Dimeric aporphine alkaloids of Phoenicanthus obliqua from Sri Lanka.

A new dimeric aporphine alkaloid, phoenicanthusine (1), and six known alkaloids were isolated from the stem bark of Phoenicanthus obliqua. The structure of 1 was elucidated by 1D ((1)H, (13)C) and 2D ((1)H-(1)H COSY, HMQC, HMBC, and NOESY) NMR and HRMS studies. Phoenicanthusine represents the first example of a N-6--C-4' and C-7--C-5' linked dimeric aporphine alkaloid.     

Iridoids from the green leaves of Eucommia ulmoides

The bark of Eucommia ulmoides is a well-known crude drug in oriental medicine, and its leaves have been consumed as a beverage. From the green leaves of this plant, three new iridoids (1-3) were isolated, together with 12 known compounds. Compound 1 is the first iridoid possessing a saturated bond between C-3 and C-4 and having an ether linkage between C-3 and C-2 of the glucose unit. Furthermore, 2 and 3 may be regarded as the first naturally occurring conjugates of an iridoid and an amino acid.     

狭序唐松草中三类生物碱对血小板聚集的影响

目的：研究狭序唐松草中三类生物碱ＢＢＩ、ＡＢＩ、ＡＰ的抗血小板聚集作用。方法：采用比浊法进行体外抗血小板聚集研究。结果：ＢＢＩ类和ＡＢＩ类能够抑制ＡＤＰ、Ｃｏｌｌ诱导的大鼠血小板聚集,ＡＰ类与正常对照相比则无显著差异。结论：ＢＢＩ类和ＡＢＩ类具有抗血小板聚集作用。且ＢＢＩ类作用强于ＡＢＩ类,ＡＰ类则几乎无作用。     

Lakshminine,a new rare oxoisoaporphine alkaloid from Sciadotenia toxifera,and structural revisions of telazoline and teladiazoline,two related oxoaporphines from Telitoxicum peruvianum and T. glaziovii

Lakshminine (1), a novel oxoisoaporphine alkaloid possessing a C-6 amine substituent, was isolated from a basic fraction from the woody vines (collected from two bush-ropes) of Sciadotenia toxifera. This compound represents the first documented occurrence of an oxoisoaporphine from any Menispermaceae species other than Menispermum dauricum. The structures of two related aporphine alkaloids, telazoline (3) and teladiazoline (5), were revised on the basis of a comparison of their spectral data with that of lakshminine (1).     

陵水暗罗枝、叶中的阿朴菲生物碱

目的:对陵水暗罗Polyalthia nemoralis枝、叶中的阿朴菲生物碱进行分离和鉴定,并测细胞毒活性.方法:采用硅胶和凝胶柱色谱方法进行分离纯化,利用波谱数据和理化常数鉴定化合物的结构;MTT法测试细胞毒活性.结果:从乙醇提取物中分离鉴定了5个阿朴菲生物碱,分别为bidebiline A(1),annobrajne(2),lanuginosine(3),鹅掌楸碱(liriodenine,4),oxostephanosine(5).结论:化合物2,5为首次从该属中分到,1,3,4为首次从该植物中分离得到;化合物3～5对多种癌细胞生长有抑制作用.     

Iridoids from Rothmannia macrophylla.

A new iridoid glucoside with an ether linkage between C-3 and C-10 and a novel nonglycosidic iridoid with an ether linkage between C-3 and C-6 and a lactonic linkage at C-1, named macrophylloside (1) and macrophyllide (2), respectively, were isolated from the leaves of Rothmannia macrophylla, along with six known iridoids. Their structures were established by NMR and MS spectroscopies.     

瓜馥木中阿朴菲类生物碱的研究

目的:研究广西特色植物瓜馥木Fissistigma oldhamii(Helms.)Merr.中的阿朴菲类生物碱。方法:利用各种色谱技术进行分离纯化,根据理化性质和光谱数据进行结构鉴定。结果:从瓜馥木总生物碱部分分离纯化得到4个阿朴菲类生物碱,分别鉴定为:1,2-亚甲二氧基-N-甲氧酰基-阿朴菲生物碱(romucosine)(Ⅰ),甲氧番荔枝碱(xylopine)(Ⅱ),1,2,3-三甲氧基氧化阿朴菲生物碱(O-methylmoschatoline)(Ⅲ),毛叶含笑碱(oxoxylopine)(Ⅳ)。结论:化合物Ⅰ为首次从该植物中分离得到。     

Alkaloids from Eschscholzia californica and their capacity to inhibit binding of [3H]8-Hydroxy-2-(di-N-propylamino)tetralin to 5-HT1A receptors in Vitro

A 70% ethanol extract of California poppy (Eschscholzia californica) was able to bind to 5-HT(1A) and 5-HT(7) receptors at 100 mug/mL. The subsequent isolation procedure yielded the known alkaloids californidine (1), escholtzine (2), N-methyllaurotetanine (3), caryachine (4), and O-methylcaryachine (5), along with a new pavine alkaloid, 6S,12S-neocaryachine-7-O-methyl ether N-metho salt (7). The structure of 7 was determined by spectroscopic data interpretation, while the absolute stereochemistry was determined by means of circular dichroism. From the results obtained from the radioligand-binding assay of the pure compounds, including the commercially available protopine (6), it was evident that the activity on the 5-HT(1A) receptor was at least partly due to the presence of the aporphine alkaloid 3, which showed the highest inhibition of [(3)H]8-hydroxy-2-(di-N-propylamino)tetralin ([(3)H]8-OH-DPAT) binding with an EC(50) value of 155 nM and a K(i) of 85 nM.     

荷叶中的一个新阿朴啡型生物碱

目的荷叶为睡莲科植物莲Nelumbo nucifera的叶,本实验对其化学成分进行研究。方法应用多种色谱技术进行分离纯化,通过理化方法和波谱数据进行结构鉴定。结果分离鉴定出9个生物碱类成分,分别为2-羟基-1-甲氧基-6-甲基-6a,7-去氢阿朴啡(2-hydroxy-1-methoxy-6-methyl-6a,7-dehydroaporphine,1)、杏黄罂粟碱(armepavine,2)、去氢莲碱(dehydroroemerine,3)、去氢荷叶碱(dehydronuciferine,4)、2-羟基-1-甲氧基阿朴啡(2-hydroxy-1-methoxyaporphine,5)、鹅掌楸碱(liriodenine,6)、原荷叶碱(pronuciferine,7)、莲碱(roemerine,8)和荷叶碱(nuciferine,9)。结论化合物1为一新的阿朴啡型生物碱,命名为睡莲碱(nelumnucine)。     

Ancistrotanzanine C and related 5,1'- and 7,3'-coupled naphthylisoquinoline alkaloids from Ancistrocladus tanzaniensis

Three new naphthylisoquinoline alkaloids, the 7,3'-coupled ancistrotanzanine C (6), the 5,1'-coupled O-methylancistrocladinine (7), and the likewise 5,1'-coupled O,N-dimethylancistrocladine (8, previously known only as a partial-synthetic compound), have been isolated from the highland liana Ancistrocladus tanzaniensis, along with the two known 7,3'-coupled naphthylisoquinoline alkaloids ancistrocladidine (4) and ancistrotectorine (5). All of the compounds are S-configured at C-3 and bear an oxygen at C-6, and thus belong to the so-called Ancistrocladaceae type, similar to 1-3 previously isolated from this newly discovered plant species. The structural elucidation was achieved by chemical, spectroscopic, and chiroptical methods. The biological activities of the alkaloids against the pathogens causing malaria tropica, leishmaniasis, Chagas' disease, and African sleeping sickness were evaluated.     

Terpenoid indole alkaloids from Winchia calophylla

Three new indole alkaloids, N(4)-demethyl-12-methoxyalstogustine (1), 17-carboxyl-N(4)-methylechitamidine chloride (2), and 17-carboxyl-12-methoxy-N(4)-methylechitamidine chloride (3), along with 15 known alkaloids, were isolated from the ethanolic extract of the stem bark of Winchia calophylla. The structures of 1-3 were elucidated on the basis of spectroscopic means and chemical methods. The determination of relative configurations at C-19 and C-20 for 1-3 was aided by 13C NMR spectroscopic data. The absolute configurations of alkaloids 1-3 were determined by direct comparison of their CD spectra with those of known alkaloids. All the alkaloids were tested in cytotoxic assays against P-388 and A-549 tumor cell lines, and only two of them showed weak activity against the A-549 cell line.     

Daphnipaxianines A-D, alkaloids from Daphniphyllum paxianum

Four new Daphniphyllum alkaloids, daphnipaxianines A-D ( 1- 4), along with six known ones, have been isolated from the leaves and fruits of Daphniphyllum paxianum. Daphnipaxianines A and B ( 1, 2), a pair of epimers differing at C-10, are the first caliciphylline A type Daphniphyllum alkaloids with a Delta (9(15))-unsaturated cyclic ketone unit, and daphnipaxianine D ( 4) is the first yuzurine-type Daphniphyllum alkaloid containing a hexacyclic ring system. The structures of these alkaloids were characterized by spectroscopic methods, especially 2D NMR techniques. A single-crystal X-ray diffraction analysis was used to confirm the structure of 1.     

Resin glycosides from the herbal drug jalap (Ipomoea purga)

Three new resin glycosides, purginosides I and II (1 and 2) and purgin I (3), were isolated from the aerial parts of Ipomoea purga and purified by preparative-scale recycling HPLC from a chloroform-soluble extract. Their structures were established through NMR spectroscopy and mass spectrometry. Purginosides I and II (1 and 2) are partially acylated branched pentasaccharides derived from operculinic acid A, which is composed of one D-fucose, one D-glucose, and three l-rhamnose units. The site of the aglycon macrolactonization is at C-2 of the second saccharide (rhamnose). In both compounds 1 and 2, three different esterifying residues were located at C-2 of the second rhamnose unit and at C-2 (or C-3) and C-4 on the third rhamnose moiety. The acylating residues were characterized as trans-cinnamic, n-decanoic, and either (+)-(2S)-2-methylbutanoic or n-hexanoic acid. Purgin I (3) was found to be an ester-type dimer of operculinic acid A, acylated by n-dodecanoic, (+)-(2S)-2-methylbutanoic, and trans-cinnamic acids at the same oligosaccharide core positions found in compounds 1 and 2. The site of lactonization by the aglycon in unit A was placed at C-2 of the second saccharide. The position for the ester linkage for the monomeric unit B on the macrocyclic unit A was identified as C-4 of the terminal glucose. This is the first report on the isolation, purification, and structure elucidation of intact individual resin glycoside constituents from the herbal drug jalap.     

Batatins I and II, ester-type dimers of acylated pentasaccharides from the resin glycosides of sweet potato

Batatins I (1) and II (2), two ester-type dimers of acylated pentasaccharides, have been isolated by recycling HPLC from the hexane-soluble extract of sweet potato (Ipomoea batatas var. batatas). The structures were elucidated by a combination of high-resolution NMR spectroscopy and mass spectrometry. Complete analysis and unambiguous assignments of the 1H and 13C NMR spectra of 1 and 2 were achieved by 2D shift correlation measurements. The glycosidic acid forming each branched pentasaccharide monomeric unit was confirmed as simonic acid B. Three different fatty acids esterify this core at the same positions in both batatins: C-2 on the second rhamnose unit and C-4 and C-2 (or C-3) on the third rhamnose moiety. The acylating residues were identified as (+)-(2S)-methylbutanoic, dodecanoic (lauric), and cinnamic acids. The site of lactonization by the aglycon in unit A was placed at C-3 of the second saccharide. The position for the ester linkage for monomeric unit B on the macrocylic unit A was identified as C-3 of the terminal rhamnose' '. Through spectroscopic simulation of these complex oligosaccharides, the chemical shifts and coupling constants were deduced for the overlapped proton resonances with a non-first-order resolution. The experimental NMR spectroscopic values registered for batatinoside I (3), a new polyacylated macroyclic pentasaccharide also isolated from this plant, were used as the starting point for spectral simulation of 1 and 2. Both polymers 1 and 2 represent dimers of compound 3.     

Perhentidines A-C: macroline-macroline bisindoles from Alstonia and the absolute configuration of perhentinine and macralstonine

Three new bisindole alkaloids of the macroline-macroline type, perhentidines A-C (1-3), were isolated from the stem-bark extract of Alstonia macrophylla and Alstonia angustifolia. The structures of these alkaloids were established on the basis of NMR and MS analyses. The absolute configurations of perhentinine (4) and macralstonine (5) were established by X-ray diffraction analyses, which facilitated assignment of the configuration at C-20 in the regioisomeric bisindole alkaloids perhentidines A-C (1-3). A potentially useful method for the determination of the configuration at C-20 based on comparison of the NMR chemical shifts of the bisindoles and their acetate derivatives, in these and related bisindoles with similar constitution and branching of the monomeric units, is also presented.     

Vasorelaxing alkaloids and flavonoids from Cassytha filiformis

Two new aporphine alkaloids, isofiliformine ( 1) and cassythic acid ( 3), along with 22 known compounds were isolated from whole herb of Cassytha filiformis. Cassythic acid ( 3), cassythine ( 4), neolitsine ( 7), and dicentrine ( 8) had potent vasorelaxing effects on precontracted rat aortic preparations with mean IC 50 values between 0.08 and 2.48 microM. Compounds 1, 1,2-methylenedioxy-3,10,11-trimethoxyaporphine ( 2), (-)- O-methylflavinatine ( 10), (-)-salutaridine ( 11), isohamnetin-3- O-beta-glucoside, and isohamnetin-3- O-rutinoside exerted moderate vessel-relaxing activities with IC 50 values from 16.50 to 32.81 microM at the test concentrations.     

Two new natural azafluorene alkaloids and a cytotoxic aporphine alkaloid from Polyalthia longifolia

The stem and stem bark of Polyalthia longifolia afforded the cytotoxic aporphine alkaloid liriodenine [1], as well as two aporphine alkaloids, noroliveroline [2] and oliveroline-beta-N-oxide [3] and three azafluorene alkaloids, darienine [4], polyfothine [6], and isooncodine [7], which are not bioactive. Polyfothine [6] and isooncodine [7] are new natural compounds.     

德钦乌头中的二萜生物碱

目的 研究乌头属植物德钦乌头Aconitum ouvrardianum根的二萜生物碱类化学成分.方法 采用反复硅胶柱色谱进行分离纯化,根据谱学数据和对照TLC分析鉴定化合物的结构.结果 从德钦乌头根的醋酸乙酯提取物中分离得到12个化合物,分别鉴定为塔拉乌头胺(1)、彭乌碱乙(2)、卡马考宁(3)、黄草乌碱亭(4)、粗茎乌头碱甲(5)、贡乌生(6)、14-乙酰黄草乌碱亭(7)、展花乌头碱(8)、黄乌宁(9)、膝乌亭丁(10)、异塔拉乌头定(11)、翠雀它灵(12).结论 12个化合物均为C-3位或C-6位无含氧取代的C19-二萜生物碱,且均为首次从该植物中分离得到.乌头碱型C19-二萜生物碱为德钦乌头药材的主要药用化学成分.     

Bioactive constituents of the roots of Polyalthia cerasoides

A new dimeric aporphine alkaloid, bidebiline E (1), and a new natural product, octadeca-9,11,13-triynoic acid (2), along with three known sesquiterpenes, alpha-humulene (3), caryophyllene oxide (4), and (-)-alpha-cadinol (5), and four known isoquinoline alkaloids, laudanosine (6), codamine (7), laudanidine (8), and reticuline (9), were isolated from the roots of Polyalthia cerasoides. The structures of compounds 1 and 2 were established on the basis of their 1D and 2D NMR spectroscopic data. Among these isolates, 1, 2, 4, 7, and 8 exhibited antimalarial activity against Plasmodium falciparum, while 1- 3 showed antimycobacterial activity against Mycobacterium tuberculosis using in vitro assays.     

Daphniyunnines A-E, alkaloids from Daphniphyllum yunnanense

The first chemical study on the stems and leaves of Daphniphyllum yunnanense led to the isolation of five new alkaloids, daphniyunnines A-E (1-5). Daphniyunnines B-E (2-5) are four unusual C-22 nor-Daphniphyllum alkaloids. The structures of these alkaloids were characterized by spectroscopic methods, especially 2D NMR techniques. A single-crystal X-ray diffraction analysis was used to confirm the structure of 1. Daphniyunnine D (4) showed cytotoxicity against two tumor cell lines, P-388 and A-549, with IC(50) values of 3.0 and 0.6 microM, respectively.