Chemical Constituents Of Three Medicinal Plants With Their Biological Activities

In this paper,the chemical constituents and biological activities of three traditional Chinese medicines（Solidago canadensis L.,Dendrobium nobile and Craibiodendron Yunnanese W.W.Smith）,which are rich in natural resources,were systematically studied.A total of 63compounds（including 6 new compounds）were isolated from the three plants by means of Macro-porous resin column chromatography,polyamide column chromatography,silica gel column chromatography,Sephadex LH-20 and high performance liquid chromatography.Their structures were established by spectroscopic means including 1D/2D-NMR,HR-ESIMS analyses.IR and UV.Most of the isolated compounds were evaluated for their antitumor,antifungal assay and phytoallelopathic activities,and the results showed that some of the compounds had significant biological activities.Chapter One,we studied the chemical constituents of the whole invasive plant Solidago canadensis L.A total of 39 compounds were isolated and identified.There were 6 compounds with novel structure（1-2,4,31,35-36）.They were eudesmane sesquiterpenes,chromolaevanetype sesquiterpenes,carotane sesquiterpenes and three stigmasterols.There were 33 known compounds,including 21 sesquiterpenes（3,5-24）,9 steroid compounds（25-30,32-34）,and 3 ursane type triterpenes（37-39）.The known compounds were identified as（2R,3S）-3-methyl-2-（5-oxo-2-isopropenylhexyl）-cyclopentanone（3）,（1R,5R,6R,7R,10S）-1,6-Dihroxyeudesm-4（15）-ene（5）,Eudesm-4（15）-ene-1β,6α-diol（6）,7-epi-eudesm-4（15）-ene-1β,6β-diol（7）,6α-hydroxy-4（15）-eudesmen-1-one（8）,Cosmosoicacid（9）,15-hydroxy-α-cadinol（10）,15-oxo-T-cadinol（11）,10-hydroxyl-15-oxo-α-cadinol（12）,Canangaterpenes III（13）,（3R,3a R,8a S）-3-isopropyl-8a-methyl-8-oxo-1,2,3,3a,6,7,8,8a-octahydroazulene-5-carbal-dehyde（14）,（+）-2-oxo-isodauc-5-en-12-a1（15）,Aphanamol II（16）,10β-hydroxy-isodauc-6-en-14-al（17）,Canangaterpenes VI（18）,（-）-Dehydrololiolide（19）,Loliolide（20）,Isololiolide（21）,5α,6α-epoxy-3β-hydroxy-7-megastimen-9-one（22）,Opposit-4（15）-en-1β,11-diol（23）,Saniculamoid D（24）,α-Spinasterol（25）,Stigmasterol（26）,Stigmasta-4,22-dien-3-one（27）,Stigmasta-4-en-3-one（28）,Stigmasta-4,6,8（14）,22-tetraen-3-one（29）,（22E,24R）-ergosta-6,9,22-trien-3β,5α,8α-triol（30）,Stigmast-5,22-dien-3β,7β-diol（32）,α-Tocospiro A（33）,（-）-α-Tocospirone（34）,Erythrodiol（37）,Triptohypol F（38）,Erythrotriol（39）.Antifungal activities of all the isolated compounds were tested.Two（11,13）of these compounds were active in an in vitro synergistic antifungal assay,and compound 11 displayed the most potent activity in combination with Fluconazole against C.albicans,with a FIC value of<0.15625.Meanwhile,the potential allelopathic effects of those compounds（new compounds removed in small amounts）on Arabidopsis seed germination were tested.Two eudesmane sesquiterpenes（6,8）,two carotenoids sesquiterpenes（20,21）andα-Spinasterol（25）retarded the Arabidopsis seed germination with IC₅₀ values ranging from 9.1 to 41μg/m L,while other compounds showed no obvious inhibitory effects.In addition,in vitro anti-tumor experiments were carried out on all the isolated compounds.A cadinane-type sesquiterpene（12）and a carotane-type sesquiterpene（14）were found to have strong potential antitumor activity against A549 and MDA-MB-231,with IC₅₀ values ranging from 0.72 to 5.37μM.Chapter two conducts a systematic chemical composition study on the leaves of Craibiodendron yunnanese W.W.Smith（Chrysophyllum Linn）in the Rhododendron L.family.A total of 19 compounds were isolated and identified from the ethyl acetate extract of the Craibiodendron yunnanese W.W.Smith.Including 11 known ursane triterpenoids（40-50）,eight oleanane triterpenoids（37,38,51-56）,two Sterols（57-58）.The known compounds were identified as 3β,13β-dihydroxy-urs-11-en-28-oic acid（40）,Yielded-28-nor-urs-12-ene-3β,17β-diol（41）,3β,28-Dihydroxy-urs-12-ene（42）,3β-Hydroxy-11α-methoxyurs-12-ene（43）,3β,11α-dihydroxy-urs-12-ene（44）,（3β）,13,28-Epoxyurs-11-en-3-ol（45）,Taraxast-20（30）-en-3β,12β-diol（46）,12-dien-3β-ol（47）,11α-Methoxyurs-12-ene-3β,12-diol（48）,3β-Hydroxy-11α-ethoxyurs-12-ene（Triptohypol D）（49）,α-Amyrin（50）,11α-methoxy derivatives（51）,Oleuna-9（11）:12-dien-3β-ol（52）,3β-hydroxy-olean-9（11）,12-dien（53）,Oleanolic acid（54）,3β-hydroxy-11α-ethoxy-olean-12-ene（55）,β-Amyrin（56）,β-Sitosterol（57）,7β-hydroxy-β-sitosterol（58）.We screened these compounds for their anti-tumor and anti-inflammatory activity,and the results showed that compound 58 showed good cytotoxicity to MDA-MB-231 cancer cell,IC₅₀ value is 14.19μM,it has a weak effect on the BT-549 cancer cell line and its IC₅₀ value is21.45μM.Third chapter selects the traditional Chinese medicine Dendrobium nobile,conducts a chemical composition study on its stems,and the isolated monomer compounds were evaluated for their anti-tumor activity.A total of 5 compounds（59-63）were isolated and identified from the ethanol extracts of Dendrobium nobile stem.The main types of compounds are phenanthrene,respectively,Nudol（59）,Confusarin（60）,3,7-dihydroxy-2,4-dimethoxy-9,10-dihydrophenanthrene（61）,3,7-dihydroxy-2,4-dimethoxy-phenanthrene（62）,3,7-dihydroxy-2,4,8-trimethoxyphenanthrene（63）.The isolated monomer compounds were studied for their anti-tumor（osteosarcoma osteosarcoma）activity,Nudol shows significant anti-proliferative activity on osteosarcoma cells and is achieved by induced cell apoptosis.Therefore,Nudol may be further studied as an effective strategy against bone tumors.