (C-24′);ESI-MSm/z:682 [ M+H] +
(positivemode).TheIRandNMRdatawerethesame
asthosereported[ 8] .
2α, 3α, 24-Trihydroxyolean-12-ene-28-oicacid(10)
Whitepowder, [ α] 20D +18.2°(c0.25, C5H5N);
IRυmaxcm -1:3434, 2926, 2856, 1694, 1634, 1453,
1033;1HNMR(C5D5N)δ:5.45 (1H, brs, H-12),
4.59 (1H, td, J=10.0, 4.0 Hz, H-2), 4.45(1H, d, J
=10.7Hz, H-24), 4.12(1H, d, J=10.7Hz, H-24),
980 NatProdResDev　　　　　　　　　　　　　　　　　　　　　 　Vol.19
and3.81 (1H, d, J=10.7Hz, H-3), 1.68 (3H, s, H-
29), 1.17 (3H, s, H-27), 1.00 (each3H, s, H-23,
30), 0.97 (3H, s, H-26), 0.90 (3H, s, H-25);13C
NMRdataseeTable1;ESI-MSm/z:487[ M-H] -(neg-
ativemode);TheIRandNMRdatawerethesameas
thosereported[ 6].
2α, 3β -Dihydroxyurs-12-ene-28-oicacid(11)　
Whitepowder, [ α] 20D +20.8°(c0.20, C5H5N);
IRυmax cm-1:3434, 2927, 2871, 1694, 1456, 1378,
1231, 1050;1HNMR(C5D5N)δ:5.45 (1H, s, H-
12), 4.09(1H, m, H-2), 3.40(1H, d, J=9.4Hz, H-
3), 2.60 (1H, d, J=11.5 Hz, H-18), 1.29 (3H, s,
H-23), 1.18 (3H, s, H-24), 1.06 (3H, s, H-26),
1.03(3H, s, H-27), 0.97 (3H, d, J=5.5 Hz, H-
29), 0.96(3H, s, H-25), 0.93 (3H, d, J=6.3 Hz,
H-30);13CNMRseeTable1;ESI-MSm/z:473[ M+
H] +(positivemode), 471[ M-H] -(negativemode)..
TheIRandNMRdatawereinconsistentwiththosere-
ported[ 9] .
2α, 3α, 24-Trihydroxyurs-12-ene-28-oicacid(12)
Whitepowder, [ α] 20D +16.0°(c0.50, C5H5N);
IRυmaxcm-1:3435, 2926, 1693, 1635, 1379, 1035;1H
NMR(C5D5N)δ:5.45 (1H, s, H-12), 4.59 (1H, br
s, H-2), 4.10 (1H, d, J=10.6 Hz, H-3), 3.80 and
4.44(each1H, d, J=10.7 Hz, H-24), 1.68 (3H, s,
H-23), 1.15 (3H, s, H-26), 1.03 (3H, s, H-27),
1.00(3H, s, H-25), 0.95 (3H, d, J=6.0 Hz, H-
29), 0.90 (3H, d, J=6.0 Hz, H-30);13CNMRsee
Table1;ESI-MSm/z:489[ M+H] +(positivemode),
487[ M-H] -(negativemode).TheIRandNMRdata
werethesameasthosereported[ 10] .
Table1　 13CNMRdataofcompounds7, 8, 10-12(C5D5N)
C-atom 7 8 10 11 12
1 43.9 42.3 42.1 47.8 43.4
2 67.0 65.4 67.1 68.4 67.1
3 80.2 85.5 75.2 83.6 75.2
4 40.4 43.8 44.2 39.2 46.1
5 49.6 56.3 49.1 55.7 50.4
6 19.3 19.0 19.8 18.6 19.8
7 34.4 33.6 34.1 33.3 38.4
8 41.1 39.8 40.9 39.6 41.1
9 48.8 47.9 48.9 47.9 49.0
10 39.5 38.0 39.4 38.2 40.3
11 24.6 23.9 24.6 23.5 24.7
12 126.5 125.2 123.0 125.3 126.8
13 140.2 139.0 145.7 139.1 140.1
14 43.5 42.3 43.1 42.3 44.2
15 29.5 28.4 29.2 28.4 30.0
16 25.8 24.7 24.7 24.7 26.1
17 48.9 47.7 47.6 47.8 49.1
18 54.5 53.3 43.4 53.3 54.5
19 40.3 39.2 47.3 39.8 40.4
20 39.7 39.3 31.8 39.2 39.8
21 32.0 30.8 34.9 30.8 31.5
22 38.4 37.2 34.1 37.2 38.4
23 30.4 23.7 24.6 29.1 24.7
24 23.2 68.4 66.1 17.2 66.1
25 17.6 17.2 18.0 17.3 18.1
26 18.4 17.1 18.1 17.5 18.1
27 24.7 23.6 27.0 23.7 24.8
28 180.8 179.6 180.8 179.6 180.8
29 18.4 17.1 34.9 16.7 18.4
30 22.3 21.1 24.8 21.2 24.7
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