全 文 ：天然产物研究与开发 NatProdResDev2009, 21:612-615
文章编号:1001-6880(2009)04-0612-04
　
　
　ReceivedJanuary24, 2008;AcceptedFebruary29, 2008
　FoundationItem:ThisprojectwasfinanciallysupportedbytheScientif-
icFoundationofShanghaiChina(06DZ19717).
＊CorrespondingauthorTel:86-21-81871244;E-mail:wdzhangy@hotmail.com
樱草杜鹃中的黄酮类化合物
李雪峰 1, 2 ,金慧子 1 ,陈　刚 1 ,杨　明 2 ,朱　燕 1 ,沈云亨 3 ,严诗楷1 ,张卫东1, 3＊
1上海交通大学药学院 , 上海 200240;2江西中医学院现代中药制剂
教育部重点实验室 ,南昌 330004;3第二军医大学药学院 , 上海 200433
摘　要:从樱草杜鹃(Rhododendronprimulaeflorum)地上部分的乙醇提取物中分离得到 10个黄酮类化合物 , 经理
化性质及波谱分析 ,鉴定为杜鹃素(1)、4′, 5, 7-三羟基-8-甲基黄烷酮(2)、二氢山柰酚(3)、异鼠李素(4)、槲皮素
(5)、陆地棉苷(6)、瑞诺苷(7)、(2R, 3R)-花旗松素-3-O-α-L-吡喃阿拉伯糖苷(8)、(2R, 3S)-花旗松素-3-O-α-L-
吡喃阿拉伯糖苷(9)、(2S, 3R)-花旗松素-3-O-α-L-吡喃阿拉伯糖苷(10)。 所有化合物均为首次从该植物中分
得。
关键词:杜鹃花科;樱草杜鹃;化学成分;黄酮类化合物
中图分类号:R284.1;Q949.9 文献标识码:A
FlavonoidsfromtheAerialPartsofRhododendronprimulaeflorum
LIXue-feng1, 2 , JINHui-zi1 , CHENGang1 , YANGMing2 , ZHUYan1 ,
SHENYun-heng3 , YANShi-kai1 , ZHANGWei-dong1, 3 ＊
1SchoolofPharmacy, ShanghaiJiaotongUniversity, Shanghai200240 , China;2JiangxiUniversityofTraditional
ChineseMedicine, KeyLaboratoryofModernChinesePreparation, MinistryofEducation, Nanchang330004 , China;
3DepartmentofPhytochemistry, SecondMilitaryMedicalUniversity, Shanghai200433 , China
Abstract:TenflavonoidswereisolatedfromtheethanolextractsoftheaerialpartsofRhododendronprimulaeflorumBur.
etFranch.Theirstructureswereelucidatedbyphysicochemicalpropertiesandspectroscopicanalysisasfarrerol(1), 4′,
5, 7-trihydroxy-8-methylflavanone(2), dihydrokaempferol(3), isorhamnetin(4), quercetin(5), hirsutine(6), reynoutin
(7), (2R, 3R)-taxifolin-3-O-α-L-arabinopyranoside(8), (2R, 3S)-taxifolin-3-O-α-L-arabinopyranoside(9), (2S, 3R)-
taxifolin-3-O-α-L-arabinopyranoside(10).Alcompoundswereisolatedfromthisplantforthefirsttime.
Keywords:Ericaceae;RhododendronprimulaeflorumBur.etFranch;chemicalconstituents;flavonoids
Introduction
AsapartofoursystematicinvestigationonEricaceae
plants, theRhododendrongenusplantRhododendron
primulaeflorumBur.etFranch.wasselected.R.primu-
laeflorumisashrubmainlydistributedinthesouthwest
districtofChina, especialyinTibetanAutonomousRe-
gion, YunnanandSichuanprovinces[ 1] .Itsleavesand
sproutsareusedasatraditionalChinesefolkdrugfor
treatingchronictracheitis, relievingcoughandasth-
ma[ 2] .Nochemicalstudiesonthisplanthavebeen
documented.Inourstudiesofthechemicalconstituents
fromthisplant, farrerol(1), 4′, 5, 7-trihydroxy-8-meth-
ylflavanone(2), dihydrokaempferol(3), isorhamnetin
(4), quercetin(5), hirsutine(6), reynoutin(7), (2R,
3R)-taxifolin-3-O-α-L-arabinopyranoside(8), (2R,
3S)-taxifolin-3-O-α-L-arabinopyranoside(9), (2S,
3R)-taxifolin-3-O-α-L-arabinopyranoside(10)wereiso-
latedandidentified.Alofthemwereisolatedfromthis
plantforthefirsttime.
Experimental
General
X-4 micromeltingpointapparatus(uncorrected);
BrukerVector22 IRspectrometer;Agilent1100 series
massspectrometer.NMRspectraweremeasuredona
BrukerDRX-500 instrument.Alsolventsusedwereof
analyticalgrade(ShanghaiChemicalCompany, Ltd.).
DOI :10.16333/j.1001-6880.2009.04.034
Silicagelwasusedforcolumnchromatography, and
precoatedsilicaGF254 platesusedforTLC(Qingdao
HaiyangChemicalCompany, Ltd.).
Plantmaterial
TheaerialpartsofR.primulaeflorumBur.etFranch.
werecolectedinXianggelila, Geza, YunnanProvince
ofChina, inJuly, 2006.Theplantmaterialwasidenti-
fiedbyProf.ZhengHanchen, DepartmentofPhytochemis-
try, SecondMilitaryMedicalUniversity.Thevoucher
specimens(colectionNo.SJTULXDJ)weredepositedat
HerbariumofSchoolofPharmacy, ShanghaiJiaotongU-
niversity, Shanghai, China.
Extractionandisolation
ThedriedaerialpartsofR.primulaeflorum(15.0 kg)
wereextractedwith95% ethanolthreetimesatroom
temperature, andeachprocesslastedtwohours.After
removalofthesolventbyevaporation, themethanolex-
tract(2019.3 g)wasaforded.Thentheextractwas
suspendedin4 Laqueousandpartitionedsuccessively
withpetroleumether, chloroform, ethylacetateandn-
butanol, afordingfourextracts721.7 , 1041.4, 17.5
and520.3 g, respectively.Partofthechloroformlayer
(200.0 g)wassubjectedtoaseriesofchromatographic
techniques, includingsilicagelcolumn(mesh200-
300), SephadexLH-20andprep-HPLCtoobtaincom-
pounds1(17mg), 2(60 mg), 3(12 mg), 4(9 mg), 5
(1.1 g), 6(21 mg), 7(24 mg), 8(44 mg), 9(19
mg), 10(15mg).
ResultsandDiscussion
Farrerol(1)　Yelowneedles, mp.229-232℃, IRυKBrmax
cm-1:3320, 1656, 1600, 1460 , 1380 , 1330, 1180, 1030,
980, 830;ESI-MSm/z:299.0 [ M-H] -;1HNMR(500
MHz, CD3OD)δ:1.99(3H, s, 8-CH3), 2.00(3H, s, 6-
CH3), 2.72(1H, dd, J=17.0, 3.0 Hz, H-3b), 3.07
(1H, dd, J=17.0, 12.8 Hz, H-3a), 5.31(1H, dd, J=
12.8, 3.0 Hz, H-2), 6.83(2H, d, J=8.5 Hz, H-3′,
5′), 7.32(2H, d, J=8.5 Hz, H-2′, 6′);13 CNMR
(125 MHz, CD3OD)δ:7.4(8-CH3), 8.1(6-CH3),
44.1(C-3), 80.1(C-2), 103.3(C-10), 104.1(C-8),
104.8(C-6), 116.3(C-3′, 5′), 128.8(C-2′, 6′),
131.6(C-1′), 158.9(C-4′), 159.3(C-5), 160.3(C-
7), 164.1(C-9), 198.4(C-4).Althedataofcom-
pound1wereinagreementwiththeliterature[ 3] .
4′, 5, 7-Trihydroxy-8-methylflavanone(2)　Yelow
powder, mp.195-200 ℃, IRυKBrmax cm-1:3500, 3400-
3050, 1635, 1610;ESI-MSm/z:285.1 [ M-H] -;1H
NMR(500 MHz, acetone-d6)δ:1.99(3H, s, 8-CH3),
2.65(1H, dd, J=17.0 , 3.0 Hz, H-3b), 3.17(1H,
dd, J=17.0, 13.0 Hz, H-3a), 5.42(1H, dd, J=
13.0, 3.0 Hz, H-2), 6.04(1H, s, H-6), 6.90(2H, d,
J=8.0 Hz, H-3′, 5′), 7.39(2H, d, J=8.0 Hz, H-2′,
6′), 8.49(1H, s, 4′-OH), 9.48(1H, s, 7-OH), 12.46
(1H, s, 5-OH);13 CNMR(125 MHz, acetone-d6 )δ:
7.7(8-CH3), 44.3(C-3), 80.6(C-2), 95.8(C-6),
103.7(C-10), 105.4(C-8), 116.9(C-3′, 5′), 129.7
(C-2′, 6′), 131.7(C-1′), 159.3(C-4′), 162.5(C-
9), 163.2(C-5), 165.7(C-7), 180.0(C-4).Thedata
abovewereinagreementwiththeliterature[ 4] .
Dihydrokaempferol(3)　Yelowpowder, mp.204-
207 ℃, IRυKBrmaxcm-1:3414, 1620, 1514, 1468;ESI-MS
m/z:287.0 [ M-H] -;1HNMR(500 MHz, CD3OD)δ:
4.54(1H, d, J=11.0 Hz, H-3), 4.98(1H, d, J=11.0
Hz, H-2), 5.87(1H, d, J=2.0 Hz, H-6), 5.93(1H,
d, J=2.0 Hz, H-8), 6.84(2H, d, J=8.0 Hz, H-3′,
5′), 7.36(2H, d, J=8.0 Hz, H-2′, 6′);13 CNMR
(125 MHz, CD3OD)δ:73.7(C-3), 85.0(C-2), 96.3
(C-8), 97.3(C-6), 101.9(C-10), 116.2(C-3′, 5′),
129.3(C-1′), 130.4(C-2′, 6′), 159.2(C-4′), 164.6
(C-9), 165.3(C-5), 168.7(C-7), 198.5(C-4).The
dataabovewereinagreementwiththoseofdihydro-
kaempferolreported[ 5] .
Isorhamnetin(4)　Yelowpowder, mp.303-305 ℃,
IRυKBrmaxcm-1:3228 , 1655, 1616, 1560, 1508;ESI-MSm/
z:315.5 [ M-H] -;1HNMR(500 MHz, acetone-d6)δ:
3.95(3H, s, 3′-OCH3), 6.28(1H, d, J=2.0 Hz, H-
6), 6.56(1H, d, J=2.0 Hz, H-8), 7.02(1H, d, J=
9.0 Hz, H-5′), 7.83(1H, d, J=9.0, 2.0 Hz, H-6′),
7.90(1H, d, J=2.0 Hz, H-2′), 8.02(1H, s, 3-OH),
8.26(1H, s, 4′-OH), 9.59(1H, s, 7-OH), 12.16
(1H, s, 5-OH);13 CNMR(125 MHz, acetone-d6 )δ:
56.5(3′-OCH3), 94.6(C-8), 99.2(C-6), 104.2(C-
10), 112.1(C-5′), 116.1(C-2′), 122.8 (C-6′),
122.9(C-1′), 136.8(C-3), 147.8(C-4′), 148.6(C-
2), 149.8(C-3′), 157.5(C-9), 162.4(C-5), 165.0
(C-7), 176.6(C-4).Fromthespectraldata, com-
613Vol.21 　　　　　　LIXue-feng, etal:FlavonoidsfromtheAerialPartsofRhododendronprimulaeflorum 　
pound4 wasevidencedasisorhamnetin, inagreement
withtheliterature[ 6] .
Quercetin(5)　 Yelowpowder, mp.310-312 ℃,
IRυKBrmaxcm-1:3400, 1660, 1608, 1557, 1518;ESI-MSm/
z:301.0 [ M-H] -;1HNMR(500 MHz, CD3OD)δ:
6.18(1H, d, J=2.0 Hz, H-6), 6.38(1H, d, J=2.0
Hz, H-8), 6.88(1H, d, J=8.0 Hz, H-5′), 7.63(1H,
dd, J=8.0, 2.0 Hz, H-6′), 7.73(1H, d, J=2.0 Hz,
H-2′);13CNMR(125 MHz, CD3OD)δ:94.4(C-6),
99.2(C-8), 104.5(C-10), 116.0(C-2′), 116.2(C-
5′), 121.7(C-6′), 124.2(C-1′), 137.2(C-3), 146.2
(C-3′), 148.0(C-2), 148.8(C-4′), 158.2(C-5),
162.5(C-9), 165.6(C-7), 177.3(C-4).Thedataa-
bovewereinagreementwithquercetinreported[ 7] .
Hirsutine(6)　 Yelow powder, mp.213-216 ℃,
IRυKBrmaxcm-1:3400-3200, 2925 , 1660, 1605, 1570, 1500;
ESI-MSm/z:463.1 [ M-H] -;1HNMR(500 MHz,
CD3OD)δ:3.46-3.86(m, sugarmoietyproton), 5.16
(1H, d, J=8.0 Hz, H-1″), 6.21(1H, d, J=2.0 Hz,
H-6), 6.40(1H, d, J=2.0 Hz, H-8), 6.87(1H, d, J
=8.0 Hz, H-5′), 7.59(1H, dd, J=8.0, 2.0 Hz, H-
6′), 7.84(1H, d, J=2.0 Hz, H-2′);13CNMR(125
MHz, CD3OD)δ:62.0(C-6″), 70.0(C-4″), 73.2(C-
2″), 75.1(C-3″), 77.2(C-5″), 94.8(C-8), 100.0(C-
6), 105.4(C-1″), 105.6(C-10), 116.1(C-2′), 117.8
(C-5′), 122.9(C-1′), 123.0(C-6′), 135.8(C-3),
145.8(C-3′), 150.0(C-4′), 158.5(C-2), 158.8(C-
9), 163.0(C-5), 166.3(C-7), 179.5(C-4).Alof
thesewereinagreementwiththosereportedinlitera-
ture[ 8] .
Reynoutrin(7)　Yelowpowder, mp.205-206 ℃,
IRυKBrmaxcm-1:3445, 1657, 1610, 1558 , 1506 ;ESI-MSm/
z:433.1 [ M-H] -;1H NMR(500 MHz, CD3OD)δ:
3.35-3.91(m, sugarmoietyproton), 5.16(1H, d, J=
6.0Hz, H-1″), 6.20(1H, d, J=2.0 Hz, H-6), 6.39
(1H, d, J=2.0Hz, H-8), 6.87(1H, d, J=8.0Hz, H-
5′), 7.58(1H, dd, J=8.0, 2.0 Hz, H-6′), 7.74(1H,
d, J=2.0Hz, H-2′);13CNMR(125 MHz, CD3OD)δ:
66.9(C-5″), 69.1(C-4″), 72.9(C-3″), 74.1(C-2″),
94.7(C-8), 100.0(C-6), 104.7(C-1″), 105.6(C-
10), 116.2(C-2′), 117.5(C-5′), 122.9(C-1′),
123.0(C-6′), 135.7(C-3), 146.0(C-3′), 149.9(C-
4′), 158.4(C-2), 158.7(C-9), 163.0(C-5), 166.1
(C-7), 179.5(C-4).Thesedatawereinaccordance
withthosereportedintheliterature[ 9] .
(2R, 3R)-Taxifolin-3-O-α-L-arabinopyranoside(8)
　Whitecrystal, mp.180-185 ℃, IRυKBrmaxcm-1:3372,
2924, 1642, 1284 , 1084;ESI-MSm/z:435.1 [ M-
H] -;1HNMR(500 MHz, CD3OD)δ:3.39(1H, dd, J
=11.0, 9.0 Hz, eq:H-5″), 3.56(1H, m, H-3″), 3.82
(1H, d, J=3.0 Hz, H-1″), 3.92(1H, dd, J=12.0,
8.0 Hz, ax:H-5″), 4.79(1H, d, J=11.0 Hz, H-3),
5.11(1H, d, J=11.0 Hz, H-2), 5.89(1H, d, J=2.0
Hz, H-8), 5.92(1H, d, J=2.0 Hz, H-6), 6.80(1H,
d, J=8.0 Hz, H-5′), 6.85(1H, dd, J=8.0, 2.0 Hz,
H-6′), 6.98(1H, d, J=2.0 Hz, H-2′);13CNMR(125
MHz, CD3OD)δ:63.4(C-5″), 66.9(C-3″), 71.1(C-
4″), 73.1(C-2″), 76.3(C-3), 83.7(C-2), 96.5(C-
8), 97.3(C-6), 101.4(C-1″), 102.3(C-10), 115.7
(C-2′), 116.3(C-5′), 120.8(C-6′), 129.0(C-1′),
146.5(C-3′), 147.4(C-4′), 164.2(C-9), 165.3(C-
5), 169.0(C-7), 196.1(C-4).Thesedataabovewere
similartothosereportedintheliterature[ 10, 11] .
(2R, 3S)-Taxifolin-3-O-α-L-arabinopyranoside(9)　
Whitecrystal, mp.165-169 ℃, ESI-MSm/z:435.1
[ M-H] -;1HNMR(500 MHz, CD3OD)δ:3.40-3.78
(m, sugarmoietyproton), 4.55(1H, d, J=6.0 Hz, H-
1″), 4.58(1H, d, J=3.0 Hz, H-3), 5.46(1H, d, J=
3.0 Hz, H-2), 5.90(1H, d, J=2.0 Hz, H-6), 5.93
(1H, d, J=2.0Hz, H-8), 6.73(1H, d, J=8.0Hz, H-
5′), 6.85(1H, dd, J=8.0, 2.0Hz, H-6′), 7.05(1H,
d, J=2.0 Hz, H-2′);13CNMR(125MHz, CD3OD)δ:
65.8(C-5″), 68.6(C-4″), 72.0(C-2″), 73.6(C-3″),
76.6(C-3), 81.9(C-2), 96.3(C-8), 97.2(C-6),
102.2(C-10), 102.8(C-1″), 115.9(C-2′), 116.1(C-
5′), 120.4(C-6′), 128.4 (C-1′), 146.0(C-3′),
146.6(C-4′), 164.2(C-9), 165.8(C-5), 168.7(C-
7), 194.4(C-4).Thesedataabovewereequaltothose
reportedintheliterature[ 10-12] .
(2S, 3R)-Taxifolin-3-O-α-L-arabinopyranoside(10)
　Whitecrystal, mp.174-178 ℃, ESI-MSm/z:435.1
[ M-H] -;1HNMR(500 MHz, CD3OD)δ:3.37-3.73
(m, sugarmoietyproton), 4.15(1H, d, J=6.0 Hz, H-
1″), 4.41(1H, d, J=2.0 Hz, H-3), 5.35(1H, d, J=
2.0 Hz, H-2), 5.87(1H, d, J=2.0 Hz, H-6), 5.90
(1H, d, J=2.0Hz, H-8), 6.74(1H, d, J=8.0Hz, H-
614 NatProdResDev　　　　　　　　　　　　　　　　　　　　 　Vol.21
5′), 6.85(1H, dd, J=8.0, 2.0 Hz, H-6′), 7.00(1H,
d, J=2.0Hz, H-2′);13CNMR(125 MHz, CD3OD)δ:
65.5(C-5″), 68.5(C-4″), 71.8(C-2″), 73.6(C-3″),
78.0(C-3), 81.7(C-2), 96.3(C-8), 97.2(C-6),
102.4(C-1″), 103.9(C-10), 115.8(C-2′), 116.1(C-
5′), 120.2 (C-6′), 128.3(C-1′), 146.2 (C-3′),
146.7(C-4′), 164.1(C-9), 165.7(C-5), 168.7(C-
7), 194.6(C-4).Thedataabovewereinagreement
withthosereportedintheliterature[ 10-12] .
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615Vol.21 　　　　　　LIXue-feng, etal:FlavonoidsfromtheAerialPartsofRhododendronprimulaeflorum