β-蜕皮甾酮的分离及结构修饰

目的从露水草总甾酮中分离β蜕皮甾酮并对其进行结构修饰。方法采用硅胶柱色谱分离β蜕皮甾酮,并以其为原料通过化学合成的各种手段合成结构类似物,利用光谱分析方法对所得化合物进行结构确证。结果与结论从露水草总甾酮中分离了β蜕皮甾酮(20 hydroxyecdysone)及另一含量较大的筋骨草甾酮C(ajugasterone C)。以分离的β蜕皮甾酮为原料化学合成了5种植物甾酮。分别是2,3,20,22双异丙叉基β蜕皮甾酮(20 hydroxyecdysone 2,3,20,22 diacetonideⅠ)、20,22异丙叉基β蜕皮甾酮(20 hydroxyecdysone 20,22 acetonideⅡ)、2,3,20,22双异丙叉基25乙酰基β蜕皮甾酮(viticosterone E 2,3,20,22 diacetonideⅢ)、2,3异丙叉基β蜕皮甾酮(20 hy-droxyecdysone 2,3 acetonideⅣ)、2,3异丙叉基22羰基β蜕皮甾酮(22 oxo 20 hydroxyecdysone2,3 acetonideⅤ)。     

Non-taxane compounds from the bark of Taxus yunnanensis

From the bark of Taxus yunnanensis, 15 non-taxane compounds were isolated. Through spectroscopic methods such as ID and 2D NMR and MS experiments, one of them was determined as a new abietane-type diterpenoid named taxayunnin (1). The other 14 known compounds were identified as taxamairin C (2), taxamairin A (3), 3beta-hydroxy-sandaracopimaric acid (4), (+)-3-hydroxy-isodrimenin (5), rubrosterone (6), ponasterone A (7), ecdysterone (8), 20-hydroxy-echysone-20,22-monoacetonide (9), 7-oxositosterol (10), stigmast-4-en-6beta-ol-3-one (11), 5alpha,6beta-dihydroxy-daucosterol (12), beta-sitosterol (13), daucosterol (14), 1-O-beta-D-glucopyranosyl-(2S, 3R, 4E, 8Z)-2-N-(2'-hydroxypalmitoy])-octadeca-sphinga-4,8-dienine (15), respectively. Compounds 4-6, 9-12 and 15 were isolated from Taxus plants for the first time.     

Non-taxane compounds from the bark of Taxus yunnanensis

From the bark of Taxus yunnanensis , 15 non-taxane compounds were isolated. Through spectroscopic methods such as 1D and 2D NMR and MS experiments, one of them was determined as a new abietane-type diterpenoid named taxayunnin ( 1 ). The other 14 known compounds were identified as taxamairin C ( 2 ), taxamairin A ( 3 ), 3 g -hydroxy-sandaracopimaric acid ( 4 ), (+)-3-hydroxy-isodrimenin ( 5 ), rubrosterone ( 6 ), ponasterone A ( 7 ), ecdysterone ( 8 ), 20-hydroxy-echysone-20,22-monoacetonide ( 9 ), 7-oxositosterol ( 10 ), stigmast-4-en-6 g -ol-3-one ( 11 ), 5 f ,6 g -dihydroxy-daucosterol ( 12 ), g -sitosterol ( 13 ), daucosterol ( 14 ), 1- O - g - d -glucopyranosyl-(2 S , 3 R , 4 E , 8 Z )-2- N -(2'-hydroxypalmitoyl)-octadeca-sphinga-4,8-dienine ( 15 ), respectively. Compounds 4 - 6 , 9 - 12 and 15 were isolated from Taxus plants for the first time.     

Chemical composition and biological activity of total bufadienolides from the Central-Asian <Emphasis Type="Italic">Bufo viridis</Emphasis> toad venom

The chemical composition of bufadienolides isolated from the venom of Bufo viridis green toad occurring in Central Asia was determined and their biological properties were studied. Six individual bufadienolides were isolated by reverse-phase chromatography on a Lichrosorb RP-8 (10 μ) column in amounts sufficient for qualitative analysis. Two of these were previously identified as arenobufagin and gamabufotalin by NMR spectroscopy and x-ray diffraction methods. The chemical structures of four other bufadienolides are now established by NMR spectroscopy and HPLC. These compounds have been identified as telocinobufagin (3β,5β,14β-trihydroxybufa-20,22-dienolide), marinobufagin (3β, 5β-hydroxy-14,15β-epoxybufa-20,22-dienolide), bufarenogin (3β,12β,14β-hydroxybufa-20,22-dienolide), and bufalin (3β,14β-hydroxybufa-20,22-dienolide). __________ Translated from Khimiko-Farmatsevticheskii Zhurnal, Vol. 41, No. 11, pp. 33–37, November, 2007.     

露水草的化学成分露水草的化学成分

目的研究露水草的化学成分。 方法应用多种色谱技术进行分离，并结合NMR,MS等波谱解析确定其化学结构。结果分离得到6个化合物，鉴定为20，22-异丙叉基筋骨草甾酮C（1），20，22-异丙叉基β-蜕皮甾酮（2），22-羰基筋骨草甾酮C（3），22-羰基-β-蜕皮甾酮（4），β-谷甾醇（5），胡罗卜苷（6）。结论3为一新化合物，4为一新天然产物。     

华东蓝刺头根的化学成分

目的对中药华东蓝刺头根的化学成分进行分离鉴定。方法采用硅胶柱色谱、制备型反相HPLC等方法分离纯化,1H-NMR1、3C-NMR等方法进行结构鉴定。结果从华东蓝刺头根中分离并鉴定了8个化合物,分别鉴定为:5-(3,4-二羟基丁炔-1)-2,2′-联噻吩[5-(3,4-dihydroxy-but-1-ynyl)-2,2-′bithiophene,1]、2-(戊二炔-1,3)-5-(3,4-二羟基-丁炔-1)噻吩[2-(penta-1,3-diynyl)-5-(3,4-dihydroxybut-1-ynyl)thiophene,2]2、-(丙炔-1)-5-(5,6-二羟基-己二炔-1,3)噻吩[2-(pro-1-ynyl)-5-(5,6-dihydroxyhexa-1,3-diynyl)thiophene,3]、木犀草素(luteolin,4)、筋骨草甾酮C(ajugasterone C,5)、丁香苷(syringin,6)、绿原酸(chlorogenic acid,7)、菜蓟素(cynarin,8)。结论化合物5、7、8为首次从该属植物中分离得到。     

Cardenolide analogues. 4. (20R)- and (20S)-Cardanolides: on the roles of the 20(22)-ene and 14beta-hydroxyl in genin activity.

(20R)-20,22-Dihydrodigitoxigenin (3a) and (20S)-20,22-dihydrodigitoxigenin (3b) were isolated from (20R,S)-20,22-dihydrodigitoxigenin (3) by three fractional crystallizations each from ethyl acetate. The two diastereomers have distinct NMR spectra and similar (Na+,K+)ATPase inhibitory activities (I50 = 1.1-1.4 X 10(-5) M)--about 1/100 as active as digitoxigenin (1). Their activity compared with other cardenolide analogues suggests a passive geometric role for the 20(22) double bond in eliciting (Na+,K+)ATPase inhibition, keeping the lactone carbonyl in the proper orientation. (20S)-3 beta,14 beta-Dihydroxy-22-methylene-5 beta,14 beta-cardanolide (7a) was then synthesized from 3a, and (20R)-3 beta,14 beta-dihydroxy-22-methylene-5 beta,14 beta-cardanolide (7b) from 3b. They were found to be equivalently active in inhibiting (Na+,K+)ATPase, with I50 values of 7.0 x 10(-5) M. Although it has been usually believed that the 14 beta-hydroxyl of cardenolides increases binding to the receptor, 2b (the 14-ene derivative of 7b) was more than twice as active (I50 = 3.0 X 10(-5)) than either 7a or 7b.     

Triterpenoids from Salvia wagneriana

From the exudate of Salvia wagneriana Polak, beside the known ursolic acid, two pentaoxygenated triterpenoids were isolated. Their structures were determined as 3-oxo-11alpha,19beta,20,22beta-tetrahydroxy-lupane (1) and 3beta,11alpha,19beta,20,22beta-pentahydroxy-lupane (2) using a combination of one- and two-dimensional NMR techniques.     

Three new steroidal saponins from Fritillaria pallidiflora

Three new steroidal saponins, pallidiflosides A (1), B (2), and C (3), have been isolated from the dry bulbs of Fritillaria pallidiflora Schrenk. Their structures were elucidated as 26-O-β-d-glucopyranosyl-(25R)-furost-5,20(22)-dien-3β,26-diol-3-O-β-d-xylopyranosyl(1?→?4)-[α-l-rhamnopyranosyl(1?→?2)]-β-d-glucopyranoside (1); 26-O-β-d-glucopyranosyl-3β,26-dihydroxyl-20,22-seco-25(R)-furost-5-en-20,22-dione-3-O-α-l-rhamnopyranosyl(1?→?2)-β-d-glucopyranoside (2); and (25R)-spirost-5-ene-3β,17α-diol-3-O-β-d-glucopyranosyl(1?→?4)-β-d-galactopyranoside (3) by spectroscopic techniques and chemical means.     

A new phytosterone from Cyanotis arachnoidea

From Cyanotis arachnoidea C.B. Clarke, a new phytosterone named cyanosterone A (1), along with three known compounds--beta-ecdysone (2), ajugasterone C (3) and beta-sitosterol (4) were isolated. The structure of the new compound was determined as 3beta,14alpha,20R,22R-tetrahydroxy-5alpha-cholest-7-en-6-one on the basis of physicochemical properties and spectral analysis.     

祁州漏芦中的植物甾酮类成分

自祁州漏芦 (Rhaponticumuniflorum (L .)DC .)的根中分离得到 4种植物甾酮类成分 ,根据理化常数和波谱数据鉴定为蜕皮甾酮 (ecdysterone) (1) ,筋骨草甾酮C(ajugasteroneC) (2 ) ,蜕皮甾酮 3 O β D 葡萄糖苷 (ecdysterone 3 O β D glucopyranoside) (3) ,蜕皮甾酮 2 5 O β D 葡萄糖苷(ecdysterone 2 5 O β D glucopyranoside) (4) ,其中化合物 3,4,为从本属植物中首次分离     

An Investigation of the Stem Bark of Bersama abyssinica

The barks of two subspecies of BERSAMA ABYSSINICA, subspecies ABYSSINICA and subspecies PAULLINIOIDES have been shown to contain two bufadienolides: 5beta, 14beta-dihydroxy-3,6-diacetoxy-Delta (6)-bufa-20,22-trienolide ( 1) and 3-acetoxy-14beta-hydroxy-bufa-20,22-dienolide ( 2). Three sterols : beta-sitosterol, Delta (4)-stigmasten-3alpha-ol ( 3) and 4-methyl-Delta (5,23)-stigmast-dien-3beta-ol ( 4) have also been isolated. 3 is a new compound and 3 and 4 are reported for the first time from the Melianthaceae. The presence of the xanthone mangiferin is a possible taxonomic marker for the genus within this family. Differences between the two subspecies were seen on examining the glycoside fractions. The alcoholic extracts did not exhibit any anti-tumour activity in the standard test.     

Two new steroidal saponins from the rhizomes of Dioscorea panthaica and their cytotoxic activity.

Two new steroidal saponins, dioscoresides C (1) and D (2), along with a new natural product, pregnadienolone 3-O-beta-gracillimatriose (3), and two known compounds, pregnadienolone 3-O-beta-chacotrioside (4) and pseudoprotodioscin (5), were isolated from the rhizomes of Dioscorea panthaica Prain et Burkill. On the basis of extensive NMR studies and chemical evidence, dioscoresides C and D were determined to be 26-O-beta-D-glucopyranosyl-3 beta,26-dihydroxy-23(S)-methoxy-25(R)-furosta-5,20(22)-dien-3-O-alpha-L-rhamnopyranosyl-(1-->2)-[alpha-L-rhamnopyranosyl-(1-->4)]-beta-D-glucopyranoside and 26-O-beta-D-glucopyranosyl-3 beta,26-dihydroxy-20,22-seco-25(R)-furosta-5-en-20,22-dine-3-O-alpha-L-rhamnopyranosyl-(1-->2)-[alpha-L-rhamnopyranosyl-(1--> 4)]-beta-D-glucopyranoside. These compounds showed mild cytotoxicity against the cancer cell lines, A375, L929, and HeLa, in a dose-dependent manner.     

Isolated 5-hydroxytryptamine organelles of rabbit blood platelets: Physiological properties and drug-induced changes

1. In isolated 5-hydroxytryptamine (5-HT) organelles of rabbit platelets, the concentrations of 5-HT, histamine and adenosine-triphosphate (ATP) respectively are about 200 times higher than in intact platelets. Organelles incubated in plasma at 37 degrees C gradually lose endogenous 5-HT, histamine and ATP and take up (14)C-5-HT against a considerable concentration gradient. Liberation and uptake of 5-HT markedly decrease with dimishing incubation temperature.2. Exposure to reserpine in vitro strongly counteracts the uptake of (14)C-5-HT by isolated organelles, whereas the (14)C-5-HT uptake of intact isolated platelets is less affected by the drug. 5-HT organelles of platelets from reserpinized rabbits also take up very little (14)C-5-HT.3. Imipramine inhibits the uptake of (14)C-5-HT in isolated organelles less markedly than in isolated platelets.4. It is concluded that in the organelles 5-HT and possibly histamine may be associated with ATP. Reserpine probably impairs the uptake of 5-HT at the level of the organelles (possibly by interfering with the association 5-HT/ATP), whereas imipramine seems to act preferentially on the cell membrane.     

A new steroidal saponin from Dioscorea panthaica

A new steroidal saponin and three known saponins were isolated from the rhizomes of Dioscorea panthaica. Their structures were elucidated as 3-O-[α-l-rhamnopyranosyl-(1 → 2)-β-d-glucopyranosyl]-26-O-β-d-glucopyranosyl-20,22-seco-25(R)-furosta-5-ene-20,22-dione-3β,26-diol (1), pregnadienolone-3-O-β-chacotriside (2), pseudoprotodioscin (3), and dioscoreside D (4) mainly by NMR techniques and chemical methods. The inhibitory activities of the saponins against α-glucosidase were investigated, and compound 2 was found to exhibit potent activity with IC₅₀ values of 0.04 ± 0.01 mM.     

Metabolic products of microorganisms. 254. Structure of the new nikkomycins pseudo-Z and pseudo-J

Two new nikkomycins were isolated from the fermentation broth of Streptomyces tendae Tü 901/PF 53+-3. These new metabolites, nikkomycins pseudo-Z (psi-Z,1) and pseudo-J (psi-J, 2) differ from the corresponding nikkomycins Z and J by a C-glycosidic bond between C-5 of uracil and C-1' of 5-amino-5-deoxy-D-allo-furanuronic acid instead of an N-glycosidic bond. The structure elucidation was achieved by two-dimensional NMR techniques and mass spectrometry.     

Metabolic fate of N6-benzyladenosine and N6-benzyladenosine-5'-phosphate in rats.

The radiolabeled antitumor nucleoside (14C-8)-N6-benzyladenosine and its (14C-8)-5'-phosphate were administered to rats intravenously, and their metabolic fate was studied. Twenty-nine percent of the radioactivity was recovered in the 48-hr urine collection after (14C-8)-N6-benzyladenosine administration. The following metabolites were isolated: unchanged N6-benzyladenosine (20%), adenine (12%), uric acid (5%), and N6-benzyladenine (0.3%). In the case of (14C-8)-N6-benzyladenosine-5'-phosphate, a total of 28% of the radioactivity was recovered in the 48-hr urine collection and the following metabolites were isolated: N6-benzyladenosine (40%), uric acid (12%), adenine (trace), and unidentified urea derivatives (30%). Metabolism of N6-benzyladenosine appears to involve N-debenzylation to some extent, followed by conversion to adenine and uric acid. N6-Benzyladenosine and its 5'-phosphate differ from other adenosine analogs in being retained in significant amounts by the animals.     

A new diepoxy-ent-kauranoid,rugosinin, from Isodon rugosus

A new diterpenoid, rugosinin (1), isolated from Isodon rugosus, with absolute configuration was proved by single-crystal X-ray diffraction analysis, to be the member of a rare class of C-20/C-7 and C-20/C-14 diepoxy- ent-kauranoids. Effusanin A (2), effusanin B (3), effusanin E (4), lasiokaurin (5) and oridonin (6) were found as known constituents of the genus Isodon with C-20/C-7 epoxy function. These compounds have exhibited DNA-damaging activity in assay which employed DNA-repair deficient (RAD 52Y) and repair proficient (RAD +) yeast strains.     

Prenylated flavonoids from the roots of Sophora flavescens with tyrosinase inhibitory activity

Prenylated flavonoids containing the resorcinol moiety were isolated as tyrosinase inhibitors from the roots of Sophora flavescens by activity-guided fractionation. Among the 12 compounds isolated, kuraridin, kurarinone and norkurarinol showed stronger inhibitory potencies (IC 50 = 1.1, 1.3 and 2.1 microM, respectively) than that of kojic acid (IC 50 = 11.3 microM), a well known tyrosinase inhibitor. Substitution of a lavandulyl or hydroxylavandulyl group at the C-8 position and a methoxy or hydroxy group at the C-5 position are essential for the inhibitory effect.     

Dioxygenated metabolites of cannabidiol formed by rat liver.

The metabolism of cannabidiol (CBD) was studied in vitro using a 10 000 g supernatant from rat liver. After removal of unchanged CBD and its monohydroxylated metabolites, a polar fraction remained from which ten dioxygenated metabolites were isolated. Mass spectrometry and nuclear magnetic resonance spectroscopy were used to identify the following metabolites: 6,7-dihydroxy-CBD, 1 inch,7-dihydroxy-CBD, 3 inch,7-dihydroxy-CBD, 4 inch,7-dihydroxy-CBD, 5 inch,7-dihydroxy-CBD, 2 inch,6-dihydroxy-CBD, 3 inch,6beta-dihydroxy-CBD, 4 inch, 6beta-dihydroxy-CBD (tentative), 3 inch-hydroxy-6-oxo-CBD, and 4 inch-hydroxy-6-oxo-CBD. The abundance of isolated dihydroxy metabolites reflected the quantity of monohydroxy metabolites that was previously found. In both series, 7-hydroxylation occurred to the greatest extent. Side chain hydroxylation occurred predominantly at C-4 inch and to a lesser degree at C-3 inch. Trace amounts of metabolites were hydroxylated at C-1 inch,-2 inch, or 5 inch.