全 文 ：ThreenewxanthonesfromGarciniaxanthochymus
ZHONGFang-fang, CHENYu, SONGFa-jun, YANGGuang-zhong＊
(LaboratoryforNaturalProductChemistry, ColegeofLifeSciences, SouthCentralUniversityfor
Nationalities, Wuhan430074 , China)
Abstract:TostudyxanthonesfromthebarksofGarciniaxanthochymus, theconstituentswereisolated
bynormal-phaseandreverse-phasesilicagelcolumnchromatographyfromtheEtOAcextract.Their
structureswereelucidatedbyspectralanalysis.Threenewxanthoneswerepurifiedandidentifiedas1, 2, 5-
trihydroxy-6-methoxyxanthone(1), 1, 4, 6-trihydroxy-5-methoxyxanthone(2), 1, 2, 7-trihydroxy-4-(1, 1-
dimethylalyl)xanthone(3).
Keywords:Garcinia;Garciniaxanthochymus;xanthone
CLCnumber:R284.1　　　Documentcode:A　　　ArticleID:0513-4870(2008)09-0938-04
Received2008-04-16.
ProjectsupportedbyNationalNaturalScienceFoundationofChina
(30670215).
＊Corespondingauthor　Tel/ Fax:86-27-67842689,
E-mail:yanggz888@ 126.com
大叶藤黄中三个新 酮类成分
钟芳芳 , 陈　玉 , 宋发军 , 杨光忠＊
(中南民族大学 生命科学学院 天然产物化学研究室 , 湖北 武汉 430074)
摘要:为了研究大叶藤黄树皮中 酮类成分 ,运用正相和反相硅胶柱色谱法对大叶藤黄树皮乙酸乙酯萃取物进
行分离纯化 , 并用波谱技术鉴定化合物结构。共分离得到 3个新 酮类化合物 , 其结构分别鉴定为 1, 2, 5-三羟基-6-
甲氧基 酮(1), 1, 4, 6-三羟基-5-甲氧基 酮(2), 1, 2, 7-三羟基-4-(1, 1-二甲基烯丙基) 酮(3)。
关键词:藤黄属;大叶藤黄; 酮
　　ThegenusGarciniabelongstoGutiferaefamily,
whichcomprise200 speciesconfinedtothetropicsas
treesorshrubs, andrarelysubshrubs.Itiswelknown
tobearichsourceofoxygenatedandprenylated
xanthones[ 1] .Sincemostxanthoneshavephenolic
functionalgroupsonalineartricyclicring, theyoften
exhibitawiderangeofbiologicalandpharmacological
activities, such as antioxidative, antileukaemic,
antitumour, antiulcer, antimicrobial, antihepatotoxic,
andCNSdepressantactivities[ 2] .
Garcinia xanthochymusis a traditionalDai
medicinenativetothesouthandsouthwestofYunnan
Province, P.R.China, whichcangrowupto10-20
m.Itiswidelyusedasatraditionalmedicinefor
dispelingworms, clearingawayfireandremovingfood
toxin[ 3] .Previousphytochemicalstudiesoftheleaves,
seeds, fruits, twigbark, andwoodhavedemonstrated
thepresenceofbenzophenones[ 4-7] , flavonoids[ 8-10] ,
triterpenes[ 11] , andxanthones[ 12-15] .Asapartofour
searchforbioactivenaturalproductsfrom tropical
plants, acarefulexaminationofthebarkofthisplant
ledtotheisolationofthreenewxanthones.Weherein
reporttheisolationandstructureelucidationofthe
threenewxanthonesbyspectroscopicmethods.
Resultsanddiscussion
Compound1 wasobtainedasyelowamorphous
powder.ItsmolecularformulaC14H10 O6 wasdeduced
byHR-EI-MSspectrum.ItsUVabsorptionmaximaat
217, 257, and322 nmsuggestedthepresenceofa
xanthoneskeletonin1[ 16] .The1HNMRspectrumof1
showedtwosetsoforthocoupledprotonsatδH:6.96
(1H, d, J=9.0 Hz), 7.40(1H, d, J=9.0Hz), 7.20
·938· 药学学报 ActaPharmaceuticaSinica2008, 43(9):938-941DOI :10.16438/j.0513-4870.2008.09.003
(1H, d, J=9.0 Hz), 7.76(1H, d, J=9.0 Hz),
alongwithachelatedhydroxylgroupatδH 12.82anda
methoxylgroupatδH 4.03.Its13CNMRspectrumrevealedthepresenceof14 carbonsignalsincluding
onemethyl, foursp2 methines, eightsp2 quaternary
carbonsandonecarbonylgroup.Thesedatasuggested
that1 wasaxanthonederivativehavingthreehydroxyl
groupsandamethoxylgroup.InitsHMBCspectrum,
thecorelationsofH-8/C-6, C-9andC-5a, H-7/C-5,
C-6andC-8a, H-3/C-1, C-2, C-4 andC-4a, H-4 /C-
2, C-4aandC-9a, and6-OCH3 /C-6 wereobserved.
InitsROESYspectrum, NOEcorrelationswerefound
between H-8/H-7, H-3 /H-4 and H-7/6-OCH3.
Therefore, 1 wasestablishedtobe1, 2, 5-trihydroxy-6-
methoxyxanthone(Figure1).
Compound2, obtainedasayelowamorphous
powder, hadthemolecularformulaC14 H10O6 byHR-
EI-MSanalysis.TheUVspectrumat243, 282 and
301 nmof2 suggestedaxanthonestructure[ 15] .The
1H NMR spectrum of2 showedtwosetsofortho
coupledprotonsatδH:6.63(1H, d, J=8.7 Hz),
7.32(1H, d, J=8.7 Hz), 7.05(1H, d, J=8.7 Hz),
7.88(1H, d, J=8.7 Hz), alongwithachelated
hydroxylgroupatδH 12.15andamethoxylgroupatδH
4.05.The13CNMRspectrumof2 showed14 carbon
signalsincludingonemethyl, foursp2 methines, eight
sp2 quaternarycarbonsandonecarbonylgroup.Thus,
2 isasimpleoxygenatedxanthonehavingthree
hydroxylgroupsandamethoxylgroup.Comparedwith
the13CNMRdataof1, 6-dihydroxy-4 , 5-dimethoxyxan-
thone[ 15] , the13CNMRdataof2 issimilartothe
corespondingdataof1, 6-dihydroxy-4 , 5-dimethoxy-
xanthone, suggesting2hasthesamesubstituentpatern
as1, 6-dihydroxy-4, 5-dimethoxyxanthone.Thiswas
furthersupportedbytheHMBCcorrelationsofH-7/C-
5andC-8a, H-8/C-6, C-9 andC-5aand1-OH/C-1
andC-2 andNOEcorelationsbetweenH-2/H-3 and
H-7/H-8.ThemethoxylcarbonappearedatδC 61.4
indicatedtheexistenceofamethoxylgroupintwoortho
O-substituedfunctions[ 16] .Finaly, themethoxylgroup
Figure1　Chemicalstructuresofnewxanthones1, 2 and3
Table1　NMRandHMBCdataforcompounds1and2a
Position 1δCb δHc HMBC
2
δCb δHc HMBC
1 149.7 154.6
2 140.6 109.6 6.63d(8.7) C-1, 4, 9a
3 123.9 6.96d(9.0) C-1, 2, 4, 4a 121.7 7.32d(8.7) C-1, 4a
4 106.5 7.40d(9.0) C-2, 9a, 4a 137.7
4a 148.4 144.7
5 134.8 135.4
5a 146.7 151.0
6 153.3 157.1
7 109.0 7.20d(9.0) C-5, 6, 8a 115.9 7.05d(8.7) C-5, 8a
8 116.8 7.76d(9.0) C-6, 9, 5a 121.6 7.88d(8.7) C-6, 9, 5a
8a 115.0 114.3
9 182.8 181.9
9a 108.8 109.0
1-OH 12.82s 12.15s C-1, 2
6-OCH3 56.6 4.03s C-6
5-OCH3 61.4 4.05s C-5
aChemicalshifts(δ)inppm;couplingconstant(J)inHz;bMeasuredin125 MHzinMe2CO-d6;
cMeasuredin400 MHzinMe2CO-d6
·939·ZHONGFang-fang, etal:ThreenewxanthonesfromGarciniaxanthochymus
Table2　1HNMR, 13CNMRandHMBCdataof3a
Position δCb 　　δHc HMBC
1 146.2
2 139.2
3 122.9 7.38s C-1, 2, 4a, 1′
4 125.9
4a 146.0
5 119.8 7.53d(9.0) C-5a, 7, 8a
5a 150.6
6 125.8 7.43d(9.0) C-5a, 8
7 154.3
8 108.2 7.59brs C-5a, 6, 8a, 9
8a 125.7
9 183.3
9a 109.5
1′ 40.4
2′ 147.7 6.23dd(17.7, 11.1) C-1′, 4′, 5′
3′ 110.8 5.12d(17.7), 5.05d(11.1) C-1′, 2′
4′ 27.3 1.59s C-4, 1′, 2′, 5′
5′ 27.3 1.59s C-4, 1′, 2′, 4′
1-OH 12.76s C-1, 2, 9a
aChemicalshifts(δ)inppm;couplingconstant(J)inHz;
bMeasuredin125 MHzinMe2CO-d6;cMeasuredin400 MHzinMe2CO-d6
waslocatedatC-5, whichwasfurthersupportedby
the HMBC corelation of 5-OCH3 /C-5. Thus,
compound2wasdeterminedtobe1, 4, 6-trihydroxy-5-
methoxyxanthone(Figure1).
Compound3 wasobtainedasyelowamorphous
powder.ItsmolecularformulaC18H16O5 wasdeduced
byHR-EI-MS.TheUVspectrumwassuggestedthat3
wasxanthonederivative[ 17] .The1HNMRspectrumof
3 showedachelatedhydroxyatδH 12.76, onearomatic
signalassingletatδH 7.38 andatypicalsignalofa
1, 1-dimethylalylgroupatδH:6.23(1H, dd, J=
17.7, 11.1 Hz);5.12(1H, d, J=17.7 Hz);5.05
(1H, d, J=11.1 Hz)and1.59(6H, s), inaddition
toa1, 3, 4-trisubstitutedbenzeneatδH:7.53(1H, d,
J=9.0 Hz), 7.43(1H, d, J=9.0 Hz)and7.59
(1H, brs).Inthe13CNMRspectrum, 18 carbon
signalsincludingtwomethyls, onesp2 methylene, five
sp2 methines, eightsp2 quaternarycarbons, onesp3
quaternary carbon and onecarbonylgroup were
detected.From thesedata, 3 wasconsideredas
tetrasubstituted xanthone derivative having three
hydroxylgroupsandone1, 1-dimethylalylgroup.
Comparisonof13C NMR dataof3 withthoseof
globuxanthone[ 17] indicatedthatthesubstituentpatern
oftheringBwassimilartothatofglobuxanthone.This
factwassupportedbytheHMBCcorrelationsof1-OH/
C-1, C-2 andC-9a, H-3 /C-1, C-2 andC-1′, and
H3-4′, 5′/C-4.Theremaininghydroxylgroupwas
locatedontheC-7 basedontheHMBCcorelationof
H-8/C-5a, C-8a, C-6 andC-9 , H-6/C-5aandC-8
andH-5/C-5a, C-8aandC-7.Thus, thestructureof
3waselucidatedas1, 2 , 7-trihydroxy-4-(1, 1-dimethyl-
alyl)xanthone(Figure1).
Experimental
Generalexperimentalprocedures　UVspectra
weremeasuredonaSP-2102UVPCspectrometer.NMR
spectrawererunonBrukerAM-400spectrometerswith
TMSasinternalstandard.EI-MSandHR-EI-MSwere
measuredwithaFinniganMAT95 instrument.Thin-
layerchromatography(TLC)wasperformedonsilica
gel60GF254 , andcolumnchromatographywascaried
usingsilicagel(200 -300 mesh)from Qingdao
HaiyangChemicalGroupCo., P.R.ChinaandC18
reversed-phasesilicagelfrom YMCCO., LTD.,
Japan.
Plant Material　 The barks ofGarcinia
xanthochymuswere colected from Xishuangbanna
Prefecture, YunnanProvince, P.R.Chinaand
identifiedbyMrsZHAOYing-hong, Xishuangbanna
PrefectureNationalMedicineResearchInstitute.The
voucherspecimen(06061201)wasdepositedinthe
herbariumofColegeofLifeSciences, SouthCentral
UniversityforNationalities, P.R.China.
Extractionandisolation　Themiled, air-dried
barksofGarciniaxanthochymus(6.5 kg) were
poweredandthenextractedwith95% EtOH three
timesatroom temperature.ThedriedEtOH extract
(1.5kg)wassuspendedin90%MeOH-H2Oandthen
succesivelypartitionedwithpetroleum ether(PE)
(3.0 L×3), EtOAc(3.0 L×3)andn-BuOH(3.0
L×3).TheEtOAcextract(590 g)wassubjectedto
CC(silicagel, PE/acetone9∶1, 8 ∶2, 7∶3, 1∶1,
3∶7, 0∶1, v/v)togivethirteenfractions(Fr.1-Fr.
13).Fr.7 wassubjectedtoCC(silicagel, toluene-
acetone95∶1※7∶3)togive15 subfractions.Fr.7.6
wasseparatedbycolumnchromatographyonsilicagel
elutedwithacyclohexane-acetonegradient(95 ∶5※
1∶1)toprovideeightsubfractions:fr.7.6.1 -fr.
7.6.8.Fr.7.6.5 wasfurtherpurifiedbyCC(ODS,
H2O-MeOH 7 ∶3※ 3 ∶7, 10% steps)toaford
compounds1(2.3mg)and2(1.5mg).Fr.7.4was
chromatographedoversilicagel, usingacyclohexane-
CH2Cl2 gradientsystem(1∶1※0∶1)toaford3(5.6
mg).
·940· 药学学报 ActaPharmaceuticaSinica2008, 43(9):938-941
1, 2, 5-Trihydroxy-6-methoxyxanthone(1)
Yelowamorphouspowder;UVλMeOHmax (lgε)nm:217
(4.41), 257(4.18), 322(3.69);1HNMRand
13CNMR:seeTable1;EI-MS(70 eV)m/z:274
(M+;relint100), 259(42), 149(96), 91(63),
59(97);HR-EI-MSm/z274.047 7 (calcdfor
C14H10O6 , 274.047 7).
1, 4, 6-Trihydroxy-5-methoxyxanthone(2)
Yelowamorphouspowder;UVλMeOHmax (lgε)nm:243
(4.20), 282(4.03), 301(4.01);1HNMRand
13CNMR:seeTable1;EI-MS(70 eV)m/z:274
(M+;relint84), 259(100), 75(52);HR-EI-MS:
m/z274.047 6 (calcdforC14H10O6 , 274.047 7).
1, 2, 7-Trihydroxy-4-(1, 1-dimethylalyl)xanthone
(3)　Yelowamorphouspowder;UVλMeOHmax (lgε)nm:
242(4.48), 268(4.40), 304(3.85);1HNMRand
13CNMR:seeTable2;EI-MS(70 eV)m/z:312
(M+;relint52), 297(16), 279(100), 251(52),
57(52);HR-EI-MSm/z312.100 2 (calcdfor
C18H16O5 , 312.099 7).
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