全 文 ：天然产物研究与开发 NatProdResDev2008, 20:827-829, 835
文章编号:1001-6880(2008)05-0827-04
　
　
　ReceivedJune6, 2007;AcceptedOctober8, 2007
　FoundationItem:ThisworkwassupportedbytheNationalScience
FoundationofGuangxi(GuiKeZi0542021)andFundofGuangxi
LargeApparatusesCooperation(292-2005-85).
＊CorespondingauthorTel:86-771-5883405;E-mail:liubuming@ya-
hoo.com.cn
岗松化学成分的研究
陈家源 ,牙启康 ,卢文杰 ,刘布鸣＊
广西中医药研究院 ,南宁 530022
摘　要:从岗松的石油醚和氯仿提取组分中分离得到 7个化合物 ,根据 NMR、HSQC、HMBC、IR和 MS的数据分
析及与文献对照 ,确定它们的结构为白桦脂酸(betulinicacid, 1), 齐墩果酸 (oleanolicacid, 2), 没食子酸乙酯
(ethylgalate, 3), 5-羟基-6-甲基-7-甲氧基-二氢黄酮 (5-hydroxy-6-methyl-7-methoxy-flavanone, 4), 5-羟基-7-甲氧
基-8-甲基二氢黄酮 (5-hydroxy-7-methoxy-8-methylflavanone, 5), 5-羟基-7-甲氧基-2-异丙基色原酮 (5-hydroxy-7-
methoxy-2-isopropylchromone, 6)和 β-谷甾醇 (β-sitosterol, 7)。其中 , 化合物 1 ～ 5和 7为首次从该植物中分离得
到。
关键词:桃金娘科;岗松;二氢黄酮;三萜
中图分类号:Q946.91;R284.1 文献标识码:A
StudyontheChemicalConstituentsofBaeckeafrutescens
CHENJia-yuan, YAQi-kang, LUWen-jie, LIUBu-ming＊
GuangxiInstituteofChineseMedical＆PharmaceuticalScience, Nanning530022 , China
Abstract:SevencompoundswereisolatedfromBaeckeafrutescensL..onthebasisofspectroscopicanalysisandcompari-
sonwiththereporteddata.Theywereidentifiedasbetulinicacid(1), oleanolicacid(2), ethylgallate(3), 5-hydroxy-6-
methyl-7-methoxyflavanone (4), 5-hydroxy-7-methoxy-8-methylflavanone (5), 5-hydroxy-7-methoxy-2-isopropy-
lchromone(6)andβ-sitosterol(7).Compounds1-5 and7 wereisolatedfromthisplantforthefirsttime.
Keywords:Myrtaceae;BaeckeafrutescensL.;flavanones;triterpenes
Introduction
BaeckeafrutescensL.belongstofamilyMyrtaceae,
whichisanaromaticlow-growingshrubdistributingin
Guangxi, Guangdong, JiangxiandFujianProvinceof
China[ 1] andhasbeenusedinChinesetraditionalmed-
icineforcold, traumaticinjury, ostealgliaduetowind-
dampness, gonorrhea, urocystitis, scabies, tineapedis,
dermatitis, inflammatorydiarhea, eczematouspruritus,
snakebite, insectbiteandsoon[ 2] .Chromones, chro-
manones, phloroglucinols, chromoneC-glycosides, fla-
vanonesandmetaboliteshavebeenreportedinveryre-
centphytochemicalstudiesofthisspecies[ 3-7] .The
presentpaperreportstheisolationandstructuraldeter-
minationofsevencompoundsfromBaeckeafrutescens
L.1-5and7 wereisolatedfromthisplantforthefirst
time.
Experimental
General
MeltingpointswereobservedwithaChineseX-4 melt-
ingpointapparatus(un-corrected).IR(KBrdisks)
wereobtainedusingNicolet4700 FTIRspectrometer
(USA).NMR, DEPT, HSQCandHMBCspectrawere
recordedonBruker500 Hzspectrometer(German).
EI-MSwerecarriedoutonTraceDSQGC/MSspec-
trometer(USA).Silicagel(100-200 mesh)forcol-
umnchromatographyandTLCwereperformedonG
plates(QingdaoMarineChemicalFactory).
Plantmaterial
ThewholeplantofBaeckeafrutescensL.wascolected
inOctober, 2005, inNanning, GuangxiProvince, Peo-
ple sRepublicofChina, andidentifiedbyProf.Lai
MaoxiangofGuangxiInstituteofChineseMedicine＆
DOI :10.16333/j.1001-6880.2008.05.003
PharmaceuticalScience.Avoucherspecimen(No.35-
289)hasbeendepositedattheHerbariumofGuangxi
InstituteofChineseMedicine＆ PharmaceuticalSci-
ence.
Extractionandisolation
Theair-driedandpoweredBaeckeafrutescensL.(4
kg)wereextractedwith95% EtOH(10LX5).After
removingthesolvent, theextract(742.5 g)weresus-
pendedwithwaterandpartitionedwithpetroleumether
(60-90 ℃), CHCl3 , EtOAcandn-BuOH, successive-
ly.Thepetroleumetherextractwereevaporatedtogive
90 gofresidues, 50gofwhichwasisolatedonasilica
gelcolumnelutedwithpetroleumether-EtOAc(99∶1
※90∶10)togive80 fractions(1000 mLperfrac-
tion).Fraction12-13 , 14-16, 18-22 and47-49 werere-
crystalizedtogive4 (36 mg), 5 (41 mg), 6 (1016
mg), and7 (65 mg), respectively.TheCHCl3 extract
wereevaporatedtogive66gofresidues, whichwasiso-
latedonasilicagelcolumnelutedwithCHCl3-MeOH
(99∶1※90∶10)increasingpolaritytogive55 frac-
tions(1000mLperfraction).Fraction11-22wereiso-
latedonsilicagelcolumnrepeatedly(3% MeOHin
CHCl3)andrecrystalizedtogive1 (28 mg), and2
(1540 mg).Fraction42-52 wereisolatedonsilicagel
columnrepeatedly(5% MeOHinCHCl3)andrecrys-
talizedtogive3(64mg).
ResultsandDiscussion
Betulinicacid(1) 　 Colorlessneedles(CHCl3-
MeOH);mp.>250 ℃.IRυKBrmaxcm-1:3450(OH), 3075
C-H), 2942, 2896(C-H), 1689 (C=O), 1642, 1452
C=C), 1388, 1376(-CH(CH3)2), 1043 (C-O), 885
(C-H), 649 (OH).EI-MSm/z:456[ M+] .1HNMR
(CDCl3)δ:0.75 (3H, s, H-24), 0.82(3H, s, H-25),
0.93(3H, s, H-23), 0.96(3H, s, H-26), 0.97(3H, s,
H-27), 1.69(3H, s, H-30), 3.00(1H, ddd, J=
11.35, 11.35, 5.53 Hz, H-19), 3.19(1H, dd, J=
10.50, 4.75Hz, H-3), 4.60(1H, d, J=1.90 Hz, H-
29a), 4.73(1H, d, J=1.90 Hz, H-29b);13 CNMR
(CDCl3)δ:38.7(C-1), 27.2(C-2), 79.0(C-3), 38.8
(C-4), 55.3(C-5), 18.2(C-6), 34.3(C-7), 40.7(C-
8), 50.5(C-9), 37.2(C-10), 20.8(C-11), 25.5(C-
12), 38.4(C-13), 42.4(C-14), 30.5(C-15), 32.1
(C-16), 56.3(C-17), 46.9(C-18), 49.2(C-19),
150.4(C-20), 29.7(C-21), 37.0(C-22), 28.0(C-
23), 15.3(C-24), 16.0(C-25), 16.1(C-26), 14.7
(C-27), 180.1(C-28), 109.7(C-29), 19.4(C-30).
TheseMS, IRandNMRspectraldatawereidentical
withthoseofbetulinicacid[ 10]
Oleanolcacid(2)　 Colorlessneedles(CHCl3 -
MeOH);mp.>250 ℃.IRυKBrmaxcm-1:3422(OH), 3075
(C-H), 2944 (C-H), 1696 (C=O), 1642 , 1463 (C
=C), 1387, 1364 (-CH(CH3)2), 1030 (C-O), 655
(OH).EI-MSm/z:456[ M+ ] , 250, 248 (100), 208,
207, 203, 190 , 189.1HNMR(CDCl3)δ:0.75(3H, s,
H-26), 0.77(3H, s, H-23), 0.90(3H, s, H-24), 0.91
(3H, s, H-29), 0.93(3H, s, H-30), 0.99(3H, s, H-
25), 1.13(3H, s, H-27)2.80(1H, dd, J=4.00, 4.00
Hz, H-18), 3.19(1H, dd, J=11.35, 5.10 Hz, H-3),
3.50(1H, br, OH), 5.30(1H, m, H-12);13 CNMR
(CDCl3)δ:37.9(C-1), 27.1(C-2), 76.8(C-3), 38.2
(C-4), 54.7(C-5), 17.8(C-6), 31.9(C-7), 38.8(C-
8), 47.0(C-9), 36.5(C-10), 23.2(C-11), 121.3(C-
12), 143.7(C-13), 41.2(C-14), 28.0(C-15), 22.7
(C-16), 46.5(C-17), 40.7(C-18), 45.3(C-19),
30.1(C-20), 33.2(C-21), 32.6(C-22), 30.1(C-
23), 16.8(C-24), 14.9(C-25), 17.8(C-26), 26.7
(C-27), 178.2(C-28), 32.3(C-29), 23.2(C-30).
TheseMS, IRandNMRspectraldatawereinconsist-
entwiththoseofOleanolcacid[ 8] .
Ethylgalate(3)　 Colorlessneedles(CHCl3 -
MeOH);mp.160-161℃.EI-MSm/z:198 [ M+ ] .
IRυKBrmax cm-1:3452, 3299 (OH), 3061 (Ar-H), 1707
(C=O), 1621, 1535, 1470 (Ar-C=C), 1257, 1120
(C-O-C).1HNMR(CDCl3)δ:1.33 (3H, t, J=8.00
Hz, CH3 ), 4.27 (2H, q, J=8.00Hz, CH2 ), 7.04
(2H, s, H-2, 6).Theabovedatawereaccordancewith
spectraldataofethylgalate[ 8] .
5-Hydroxy-6-methyl-7-methoxyflavan-one(4)　
Colorlessneedles(petroleumether-EtOAc);mp.97-99
℃, 5% AlCl3 colortestssuggestedthatitisafla-
vone.IRυKBrmaxcm-1:3414 (OH), 2930 (C-H), 1640 (C
=O), 1620, 1577, 1507(Ar-C=C), 1450, 1427,
1083, 777, 698.EI-MSm/z:284 [ M+ ] , 269, 266,
253, 207, 180(100), 152, 104, 77.1HNMR(CDCl3)
δ:2.87 (1H, dd, J=2.40, 2.40 Hz, H-3), 3.13(1H,
828 NatProdResDev　　　　　　　　　　　　　　　　　　　　 　Vol.20
dd, J=13.20, 13.20 Hz, H-3), 2.07(3H, s, 6-Me),
3.91(3H, s, 7-OMe), 5.46(1H, dd, J=2.40, 2.40
Hz, H-2), 6.14(1H, s, 8-H), 7.31-7.53(5H, m, Ar-
H), 12.13(1H, s, 5-OH);13 CNMR(CDCl3)δ:79.4
(C-2), 43.5(C-3), 195.8 (C-4), 161.2 (C-5),
106.1 (C-6), 165.8 (C-7), 90.7(C-8), 102.8 (C-
9), 160.4(C-10), 6.8 (6-Me), 55.8 (7-OMe),
138.6(C-1′), 126.2(C-2′, 6′), 128.8(C-4′), 128.8
(C-3′, 5′).Theabovedatawereaccordancewith
spectral data of 5-hydroxy-6-methyl-7-methoxyfla-
vanone[ 11] .Moreover, TheDEPTandHSQCspectrum
werealsoidenticalwiththoseofit.
5-Hydroxy-7-methoxy-8-methylflava-none(5)　
Colorlessneedles(petroleumether-EtOAc);mp.144-
146℃, 5% AlCl3 colortestssuggestedthatitisafla-
vone.IRυKBrmaxcm-1:3448(OH), 2917, 2850(C-H), 1641
(C=O), 1611, 1494, 1459(Ar-C=C), 1438, 1382,
1078, 782 , 691.EI-MSm/z:284[ M+ ] , 269, 266, 253,
207, 180 (100), 152 , 104, 77.1HNMR(CDCl3)δ:
2.90 (1H, dd, J=3.10, 3.10 Hz, H-3), 3.10(1H,
dd, J=12.75, 12.75 Hz, H-3), 2.07(3H, s, 6-Me),
3.86(3H, s, 7-OMe), 5.48(1H, dd, J=3.10, 3.10
Hz, H-2), 6.15(1H, s, 6-H), 7.31-7.53(5H, m, Ar-
H), 12.17(1H, s, 5-OH);13CNMR(CDCl3)δ:78.5
(C-2), 43.4(C-3), 196.3 (C-4), 162.4(C-5), 92.3
(C-6), 166.0 (C-7), 105.0(C-8), 102.9 (C-9),
168.9 (C-10), 7.6 (8-Me), 55.9 (7-OMe), 139.0
(C-1′), 125.9(C-2′, 6′), 128.8(C-4′), 128.5(C-3′,
5′).Theabovedataareaccordancewithspectraldata
of5-hydroxy-7-methoxy-8-methylflavanone[ 11] .Moreo-
ver, TheDEPTandHSQCspectrumwerealsoidentical
withthoseofit.
5-Hydroxy-7methoxy-2-isopropyl-chromone(6)　
Colorlessneedles;mp.67-70 ℃, 5%AlCl3 colortests
suggestedthatitisaflavone.IRυKBrmaxcm-1:3417(OH),
2979, 2942, 2876(C-H), 1676 (C=C), 1617, 1511,
1449(Ar-C=C), 1378 , 1355(-CH(CH3)2), 1304,
798, 771.EI-MSm/z:234 [ M+ ] (100), 220, 216,
206, 203, 190, 132.1HNMR(CDCl3)δ:2.85 (1H,
qq, J=6.90Hz, H-11), 3.33(6H, d, J=6.90Hz, H-
12 , 13), 3.88 (3H, s, 7-OMe), 6.06 (1H, s, H-3),
6.34 1H, s, H-6), 6.39 (1H, s, H-8), 12.74 (1H, s,
5-OH);13CNMR(CDCl3)δ:174.9 (C-2), 105.9(C-
3), 182.8 (C-4), 162.1 C-5), 97.9 (C-6), 165.4
(C-7), 92.3 (C-8), 158.1 (C-9), 105.4 (C-10),
33.2 (C-11), 20.0 (C-12, 13), 55.7 (7-OMe).The
abovedata, DEPTandHNBCwereaccordancewith
spectraldataof5-hydroxy-7-methoxy-2-isopropylchro-
mone[ 6] .
β-Sitosterol(7)　 Colorles needles(EtOH);
mp.133-136 ℃, IRυKBrmaxcm-1:3429 (OH), 2934, 2868
(C-H), 1633 (C=C), 1464, 1381, 1059 , 1022,
957.EI-MSm/z:414[ M+ ] .Itwasidentifiedasβ-si-
tosterolbycomparisonofthemixedmeltingpoint, IR
andRfwithanauthenticsample.
Acknowledgements　WewouldliketothankProf.Lai
maoxiangatGuangxiInstituteofChineseMedicine＆
PharmaceuticalScienceforidentifyingtheplantsam-
ple, ZhaoWeiminatShanghaiInstituteofMaterial
Medical, ShanghaiInstitutesforBiologicalSciences,
ChineseAcademyofSciences, Shanghai201203, China
forhelpingidentifycompounds1 , 2 and3, andWu-
qiangatcolegeofChemistryandChemicalEngineer-
ing, GuangxiNormalUniversityforcarryingoutNMRof
compound4, 5 and6.Wealsowouldliketothank
GuangxiCenterofAnalysisandTestResearchforcar-
ryingoutEI-MS.
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829Vol.20 　　　　　　CHENJia-yuan, etal:StudyontheChemicalConstituentsofBaeckeafrutescens　
Hz, H-8), 7.68(1H, d, J=1.8 Hz, H-2′), 7.55(1H,
dd, J=8.4, 2.4 Hz, H-6′), 6.90(1H, d, J=8.4 Hz,
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α-菠甾醇(7)　白色粉末(氯仿), mp.168 ～ 170
℃。1HNMR(150MHz, CDCl3)δ:0.55(3H, s, CH3),
0.80(3H, d, J=4.2 Hz, CH3), 0.82(3H, d, J=7.2
Hz, CH3), 0.85(3H, d, J=7.8 Hz, CH3), 1.02(3H,
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(C-2), 71.1(C-3), 38.0(C-4), 40.3(C-5), 29.6(C-
6), 117.5(C-7), 139.6(C-8), 49.5(C-9), 34.2(C-
10), 21.6(C-11), 39.5(C-12), 43.3(C-13), 55.1
(C-14), 23.0(C-15), 28.5(C-16), 55.9(C-17),
12.0(C-18), 13.0(C-19), 40.8(C-20), 21.0(C-
21), 138.2(C-22), 129.4(C-23), 51.2(C-24), 31.9
(C-25), 21.4(C-26), 19.0(C-27), 25.4(C-28),
12.2(C-29)。以上数据与文献 [ 8] 报道的 α-菠甾醇
数据一致 ,故确定该化合物为 α-菠甾醇 。
豆甾醇(8)　无色针晶 (乙醇), mp.170 ～ 172
℃。与已知对照品豆甾醇的 IR谱完全一致 ,多种展
开系统下共 TLC,不同显色剂显色 ,其 Rf值相同 ,故
鉴定该化合物为豆甾醇。
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835Vol.20 朱占军等:锥叶柴胡化学成分研究