龙舌兰属植物中甾族皂甙元的研究——Ⅱ.剑麻中甾族皂甙元的分离和鉴定

从海南岛栽培的剑麻叶中分离出10个已知的甾族化合物,即新替告皂甙元酮(II,Neo-tigogenone)、β-谷甾醇(V,β-Sitosterol)、新替告皂甙元(VI_a,Neotigogenin)、替告皂甙元(VI_b,Tigogenin)、剑麻皂甙元(VII_a,Sisalagenin)、海柯皂甙元(VII_b,Hecogenin)、5α-娠烷-3β、20β-二醇(IX,5a-Pregnan-3β,20β-diol)、洛柯皂甙元(X,Rockogenin)、12-表洛柯皂甙元(XI,12-Epirockogenin)和绿莲皂甙元(XVI,Chlorogenin)以及两个新的三羟基甾族皂甙元,即海南皂甙元(Hainangenin)和红光皂甙元(Hongguanggenin),根据质谱和核磁共振谱,这两个新皂甙元的结构初步分别定为3β,6α,23β-三羟基-5α,25R-螺甾烷(XVIII_a)和3β,6α,23α-三羟基-5α,25R-螺甾烷(XVIII_b),两者为C_(23)位的差向异构体。     

3β,17-二羟基-16-氨基-5α-雄甾烷四个立体异构体的合成

以表雄酮(1)为原料,由中间体3β-羟基-5α-雄甾-16-烯(3)合成3β,17α-二羟基-16α-氨基-5α-雄甾烷(7)和它的16β-氨基异构体(10a);由中间体3β-羟基-16α-溴-5α-雄甾-17-酮(12)合成3β,17β-二羟基-16α-氨基-5α-雄甾烷(21)和它的16β-氨基异构体(15)。上述四个立体异构体均通过化学转化以及波测试谱确证了其构型。     

抗生育甾体化合物——7α-甲基-17β-羟基-雌甾-5-烯-3-酮的合成

以△~4-雌甾烯-3,17-二酮(5)为原料,经四步得到17β-羟基-△~(4,6)-雌甾二烯-3-酮(4),(4)与二甲基铜锂试剂经1,6共轭加成合成了目的物7α-甲基-17β-羟基-雌甾-5-烯-3-酮(2b)。经药理试验表明2b具有明显的抗着床及抗早孕活性。     

生物标志化合物的合成研究 Ⅹ Ⅱ.4-甲基胆甾烷的合成新路线

本文报导以胆甾醇为原料经五步反应合成了4α—甲基—5α—胆甾烷与4β—甲基—5α—胆甾烷的混合物。其关键反应是利用胆甾—4—烯—3,6—二酮和重氮甲烷反应而引入4—甲基。     

针荔海绵Raphiedotethya sp.的次生代谢产物

从海南省三亚附近海域采集的针荔海绵Raphiedotethya sp.中分离到1个新神经酰胺和1个甾醇苷.经波谱分析和化学分析确定了它们的化学结构依次为:(2s,3S,4R,2'R)-N-(2'-羟基-二十二碳酰基)-1,3,4-三羟基-2.氨基-二十一烷(1)和4-O-[β-D-吡喃木糖苷]-孕甾-20-烯-3β,4α-二醇(2).     

海星动物化学成份的研究-罗氏海盘车中的皂苷元

报导了从罗氏海盘车中分离得到二个甾体皂苷元;20(R)-5α-孕甾-9(11)-烯-3β,6α,20-三醇和5α-孕甾-9(11)-烯-3β,6α-二醇-20-酮,并测定了它们的结构.     

一种合成4β-甲基-5α胆甾烷的新路线

本文报道以胆甾醇为原料经四步反应立体控制合成4β-甲基-5α-胆甾烷(6)的新路线。4-甲基胆甾-4-烯-3-酮(3)经Clemmensen还原,得4-甲基胆甾-4-烯(4)(65％)及4-甲基胆甾-3-烯(5)(15％)。用10％Pd-C在无水乙醇中室温催化氢化4,得6(70％)与4α-甲基-5α- 胆甾烷(7)(30％)的混合物;而选用Brown催化剂在同样条件下氢化4,得到产物6与7的比例为95:5。     

17α-羟基-16β-甲基-5,9(11)-孕甾二烯-3,20-二缩酮的D环高碳化

报导了17α-羟基-16β-甲基-4,9(11)孕甾二烯-3,20-二缩酮(1)用70%醋酸进行的水解反应. 结果得相应的3,20-二酮化合物(2). 当用98%醋酸处理(1)不能获得(2). 而是重排成17α-羟基-16β, 17β-二甲基-D-高孕甾二烯二酮(3). 当化合物(1)和(2)与含有CaCl2的70%醋酸反应获得16β, 17β-二甲-D-高-4,9(11), 15-孕甾三烯-3,17-二酮, 其得率取决于CaCl2的浓度和反应时间.     

3α-氨基-2β,17β-二羟基-16β-哌啶基-5α-雄甾烷和2β-氨基-3α,17β-二羟基-16β-哌啶基-5α-雄甾烷的合成

本文报道了3α-氨基-2β,17β-二羟基-16β-哌啶基-5α-雄甾烷和2β-氨基-3α,17β-二羟基-16β-哌啶基-5α-雄甾烷的合成方法。     

小花金挖耳地上部分萜类成分研究

本文首次报道对小花金挖耳地上部分化学成分的研究工作,采用硅胶柱色谱、Sephadex LH-20凝胶柱色谱、中压柱色谱和薄层制备色谱方法进行分离纯化,从中分离得到8个化合物:(1R,2S,4S,5R)-2,5-二羟基-p-薄荷烷(1),(1S,2S,4R,5S)-2,5-二羟基-p-薄荷烷(2),(3R,4R,6S)-3,6-二羟基-p-1-薄荷烯(3),5αH-桉烷-4(15),11(13)-二烯-12,8β-内酯(4),5α-羟基-桉烷-4(15),11(13)-二烯-12,8β-内酯(5),2α-羟基-5αH-桉烷-4(15),11(13)-二烯-12,8β-内酯(6),4β-羟基-1α,10βH-伪愈创木烷-11(13)-烯-12,8α-内酯(7),4-羰基-1α,10βH-伪愈创木烷-11(13)-烯-12,8α-内酯(8),利用波谱数据和理化性质鉴定了它们的结构.化合物1-3首次从天名精属植物中分离得到.     

Evaluation of the antiviral and antimicrobial activities of triterpenes isolated from Euphorbia segetalis

A phytochemical reinvestigation of the whole plant of Euphorbia segetalis yielded five tetracyclic triterpenes: 3beta-hydroxy-cycloart-25-en-24-one (1), cycloart-25-ene-3beta,24-diol (2), cycloart-23-ene-3beta,25-diol (3), lanosta-7,9(11),24-trien-3beta-ol (4) and lanosta-7,9(11),24(31)-trien-3beta-ol (5). beta-acetoxy-cycloart-25-en-24-one (1a) and glutinol (6), lupenone (7), dammaranodienol (9), cycloartenol acetate (10), 24-methylenecycloartanol acetate (11) and beta-sitosterol (12), isolated previously, were evaluated for their antiviral activities against Herpes simplex virus (HSV) and African swine fever virus (ASFV). Lupenone exhibited strong viral plaque inhibitory effect against HSV-1 and HSV-2. The in vitro antifungal and antibacterial activities of la, cycloart-23-ene-3beta,25-diol, 3-acetate (3a) and 6-12 were also investigated.     

Catalytic rearrangement of 1,2-orthoacetates of α-D-glucose and 20(S), 24(R)-epoxydammarane-3,12β,25-triols. I

The catalytic rearrangement of 20(S),24(R)-epoxydammarane-3,12β,25-triol 3-mono and 3,12-di(α-D-glucose 1,2-orthoacetate)s leads to the formation of the corresponding 12-mono- and 12,25-diglucosides. The anomalous regioselectivity of the catalytic rearrangements of orthoesters of 20(S),24(R)-epoxydammarane-3,12β,25-triols is evidently due to the influence of strong intramolecular hydrogen bonds. Details of the IR, PMR, and¹³C NMR spectra, and also the physicochemical constants, of the newly obtained compounds are given.     

Steroids and an oxylipin from an algicolous isolate of Aspergillus flavus

A new oxylipin, (8E,12Z)-10,11-dihydroxyoctadeca-8,12-dienoic acid (1), a new steroid, 3β,4α-dihydroxy-26-methoxyergosta-7,24(28)-dien-6-one (2), and four known steroids, episterol (3), (22E,24R)-ergosta-7,22-dien-3β,5α,6α-triol (4), (22E,24R)-ergosta-5,22-dien-3β-ol (5), and (22E,24R)-ergosta-4,6,8(14),22-tetraen-3-one (6), were isolated from the cultures of Aspergillus flavus, an endophytic fungus isolated from the marine red alga Corallina officinalis. Their structures and relative stereochemistry were elucidated by 1D, 2D NMR and mass spectroscopic techniques. 1 and 2 exhibited low activity to inhibit acetylcholinesterase and no activity against plant pathogenic fungi Colletotrichum lagenarium and Fusarium oxysporum.     

Structure elucidation and NMR assignments of two new triterpenoids from the stems of Paragonia pyramidata (Bignoniaceae)

Phytochemical investigation of dichloromethane (DCM) extract from the stems of Paragonia pyramidata var. pyramidata L. Rich. (Bur.) resulted in the isolation and characterization of two new triterpenoids 3β,19β-dihydroxylup-12, 20(29)-diene-28-oic acid (1) and 3β,19β-dihydroxylup-12-en-28-oic acid (2), three known triterpenoids lupeol (3), spinosic acid A (4) and oleanolic acid (5), together with four known steroids (20R)-22E-24-ethylcholesta-4,22-dien-3-one (6), (20R)-24-ethylcholest-4-en-3-one (7), stigmasterol (8) and β-sitosterol (9). HREIMS, GC-MS and NMR experiments including HSQC, HMBC, COSY and NOESY were used for the determination of the structures and NMR spectral assignments. This is the first report about the chemical constituents for this plant.     

Photosensitized Oxygenation of Abieta-7,9(11)-dien-13β-ol

Dehydration of abiet-8-ene-7β, 13β-diol (ibozol, 1 ) leads to abieta-7,9(11)-dien-13β-ol ( 2 ) which aromatizes slowly to the known abieta-8,11,13-triene ( 3 ). Photosensitized oxygenation of the heteroannular diene 2 yields a mixture from which three compounds were identified; abiet-7-ene-9α, 11α, 13β-triol ( 4 ), abieta-8,11,13-trien-7-one ( 5 ), and abieta-8,11,13-trien-7α-ol ( 6 ).     

Glycosylation of triterpenoids of the dammarane series. VI. 3-mono- and 3,12-di-O-β-D-glucopyranosides of pyxinol

The condensation of 20(S),24(R)-epoxydammarane-3β,12β,25-triol with α-acetobromoglucose in the presence of silver oxide, silver zeolite, and silver oxide with 4 Å molecular sieves has been studied. It has been established that the reaction takes place nonregioselectively and leads to a mixture of acetylated mono-, di-, and triglucosides with a predominance of the 3-O-mono- and 3,12-di-O-glucosides. The structures of the newly obtained 3-O-mono- and 3,12-di-O-glucosides have been established on the basis of the results of IR and¹H and¹³C NMR spectroscopy.     

Synthese eines steroidischen 17 β-Pyrrolinons. Partialsynthetische Versuche in der Reihe der Herzgifte. 10.Mitteilung

Synthesis of a steroidal 17 β-pyrrolinone We describe the synthesis of 4′-(3 β-hydroxy-androst-5-ene-17 β-yl)-3′-pyrrolin-2′-one (6) starting from 3β-acetoxy-21-hydroxy-pregn-5-ene-20-one (1).     

Two new dammarane triterpenoids from Kageneckia angustifolia D. Don

Two new dammarane triterpenoids, 20R,21-epoxydammar-24-ene-3,23-dione and 20R,21-epoxy-3beta-hydroxydammar-24-ene-23-one have been isolated from the aerial parts of Kageneckia angustifolia D. Don, Rosaceae, along with the previously reported triterpenoids oleanolic acid and 3beta-(beta-D-glucosyloxy)-16alpha,23alpha-epoxycucurbita-5,24-dien-11-one and the phenolic prunasin. The structures of these compounds were established by MS, 1D- and 2D-NMR experiments, and the structure of the new compounds were confirmed by X-ray diffraction analysis.     

Microbial Metabolism of the Diterpene Sclareol: Oxidation of the A Ring by Septomyxa affinis

Microbial metabolism of the diterpene sclareol ( 1 ) was studied. Screening studies have shown a number of microorganisms capable of metabolizing 1 . Preparative-scale fermentation with Septomyxa affinis ATCC 6737 has resulted in the production of three fungal metabolites that have been characterized by 2D-NMR techniques and chemical reactions. These metabolites have been identified as 8α,13β-dihydroxylabd-14-en-3-one ( 2 ), labd-14-ene-3β.8α,13β-triol ( 4 ), and labd-14-ene-2α,8α,13β-triol ( 6 ).     

Six new dammarane-type triterpene saponins from the leaves of Panax ginseng

Six new minor saponins, together with known ginsenosides, were isolated from the leaves of Panax ginseng. The new saponins were named as ginsenoside-Rh5, -Rh6, -Rh7 -Rh8, -Rh9 and -Rg7, and their structures were elucidated on the basis of chemical and physicochemical evidence to be as follows: ginsenoside-Rh5: 3beta,6alpha,12beta,24zeta-tetrahydroxy-dammar-20(22),25-diene 6-O-beta-D-glucopyranoside (1), -Rh6: 3beta,6alpha12beta,20(S)-tetrahydroxy-25-hydroperoxy-dammar-23-ene 20-O-beta-D-glucopyranoside (2), -Rh7: 3beta,7beta,12beta,20(S)-tetrahydroxy-dammar-5,24-diene 20-O-beta-D-glucopyranoside (3), -Rh8: 3beta,6alpha,20(S)-trihydroxy-dammar-24-ene-12-one 20-O-beta-D-glucopyranoside (4), -Rh9: 3beta,6alpha,20(S)-trihydroxy-12beta,23-epoxy-dammar-24-ene 20-O-beta-D-glucopyranoside (5) and -Rg7: 3-O-beta-D-glucopyranosyl 3beta,12beta,20(S),24(R)-tetrahydroxy-dammar-25-ene 20-O-beta-D-glucopyranoside (6).