全 文 :法 ,我们对两者的显微特征进行了观察比较 ,结果发
现正品与伪品的显微特征迥异 ,极易鉴别 。
1 实验材料
山慈菇为兰科植物杜鹃兰 Cremastraappendicu-
lata(D.Don)Makino的干燥假鳞茎 , 武汉市药品检
验所室存标本;山兰为兰科植物山兰 Oreorchispatens
Lindl.的假鳞茎 ,经武汉市药品检验所段木盛副主
任药师鉴定 。
2 显微特征
2.1 山兰假鳞茎横切面(直径 1.2 cm):最外层为
一层扁平的表皮细胞 ,外被角质层 ,其内为大的类圆
形薄壁细胞 ,含黏液质 ,并含糊化的淀粉粒 。近表皮
处的薄壁细胞中含草酸钙针晶束 ,长约 23 ~ 55μm。
维管束散在 ,外韧型 ,韧皮部外侧常有纤维束。 (图
1)
2.2 山兰假鳞茎粉末:表皮细胞顶面观垂周壁波
状弯曲 ,孔沟明显;侧面观细胞壁上面增厚 ,角质化 。
草酸钙针晶大多成束 ,存在于黏液细胞中 ,纤细 ,长
23 ~ 55 μm。纤维及含硅质块细胞 ,纤维成束 ,直径
18 ~ 25 μm,长约至 400 μm,壁薄 ,微木化 ,具斜纹
孔;含类圆形硅质块细胞小 ,类方形 ,位于纤维周围 ,
排成纵行 。导管为梯纹 、具缘纹孔及螺纹导管。淀
粉粒多糊化。 (图 2)
3 小结
毛慈菇的显微特征文献已有收载 〔1〕 ,山兰与毛
慈菇的显微特征主要区别点如下:表皮细胞内侧无
厚壁细胞;维管束外侧有纤维束;表皮细胞顶面观垂
周壁波状弯曲 ,可见纹孔 (而山慈菇表皮细胞顶面
观呈六边形 ,垂周壁平直);草酸钙针晶束较短 ,长
23 ~ 55μm;纤维成束 ,含硅质块的细胞纵行排列其
周围 。
参 考 文 献
1 国家药典委员会 .中华人民共和国药典 .一部 .北京:
化学工业出版社 , 2005∶23
2 王珏 ,等 .山慈菇与其伪品山兰的生药学鉴定 .中国药
业 , 2002, 11(8)∶64
(2004-04-01收稿)
·化学成分·
StudiesonChemicalConstituentsofRheumglabricaule
WeiYuhui1 , WuXin′an1 , ZhangChengzhong2 , LiChong2
(1.DepartmentofPharmacy, FirstHospitalofLanzhouUniversity, Lanzhou730000; 2.SchoolofPharmacy,
LanzhouUniversity, Lanzhou730000)
Abstract Objective:TostudythechemicalConstituentsintherootofRheumglabricaule.Methods:Compoundswereisolatedby
variouscolumnchromatographieswithsilicagel.Theirstructureswereidentifiedbyspectralanalysis(MS, 1HNMR, 13CNMR)and
chemicalevidences.Results:Sevencompoundswereisolatedfromthisplant, includingn-hexacosnicacid(Ⅰ ), palmiticacid(Ⅱ ),
daucosterol(Ⅲ), chrysophanol-8-Meether(Ⅳ), citreorosein(Ⅴ), chrysophanol8-O-β -D-glucopyranoside(Ⅵ )and2, 5-dimethyl-7-
methoxychromone(Ⅶ ).Conclusion:Allabovecompoundsareobtainedfromthisplantforthefirsttime.
Keywords Rheumglabricaule;Anthrapuinones;Chromone
1 Introduction
Rheum glabricauleG. Sam isdistributed in
Wudu, WenandMingcountyofGansuprovinceofChi-
na.AsaChinesefolkmedicinalherb, itcanclearaway
heatandtoxicmaterial, stanchandcooltheblood.Itis
appliedforpurgingandalkindsofhaemorrhage.The
researchshoweditspurgativeactionissimilartothatof
R.oficinaleBail.〔1〕Asapartofchemicalconstituents
research, wehavereportedfivecompoundsisolatedand
identifiedfromthisplant〔2〕.
2 Experimentalsection
2.1 Generalexperimentalprocedures Melting
pointsweredeterminedonaX-4 digitalmotormicro-
meltingpointapparatusandwereuncorected.VG
ZAB-HSmasspectrometerwasusedtorecordtheEI-
MS.NMRspectrawasmeasuredonaBurkerAM-400
spectrometer, usingTMSasinternalstandard.Coupling
constants(Jvalues)aregiveninHZ.Silicagel(100-
200mu)andSilicagelG、SilicagelHF254 (alfrom
QingdaoMarineChemicalGroupCo., Qingdao, Shan-
dongpProvince, China)wereusedforcolumnchroma-
tographyandTLC, respectively.
·658· 中药材第 28卷第 8期 2005年 8月
DOI :10.13863/j.issn1001-4454.2005.08.010
2.2 Plantmaterial AlrootsofR.glabricaulewere
colectedinWuducounty, GansuprovinceofChina, in
August, 2001, andidentifiedbyprofessorZhaoRu-
neng, fromLanzhouUniversity.Avoucherspecimenis
depositedattheMuseumofMedicinalPlant, Lanzhou
University.
2.3 Extractionandisolation Theair-driedand
pulverizedrootsofR.glabricaule(4.0kg)weresoaked
andextractedtentimeswith95% EtOHinroomtem-
perature, 24 hourseachtime.Afterremovalofsolvent,
obtained488gpowdersample.Thesamplewassubjec-
tedtocolumnchromatographyonsilicagelandeluted
withCHCl3 、EtOAcandEtOH, respectively.Theelutes
werecolected in 300mlportions, monitored by
TLC.Sevencompoundsinthisdisertationwereob-
tainedfrom twopartswhichhadbeenelutedwith
CHCl3 andEtOAc.Fromthepartwhichhadbeenelu-
tedwithCHCl3;weobtainedcompoundIbyresolving
fr13 ~ fr15 withn-BuOHandrepurifieditwithCHCl3;
fr18 ~ fr22 weresubjectedtorepeatedcolumchroma-
tographywithpetroleumether-EtOAc(20∶1, 15∶1)and
petroleumether-Acetone(5∶1)toyieldcompoundⅡ 、
Ⅶ ;compoundⅥ wasobtainedbyretreatingfr6 ~ fr15
withpetroleumether-EtOAc(5∶1)andpetroleumether-
Acetone(5∶1).Fromthepartwhichhadbeeneluted
withEtOAc, fr3wassubjectedtorepeatedcolumchro-
matogrphywithCHCl3 -MeOH(10∶1, 8∶1)toyield
compoundⅤ;compoundⅢ、 Ⅳ wereobtainedfrom
fr21 ~ fr30 withCHCl3 -MeOH(15∶1, 9∶1, 7∶1).
3 Resultsanddiscussion
CompoundⅠ (n-hexacosnicacid):C26H52 O2 ,
whiteneedles(EtOAc), mp79℃.EI-MSm/z:396
[ M+ ] , 382, 368, 354, 340, 325, 311, 297, 283, 269,
255, 241, 227, 213, 199, 185, 171, 157 , 129, 97, 85,
73 , 57 , 43.1HNMR(CDCl3 )δppm:2.35(2H, t, J=
7.2H2 , 2-H), 1.63(2H, m, 3-H), 1.25(44H, brs),
0.88(3H, t, J=6.8Hz, Me).13CNMR(CDCl3)δppm:
179.1(C-1), 33.9(C-2), 31.9(C-3), 29.1 ~ 29.7
(C-4 ~ C-23), 24.7(C-24), 22.7(C-25), 14.1(C-
26).Alabovedataarecorespondingtothoseof
hexacasnicacidinreference〔3〕.
CompoundⅡ (palmiticacid):C16H32O2 , white
powder(EtOAc), mp54℃.EI-MSm/z:256 [ M+ ] ,
242, 213, 129, 73, 60, 55, 43.1HNMR(CDCl3)δppm:
2.35(2H, t, J=7.2Hz, 2-H), 1.63(2H, m, 3-H),
1.25(20H, brs), 0.85(3H, t, J=3.6Hz, Me).
13CNMR(CDCl3)δppm:179.8(C-1), 34.0(C-2),
31.9(C-3), 29.1 ~ 29.8(C-4 ~ C-13), 24.7(C-14),
22.7(C-15), 14.1(C-16).Alabovedataarecore-
spondingtothoseofpalmiticacidinreference〔4〕.
CompoundⅢ (daucosterol):C35 H60 O6 , white
solid(CHCl3 -MeOH), mp296℃.Liebermannreaction
showspositive.EI-MSm/z:576[ M+ ] , 414[ M+-glu] ,
399[ M+-sugar-Me] .Thedataof1HNMR、13CNMRare
corespondingtothoseofβ-sitosteryl-3-O-D-glucopyr-
anosideinreference〔5〕.
CompoundⅣ (chrysophanol8-Meether):
yelowpiece(EtOAc), mp155 ~ 157℃, Bornträgerre-
actionshowsred.Mg(OAc)2 reactionshowssalmon
pink.EI-MSm/z:268[ M+ ] , 250, 239, 222, 149, 97,
69, 57, 43.1HNMR(CDCl3)δppm:12.92(1H, s, 1-
OH), 7.95(1H, dd, J=1.2.80Hz, 5-H), 7.74(1H, t,
J=8.0Hz, 6-H), 7.58(1H, d, J=1.2Hz, 4-H), 7.34
(1H, dd, J=8.0, 1.2Hz, 7-H), 7.08(1H, d, J=
1.2Hz, 2-H), 4.07(3H, s, OMe), 2.44(3H, s, Me).
13CNMR(CDCl3)seetable.Alabovedataarecore-
spondingtothoseofchrysophanol8-Meetherinrefer-
ence〔6〕.
CompoundⅤ (citreorosein):yelowneedles
(MeOH), mp278 ~ 279℃.Borntroä ogerreaction
showsred, (AcO)2 Mgreactionshowssalmonpink.EI-
MSm/z:286[ M+ ] , 270, 257, 242, 153 , 121.1HNMR
(DMSO-d6)δppm:12.06(1H, s, α-OH), 12.03(1H,
s, α-OH), 11.39(1H, s, ω-OH), 7.60(1H, brs, 5-
H), 7.22(1H, brs, 7-H), 7.09(1H, d, J=2.0Hz, 4-
H), 6.57(1H, d, J=2.0Hz, 2-H), 5.57(1H, s,
CH2OH), 4.60(2H, s, CH2OH).13CNMR(DMSO-d6)
seetable.Alabovedataarecorespondingtothoseof
citreoroseininreference〔7、8〕.
CompoundⅥ (chrysophanol8-O-β -D-glucopyr-
anoside):yelowneedles(Acetone), mp259℃.FAB-
MSm/z:416[ M+ ] , 254[ M+-glc] .1HNMR(DMSO-
d6)δppm:12.85(1H.s, 1-OH), 7.88(1H, dd, J=
1.6, 7.2Hz, 5-H), 7.83(1H, dd, J=8.0 , 7.2Hz, 6-
H), 7.71(1H, dd, J=1.6, 8.0Hz, 7-H), 7.50(1H, d,
J=2.0Hz, 2-H), 5.18(1H, d, J=7.6Hz, anomeric
H), 3.72 ~ 3.17(Sugar-H), 2.42(3H, s, Ar-Me).
13CNMR(DMSO-d6)seetable.Alabovedataarecor-
respondingtothoseofchrysophanol8-O-β -D-glucopyr-
anosideinreference〔3、 7〕.
·659·中药材第 28卷第 8期 2005年 8月
Table thespectraldatacompundⅣ ~ Ⅶ
C Ⅳ DEPT Ⅴ DEPT Ⅵ DEPT Ⅶ DEPT
1 162.6 161.5 161.6
2 124.6← 117.1 124.1← 163.8
3 147.6 152.9 147.6 116.0←
4 120.1← 120.8← 120.6← 179.8
5 118.1← 108.8← 119.4← 142.6
6 135.6← 165.5 135.9← 111.6←
7 120.0← 107.9← 122.4← 162.3
8 160.7 164.5 158.2 98.4←
9 188.5 189.7 187.6 159.7
10 182.9 181.3 182.1 116.0
4α 132.3 132.9 132.1
8α 118.1 109.0 114.8
9α 114.9 114.0 114.7
10α 135.7 135.1 134.8
CH
3 22.0← 21.5← 19.9(2)←
CH
3 23.0(5)←
OCH
3 56.6←
CH2OH 62.0↑
C′1 100.2←
C′2 73.3←
C′3 77.3←
C′4 69.5←
C′5 76.5←
C′6 60.6↑
CompoundⅦ (2, 5-dimetyl-7-methoxychromone):
C12 H12 O3 , yelowishneedles(EtOAc), mp254 ~
255℃.EI-MSm/z:204[ M+ ] , 176, 161, 136, 121,
93 , 77, 51 , 39.1HNMR(CDCl3)δppm:6.67 (2H,
brs, 6-H), 6.04(1H, s, 3-H), 3.86(3H, s, 7-OMe),
2.81(3H, s, 5-Me), 2.81(3H, s, 5-Me), 2.30(3H, s,
2-Me).13CNMR(CDCl3)seetable.Alabovedataare
correspondingtothoseof2, 5-dimetyl-7-methoxy-
chromoneinreference〔4、9〕.
Thanks ProfessorZhaoRunengforidentifyingtheplantand
stafofinstituteofLanzhouphysicalchemistry, academyofsci-
encesforNMRspectra.
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(2005-03-21收稿)
光茎大黄化学成分研究
魏玉辉 1 武新安1 张承忠2 李 冲 2
(1.兰州大学第一医院药剂科 ,甘肃兰州 730000;2.兰州大学药学院 ,甘肃兰州 730000)
摘要 目的:对光茎大黄根部的化学成分进行研究 。方法:采用硅胶柱层析 、重结晶 、MS、1HNMR、13CNMR等
技术进行分离 、结构鉴定。结果:从该植物中分离并鉴定了七个化合物 , 分别是:正二十六烷酸(n-hexacosnicacid,
Ⅰ ),棕榈酸(palmiticacid, Ⅱ), 胡萝卜甙(daucosterol, Ⅲ),大黄酚甲醚(chrysophanol-8-Meether, Ⅳ), ω羟基大黄素
(citreorosein, Ⅴ),大黄酚-8-O-葡萄糖甙(chrysophanol-8-O-β -D-glucopyranoside, Ⅵ )和 2, 5-二甲基-7-甲氧基色原酮
(2, 5-dimethyl-7-methoxychromoneⅦ )。结论:该七个化合物均为首次从该植物中分离得到。
关键词 光茎大黄;蒽醌类;色原酮
·660· 中药材第 28卷第 8期 2005年 8月