Minor sesquiterpene lactones from Centaurea pullata and their antimicrobial activity

The aerial parts of Centaurea pullata afforded, in addition to the previously isolated sesquiterpene lactones, 11beta,13-dihydrocnicin and 11beta,13-dihydro-19-desoxycnicin, three minor sesquiterpene lactones, namely, a new germacranolide, 8alpha-O-(4-acetoxy-5-hydroxyangeloyl)-11beta,13-dihydrocnicin, and two new eudesmanolides, 8alpha-O-(4-hydroxy-2-methylenebutanoyloxy)-11beta,13-dihydrosonchucarpolide and 8alpha-O-(4-hydroxy-2-methylenebutanoyloxy)-11beta,13-dihydro-4-epi-sonchucarpolide. The in vitro antimicrobial activity of all isolated sesquiterpene lactones was tested against six bacteria and eight fungal species, using a microdilution method. All compounds tested showed greater antibacterial and antifungal activities than the positive controls used.     

Cytotoxic sesquiterpene lactones from Eupatorium lindleyanum

Ten new guaiane type sesquiterpene lactones, namely, eupalinilides A-J (1-10), as well as nine known compounds, eupachinilide C (11), eupachifolin D (12), eupachinilide E (13), 2alpha-hydroxyeupatolide (14), 3-deacetyleupalinin A (15), heliangine (16), 8beta-tigloyloxy-2,3-seco-6betaH,7alphaH-helianga-4Z,11(13)-diene-3,10beta;6, 12-diolid-2-oic acid (17), 8beta-(4'-hydroxytigloyloxy)-3beta,14-dihydroxy-6betaH,7alphaH-germacra-1(10)Z,4Z,11(13)-trien-6,12-olide (18), and 8beta-tigloyloxy-3beta,14-dihydroxy-6betaH,7alphaH-germacra-1(10)Z,4E,11(13)-trien-6,12-olide (19), were isolated from the whole plant of Eupatorium lindleyanum. Eupalinilides B (2), C (3), E (5), F (6), and I (9) have been tested for cytotoxicity against P-388 and A-549 tumor cell lines. The results showed that eupalinilides B (2) and E (5) demonstrated potent cytotoxicity. The structures of these compounds were determined by spectroscopic methods including 1D and 2D NMR spectra.     

Sesquiterpene lactones from Anthemis altissima and their anti-Helicobacter pylori activity

Seven sesquiterpene lactones, (-) sivasinolide (1), a new naturally occurring eudesmanolide (altissin, 2), desacetyl-beta-cyclopyrethrosin (3), tatridin-A (4), 1-epi-tatridin B (5), 1alpha,10beta-epoxy-6-hydroxy-1,10H-inunolide (6), and spiciformin (7), were isolated from Anthemis altissima. Also isolated were 10 known flavonoids, namely, apigenin (8), kaempferol 4'-methyl ether (9), quercetin (10), quercetin 3-methyl ether (11), isorhamnetin (12), rhamnetin (13), 6-hydroxyquercetin 3,6,4'-trimethyl ether (14), isoquercetrin (15), taxifolin (16), and eriodictyol (17), and one phenolic acid, chlorogenic acid (18). The structure and the stereochemistry of compound 2 were deduced by spectroscopic methods. The in vitro activity of the sesquiterpene lactones (1-5) against Helicobacter pylori, as well as against three Gram-positive and three Gram-negative bacteria growing aerobically, was tested using the microdilution method. Compounds 8-18 have also been tested against H. pylori.     

The gastric cytoprotective effect of several sesquiterpene lactones

The aerial part of Artemisia douglasiana, used in folk medicine as a cytoprotective agent against the development of peptic ulcer, was studied, its active principle dehydroleucodine [1] isolated, and its pharmacological properties analyzed. In order to establish whether or not the reported activity is particular to sesquiterpene lactones, the study of the cytoprotective activity of several related guaianolides and pseudoguaianolides from plants was undertaken. Ludartin [3], 8-angeloyloxy-3-hydroxyguaia-3(15),10(14),11(13)-trien-6,12- olide [4], hymenin [5], mexicanin I [6], helenanin [7], and 9-O-desacetylsparthulin-2-O-angelate [8] were found to exhibit protection. Desacetoxymatricarin [2] did not show cytoprotective activity. The results obtained from the different sesquiterpene lactones studied suggest that the presence of the alpha-methylene-gamma-lactone moiety is, in principle, a requirement for the observed antiulcerogenic activity.     

Labdane-type diterpenes and a nordrimane-type sesquiterpene from the stem bark of Thuja standishii

Two new labdane-type diterpene aldehydes, 15-oxolabda-8(17),11(Z), 13(E)-trien-19-oic acid (1) and 15-oxolabda-8(17),11(Z), 13(Z)-trien-19-oic acid (2), and a new nordrimane-type sesquiterpene, 12-oxo-11-nordrim-8-en-14-oic acid (3), along with a known diterpene, 15-nor-14-oxolabda-8(17),12(E)-dien-19-oic acid (4), were isolated from the stem bark of Thuja standishii. The structures of 1-3 were established by spectroscopic methods.     

Benzoic acid derivatives from Piper species and their antiparasitic activity

Piper glabratum and P. acutifolium were analyzed for their content of main secondary constituents, affording nine new benzoic acid derivatives (1, 2, 4, 5, 7, and 10-13), in addition to four known compounds (3, 6, 8, and 9). Their structures were elucidated on the basis of spectroscopic data. Riguera ester reactions and optical rotation measurements established the new compounds as racemates. In the search for antiparasitic agents, the compounds were evaluated in vitro against the promastigote forms of Leishmania spp., Trypanosoma cruzi, and Plasmodium falciparum. Among the evaluated compounds, methyl 3,4-dihydroxy-5-(3'-methyl-2'-butenyl)benzoate (7) exhibited leishmanicidal effect (IC50 13.8-18.5 microg/mL) against the three Leishmania strains used, and methyl 3,4-dihydroxy-5-(2-hydroxy-3-methylbutenyl)benzoate (1), methyl 4-hydroxy-3-(2-hydroxy-3-methyl-3-butenyl)benzoate (3), and methyl 3,4-dihydroxy-5-(3-methyl-2-butenyl) benzoate (7) showed significant trypanocidal activity, with IC50 values of 16.4, 15.6, and 18.5 microg/mL, respectively.     

水朝阳旋覆花的倍半萜内酯类化合物

目的:研究水朝阳旋覆花Inula helianthus-aquatica地上部分中的倍半萜内酯类化学成分。方法:应用硅胶柱色谱,Sephadex LH-20柱色谱,以及高效液相制备色谱等方法分离和纯化化合物,再通过运用光谱学方法,结合化合物的理化性质来鉴定结构。结果:从水朝阳旋覆花的地上部分分离得到7个倍半萜内酯类和4个其他类的化合物,并且依次鉴定为2-desoxy-4-epi-pulchellin(1),6-acetoxy-4-hydroxy-1,10H-pseudoguaia-11(13)-en-12,8-olide(2),4-acetoxy-6-hydroxy-1,10H-pseud-oguaia-11(13)-en-12,8-olide(3),8-epi-inuviscolide(4),2,3,11,13-tetrahydroaromaticin(5),11,13-dihydro-ergolide(6),4-epip-ulchellin-2-O-acetate(7),7-差向黑麦草内酯(8),黑麦草内酯(9),β-谷甾醇(10),胡萝卜苷(11)。结论:所有化合物均为首次从该植物中分离得到。     

Neoclerodane diterpenoids from Croton eluteria

Five new neoclerodane diterpenoids, rel-(3R,4S,5R,7R,8S,9R,10S,12R,20S)-7-acetoxy-15,16,12,20-diepoxy-3,4-dihydroxy-20-methoxyneocleroda-13(16),14-diene (1), rel-(3R,4S,5R,7R,8S,9R,10S,12R,20S)-7-acetoxy-15,16,12,20-diepoxy-3,4,20-trihydroxyneocleroda-13(16),14-diene (2), rel-(3R,4S,5S,6R,7S,8S, 9R,10S,12R,20S)-6,7-diacetoxy-3,4,15,16,12,20-triepoxy-20-hydroxyneocleroda-13(16),14-diene (3), rel-(3R,4S,5R,7R,8S,9R,10S,12R,20S)-7-acetoxy-3,4,15,16,12,20-triepoxy-20-hydroxyneocleroda-13(16),14-diene (4), and rel-(3R,4S,5R,7R,8S,9R,10S,12R,20R)-7,20-diacetoxy-3,4,15,16,12,20-triepoxyneocleroda-13(16),14-diene (5), have been isolated from the bark of Croton eluteria. The structures of the compounds 1-5 (cascarillins E-I) were determined by spectroscopic data interpretation.     

Terpenoids and a diarylheptanoid from Zingiber ottensii

Four new terpenoids and a diarylheptanoid were isolated together with 16 known compounds from rhizomes of Zingiber ottensii. The structures of the new compounds were determined to be 1,10,10-trimethylbicyclo[7,4,0]tridecane-3,6-dione (1), (E)-14-hydroxy-15-norlabda-8(17),12-dien-16-al (2), (E)-labda-8(17),12,14-trien-15(16)-olide (3), (E)-14,15,16-trinorlabda-8(17),11-dien-13-oic acid (4), and rel-(3R,5S)-3,5-dihydroxy-1-(4-hydroxy-3-methoxyphenyl)-7-(3, 4-dihydroxyphenyl)heptane (5) by spectroscopic evidence.     

Sesquiterpenes and aliphatic diketones from cultures of the basidiomycete Conocybe siliginea

Five new tremulane-type sesquiterpenes, 11,12-dihydroxy-1-tremulen-5-one (1), 11,12-epoxy-12beta-hydroxy-1-tremulen-5-one (2), 5alpha,12-dihydroxy-1-tremulen-11-yl 2(S)-pyroglutamate (3), 2alpha,11-dihydroxy-1(10)-tremulen-5,12-olide (4), and 10beta,11-dihydroxy-5,6- seco-1,6(13)-tremuladien-5,12-olide (5), as well as three new aliphatic diketones, 2,3-dihydroxydodecane-4,7-dione (9 and 10) and 1-hydroxydecane-2,5-dione (11), together with three known sesquiterpene analogues, tremulenediol A (6), conocenol B (7), and conocenolide A (8), were isolated from cultures of the basidiomycete Conocybe siliginea.     

Cytotoxic flavonoids from Platymiscium floribundum

Two new isoflavonoids, 7-hydroxy-6,4'-dimethoxy-isoflavonequinone (1) and 2'-hydroxy-6,4',6' ',4' '-tetramethoxy-[7-O-7' ']-bisisoflavone (2), and seven other known flavonoids, 3-hydroxy-9-methoxypterocarpan (medicarpin), 3,10-dihydroxy-9-methoxypterocarpan, 3,9-dimethoxypterocarpan (homopterocarpin) (3), 2,3,9-trimethoxypterocarpan (4), 3,4-dihydroxy-9-methoxypterocarpan (vesticarpan) (5), 2',4,4'-trihydroxychalcone (isoliquiritigenin), and 7,4'-dihydroxyflavanone (liquiritigenin) (6), were isolated from the heartwood of Platymiscium floribundum. The structures of compounds 1 and 2 were established by spectroscopic methods. Compounds 3-6 showed cytotoxic activity when evaluated against five human cancer cell lines in vitro.     

毛叶香茶菜中的二萜化合物

目的：对河南产毛叶香茶菜化学成分进行研究。方法：运用各种色谱技术和波谱分析对其化学成分进行分离鉴定。结果：分离鉴定了20个二萜化合物。结论：化合物1—3为三个新的对映-贝壳杉烷二萜类化合物，结构分别为7β，15β，16β—三羟基—6β，17β—二乙酰氧基—7α，20-环氧—对映—贝壳衫烷(1)、16（S)—6β，11α，17β—三羟基-6，20-环氧—1α，7β—内酯—6，7—断裂—对映—贝壳杉-15酮(2)和6α，11α—二海基—1α—乙酰氧基—7，20内酯—6，7—断裂—对映—贝壳杉—16—烯—15—酮(3)，依次命名为毛叶香茶菜丙素、丁素和戊素；化合物4和5为—对新化合物，其结构为3α，15α，1β6，17β，18β—五羟基。对映—松香—7(8)—烯的丙酮化物，其丙酮化缩合部分互为对映体，分别命名为毛叶香茶菜庚素(4)和辛素(5)。     

Ymf 1029A-E, preussomerin analogues from the fresh-water-derived fungus YMF 1.01029

Five new preussomerin analogues, ymf 1029A (1), B (2), C (3), D (4), and E (5), were isolated from the liquid cultures of an unidentified freshwater fungus YMF 1.01029, along with four known compounds, preussomerin C (6), preussomerin D (7), (4RS)-4,8-dihydroxy-3,4-dihydronaphthalen-1(2H)-one (8), and 4,6,8-trihydroxy-3,4-dihydronaphthalen-1(2H)-one (9). The structures of new metabolites were determined by analysis of NMR and MS data and by analogy with the data for the known bis-spirobisnaphthalene preussomerins. In vitro immersion experiments showed that these metabolites displayed weak nematicidal activity against Bursaphelenchus xylophilus, while compound 7 was the most potent. This is the first report of these compounds, which antagonize the Bursaphelenchus xylophilus nematode.     

Lanostane and hopane triterpenes from the entomopathogenic fungus Hypocrella sp. BCC 14524

Seven new lanostane-type triterpenes, hypocrellols A-G (1-7), and six new hopane-type triterpenes, 7β,15α-dihydroxy-22(29)-hopene (8), 3β,7β-dihydroxy-22(29)-hopene (9), 3β-acetoxy-15α-hydroxy-22(29)-hopene (10), 3β,7β,15α,22-tetrahydroxyhopane (11), 3β-acetoxy-7β,15α,22-trihydroxyhopane (12), and 7β,15α,22-trihydroxyhopane (13), were isolated from the scale insect pathogenic fungus Hypocrella sp. BCC 14524. The structures of the new compounds were elucidated by analyses of the NMR spectroscopic and mass spectrometry data. The structure of 1 was confirmed by X-ray crystallography.     

Ardisinones A-E, novel diarylundecanones from Ardisia arborescens

A phytochemical study on an ethanol extract of Ardisia arborescens resulted in the isolation of five new diarylundecanones, named ardisinones A-E (1-5). The structures were established by HRESIMS and NMR ((1)H, (13)C, DEPT, HSQC, HMBC) as 11-(2-acetoxy-6-hydroxyphenyl)-1-(2,4,6-trihydroxyphenyl)undecan-1-one (1), 11-(2-acetoxy-6-hydroxyphenyl)-1-(2,6-dihydroxy-4-methoxyphenyl)undecan-1-one (2), 1-(2,6-dihydroxy-4-methoxyphenyl)-11-(2,6-dihydroxyphenyl)undecan-1-one (3), 1-(2,4,6-trihydroxyphenyl)-11-(2,6-dihydroxyphenyl)undecan-1-one (4), and 1-(2,4,6-trihydroxyphenyl)-11-(2-hydroxyphenyl)undecan-1-one (5). In our in vitro disk diffusion assay, compounds 1 and 4 showed some slight inhibition of three bacteria, while 2 and 3 did not show antimicrobial activity.     

零余子化学成分研究

目的 研究薯蓣(Dioscorea opposite Thunb.)叶腋间珠芽(零余子)的化学成分。方法 采用硅胶、Toyopearl HW-40C、Sephadex LH-20、MCI gel CHP-20及ODS等柱色谱技术结合半制备液相色谱进行分离纯化,根据其理化性质、核磁共振(NMR)谱、质谱鉴定所得化合物结构。结果 从零余子中分离得到16个化合物,分别鉴定为吐叶醇(1)、长寿花糖苷(2)、苯乙醇-8-O-β-D-葡萄糖苷(3)、artselaeroside A(4)、benzyl-O-β-D-apiofuranosyl-(1→2)-β-D-glucopyranoside(5)、seguinoside E(6)、dioscorolide A(7)、芹菜素(8)、5,7-dihydroxy-2-[2-(4-hydroxyphenyl)ethyl]chromone(9)、2,7-dihydroxy-4,6-dimethoxyphenanthrene(10)、对羟基苯乙酮(11)、2-hydroxy-3,5,7-trimethoxy-9,10-dihydrophenanthrene(12)、杜鹃醇(13)、3-甲氧基-4-羟基-苯乙醇(14)、3,5-二甲氧基-4-羟基-苯乙醇(15)、4-(3,4-二羟基苯基)-2-丁酮(16)。结论 化合物2～6、9、11～16为首次从薯蓣属中分离得到,其他化合物为首次从薯蓣中分离得到。     

南川斑鸠菊中的抗肿瘤倍半萜内酯（英文）

目的：研究南川斑鸠菊中的抗肿瘤活性成分方法：采用层析柱和制备高效液相进行化合物分离,运用1H和13CNMR及MS等波谱分析技术鉴定化合物结构;采用MTT法进行7个化合物对人骨髓白血病细胞（HL-60）的体外细胞毒实验。结果：分离得到6个倍半萜内酯[8α-（4-hydroxymethacryloyloxy）-10α-hydroxy-13-methoxyhirsutinolide（1）,8α-methacry-loyloxy-10α-hydroxy-13-O-methylhirsutinolide（2）,piptocarphin A（3）,8α-[4-hydroxymethacryloyloxy]-10α-hydroxyhisutinolide-13-O-acetate（4）,piptocarphin F（5）以及8α-acetoxy-10α-hydroxy-13-O-methylhirsutinolide（6）]和1个inone苷saussureosides B（7）;6个倍半萜内酯（1-6）具有抑制人骨髓白血病细胞（HL-60）的活性（IC503.87-12.5μmol·L-1）,但inone苷saussureosides B（7）对HL-60没有抑制活性。结论：化合物1,2,6和7首次从该植物中得到;南川斑鸠菊中的倍半萜内酯类化合物具有抗肿瘤活性。     

Potential antitumor-promoting diterpenoids from the stem bark of Picea glehni

A novel rearranged labdane-type diterpenoid, 19(4-->3)abeo-8alpha, 13(S)-epoxylabda-4(18),14-diene (1), and two new abietane-type diterpenoids, 19-nor-abieta-4(18),8,11,13-tetraen-7-one (2) and 12-hydroxydehydroabietic acid (3) were isolated from the stem bark of Picea glehni, together with seven known diterpenoids-13-epimanoyl oxide (4), dehydroabietic acid (5), (11E)-14, 15-bisnor-8alpha-hydroxy-11-labden-13-one (6), abieta-8,11, 13-trien-7-one (7), 9alpha,13alpha-epidioxyabiet-8(14)-en-18-oic acid (8), 9,10alpha-epoxy-9,10-seco-abieta-8,11,13-trien-18-oic acid (9), and methyl 15-hydroxy-7-oxo-dehydroabietate (10). Compounds 5-8 and 10 showed potent inhibitory effects on Epstein-Barr virus early antigen (EBV-EA) activation induced by the tumor promoter 12-O-tetradecanoylphorbol 13-acetate.     

Flavones and sesquiterpene lactones from Achillea atrata subsp. multifida: antimicrobial activity.

Four flavones (1-4) and nine sesquiterpene lactones (5-13), one of them (5) a new compound, were isolated from the aerial parts of Achillea atrata L. subsp. multifida. Although the crude extract demonstrated in vitro inhibitory activity against Candida albicans and Bacillus subtilis, all isolated flavones were active against B. subtilis. Flavones 1, 2, and 3 were also active against C. albicans, while 1 and 3 exhibited activity against E. coli, as well. None of the tested lactones (7, 9, 12, and 13) showed any antimicrobial activity.     

喜树中两个DNA拓扑异构酶Ⅰ抑制剂

目的：以生物活性为向导在喜树中寻找天然的DNA拓扑异构酶Ⅰ抑制剂。方法：用各种层析方法和波谱方法从喜树中分离并鉴定了14个化合物。结果：其结构分别鉴定为喜树碱(1)，肌醇(2)，喜果苷(3)，3’甲基3，4O，O-亚甲基鞣花酸-4’-D-β-D-吡喃葡萄糖苷(4)，2-氧-1，2-二氢．喹啉4酸(5)，马钱子酸(6)，4-甲基-1，2-环己烷二甲醇(7)，strictosamide(8)，獐芽菜苷(9)，乙酰胺(10)，氯原酸(11)，strictosidinic acid(12)，1-咖啡酰基奎宁酸(13)和10-羟基喜树碱(14)。结论：化合物4-13为首次从该植物中分得，化合物4的核磁数据在文献中有误，本文对其进行了重新归属。经体外活性测试，化合物1对DNA拓扑异构酶Ⅰ有中等程度的抑制作用，化合物4，14对DNA拓扑异构酶Ⅰ有强的抑制作用。