Studies On The Active Constituents Of Carthamus Tinctorius L. And The Chemical Constituents Of Dregea Sinensis Var. Corrugata

Carthamus tinctorius L.belongs to the family Compositae,which is widely distributed in the province of Henan,Zhejing,and Sichuan,etc.in China,and its flowers are used as traditional Chinese medicine for treatment of heart and brain blood vessel diseases.In our investigations,the H₂O extract exhibited potential protective action against hear and brain blood vessel diseases in rats,and the 50%EtOH eluate on macroporous resin was active fraction.HPLC-DAD-ESI-MSⁿ method was used to identify its constituents.To identify the constituents in the active fraction of Carthamus tinctorius L rapidly,ESI-MSⁿ fragmentation behaviors of the high-content constituents were investigated firstly,and the characteristic fragmentation patterns and UV spectra of these compounds were summarized; the structures of the low-content compounds of the same classes in the active fraction were detected.Their structures were 6-hydroxykaempferol-3-O-β-D-sophoroside-7-O-β-Dglucuronide（H1）, 6-hydroxykaempferot-3-O-（2-O-β-D-glucosyl-α-L-rhamnoside）-7-O-β-Dglucuronide（H2）, 6-hydroxykaempferol-3,6,7-tri-O-β-D-glucoside（H3）,kaempferol -3-O-β-D-glucoside-7-O-β-D-glucuronide（H4）,6-hydroxylkaempferol-3-O-β-rutinoside-6-Oβ-D-glucoside（H5）, 6-hydroxykaempferol-3,6-di-O-β-D-glucoside（H6）,kaempferol-3-Oβ-D-sophoroside（H7）, kaempferol-3-O-β-rutinoside（H8）,6-hydroxyquercetin-3-O-β-D -sophoroside-7-O-β-D-glucuronide（H9）,6-hydroxykaempferol-3-O-β-D-glucoside-7-O-βD-glucuronide（H10）, 3’,6-dimethoxylkaempferol-3,7-di-O-β-D-glucoside（H11）, 6-hydroxykaempferol-6,7-di-O-β-D-glucoside（H12）,3’,5-dihydroxy-4’,6,7-trimethoxy flavonol-3-O-β-D-sophoroside（H13）,hydroxysafflor yellow A（H14）,anhydrosafflor yellow B（H15）,cartormin（H16）,hydroxy safflor yellow B（H17）,safflor yellow A（H18）, cartormin B（H19）,tinctormine（H20）,safflomin C（H21）,safflomin D（H22）.safflor yellow D（H23）,cartormin C（H24）,and tinctormine B（H25）.Among them,H17,H19,H22,H23, H24 and H25 are new compounds,H9,H10,H11 and H13 are reported for the first time, others are known compounds isolated from this plant.Ten compounds were isolated from the active fraction of Carthamus tinctorius L by chromatographic methods such as ODS,Sephadex LH-20 and so on.On the basis of chemical evidence and spectral analysis,the structures of ten compounds were elucidated as hydroxysaffior yellow A（1）,P-hydroxy benzaldehyde（2）,6-hydroxykaempferol-3-O-β-rutinoside-6-O-β-D-glucoside（3）, 6-hydroxykaempferol-3,6-di-O-β-D-glucoside（4）,P-coumaric acid（5）,（E）-3-（4-hydroxy-3-methoxy-phenyl）-2-propenolic acid（6）,kaempferol-3-O-β-rutinoside（7）, kaempferol-3-O-β-D-glucoside（8）,cartormin（9）,and anhydrosafflor yellow B （10）.The ESI-MSⁿ fragmentation behaviors of six compounds（1,3,4,7,9 and 10）isolated from Cartharnus tinctorius were investigated.The characteristic fragmentation patterns of these compounds were discussed in detail to give some valuable conclusions and prove the results from on-line detection.Dregea sinensis var.corrugata belongs to the genus Dregea in the family Asclepiadaceae.Which is distributed in Shanxi,Gansu,Jiangsu,Zhejiang,Hubei,Guangxi, Yurman,Guizhou Provinces,and the Southwest in China.It has been used for expelling wind to relieve spasm,eliminating sputum and stopping coughing,detoxicating,and promoting blood flow in China.In our investigation,the chemical constituents of the EtOAc extract of Dregea sinensis var.corrugata were studied.Eight compounds were isolated by column chromatographic methods such as silica gel and Sephadex LH-20.Their structure were identified as syringaresinol（K1）,pinoresinol（K2）,syringaresinol-4’-O-β-D-glucoside（K3）,3,4’ -dimethoxyt-4,9,9’-trihydroxy-benzofuranlignan-7’-ene（K4）,coniferaldehyde（K5）,sinapic aldehyde（K6）,coniferyl alcohol（K7）,and 3-hydroxy-l-（4-hydroxy-3- methoxyphenyl） -propan-1-one（K8）.Compounds K1～K8 were isolated from Dregea sinensis vat.corrugata for the first time.