樟子松针叶中二萜类成分研究

目的：研究樟子松针叶中的化学成分。方法：以硅胶柱色谱、制备高效液相色谱纯化,得到单体化合物,根据各种有机波谱鉴定结构。结果：分离鉴定了6个化合物,分别为松叶酸(pinifolic acid,1),15-oxo-8(17)-labden-18-oic acid(2),15-acetoxy-labd-8(17)-en-18-oic acid(3),去氢松香酸(dehydroabietic acid,4),7α-羟基去氢松香酸(7α-hydroxydehydroabietic acid,5),7β-羟基去氢松香酸(7β-hydroxydehydroabietic acid,6)。结论：化合物3～6均为首次从该植物中分离鉴定,化合物3为新天然产物。细胞毒实验显示化合物2,4～6对Hela和A549细胞具有一定的细胞毒作用。     

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??OBJECTIVE To study the terpene constituents from Cunninghamia lanceolata (Lamb.) Hook. METHODS The ethanol crude extract was fractionalized by using EtOAc, then a series of chromatography methods were used to isolate the terpene compounds and the structures were elucidated by their physicochemical properties and spectroscopic data. RESULTS Nine terpenes were isolated and identified as 8(17),12E,14-labdatrien-18-al (1), 4S,5R,9S,10R-8(17),12,14-labdantrien-18-ol acetate (2), 4S,5R,9S,10R-8(17),12,14-labdantrien-18-ol (3), 4S,5R,9S,10R-8(17),12,14-labdantrien-18-oic acid (4), 3??-hydroxy-8(17),13E-labdandien-15-oic acid (5), hinokiol (6), 8,15-pimaradien-18-oic acid (7), 15-nor-14-oxo-8(17), 12-labdandien-18-oic acid (8), and 15-nor-14-oxo-8(17),12-labdan-dien-18-ol (9). CONCLUSION Compounds 1, 2, 5-7 and 9 are isolated from this plant for the first time.     

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.     

Antiproliferative triterpenes from the leaves and twigs of Juglans sinensis on HSC-T6 cells

Bioassay-guided fractionation of an 80% MeOH extract of leaves and twigs of Juglan sinensis has resulted in the isolation of four new triterpenes (1-4) and 17 known triterpenes (5-21). The new compounds were determined to be 1-oxo-3β,23-dihydroxyolean-12-en-28-oic acid 28-O-β-D-glucopyranoside (1), 1-oxo-3β-hydroxyolean-18-ene (2), 3β,23-dihydroxyurs-12-en-28-oic acid 28-O-β-D-glucopyranoside (3), and 3β,22α-dihydroxyurs-12-en-28-oic acid 28-O-β-D-glucopyranoside (4) by spectroscopic analysis. Compounds 2, 13, 15, and 21 showed antiproliferative activities (14.2, 14.8, 15.6, and 11.0% at 100 μM, respectively) in HSC-T6 cells. Flow cytometry assays revealed that these compounds inhibited HSC-T6 proliferation by inducing apoptosis.     

Bioactive constituents of Thuja occidentalis

An ethyl acetate-soluble extract of the combined leaves and twigs of Thuja occidentalis was found to inhibit 12-O-tetradecanoylphorbol 13-acetate (TPA)-induced ornithine decarboxylase (ODC) in cultured mouse epidermal ME 308 cells. Bioassay-guided fractionation of this extract led to the isolation of six active constituents (1-6), namely, (+)-7-oxo-13-epi-pimara-14,15-dien-18-oic acid (1), (+)-7-oxo-13-epi-pimara-8,15-dien-18-oic acid (2), (+)-isopimaric acid (3), (1S,2S,3R)-(+)-isopicrodeoxypodophyllotoxin (4), (-)-deoxypodophyllotoxin (5), and (-)-deoxypodorhizone (6). Compounds 1 and 4 are new natural products, and their structures and stereochemistry were determined using spectroscopic methods. Compounds 1-6 were evaluated for inhibition of the transformation of murine epidermal JB6 cells, inhibition of ornithine decarboxylase induction with murine epidermal ME 308 cells, and cytotoxic activity against KB cells.     

Isolation and absolute configuration of ent-Halimane diterpenoids from Hymenaea courbaril from the Suriname rain forest.

Bioactivity-directed fractionation of a methanol extract of Hymenaea courbaril afforded the three new diterpenoids (13R)-13-hydroxy-1(10),14-ent-halimadien-18-oic acid (1), (2S,13R)-2,13-dihydroxy-1(10),14-ent-halimadien-18-oic acid (2), and (13R)-2-oxo-13-hydroxy-1(10),14-ent-halimadien-18-oic acid (3). The configurations of these compounds were determined from X-ray crystallography of 1, circular dichroism of 2 and 3, and spectral studies of prepared derivatives. Compound 1 exhibited weak cytotoxicity toward the 1138 mutant yeast strain and the A2780 human ovarian cancer cell line.     

秦岭冷杉茎叶的化学成分研究

目的研究秦岭冷杉Abies chensiensis茎叶的化学成分。方法利用大孔吸附树脂、葡聚糖凝胶、硅胶柱色谱、半制备高效液相色谱等多种色谱方法分离纯化,根据理化性质及波谱数据对化合物进行结构鉴定。结果从秦岭冷杉95%乙醇提取物中分离得到24个化合物,分别鉴定为7,14,24-mariesatrien-26,23-olide-3α,23-diol(1)、(23R)-3α-hydroxy-9,19-cyclo-9β-lanost-24-en-26,23-olide(2)、7-oxocallitrisicacid(3)、23-hydroxy-3-oxomariesia-8(9),14,24-trien-26,23-olide(4)、紫果冷杉三萜E(5)、3-oxo-9β-lanosta-7,24-dien-26,23R-olide(6)、7,14,22Z,24-mariesatetraen-26,23-olide-3-one(7)、(+)-rel-3α-hydroxy-23-oxocycloart-25 (27)-en-26-oic acid(8)、cycloart-25-en-3β,24-diol(9)、紫果冷杉三萜H(10)、3-oxo-24,25,26,27-tetranolanost-8-en-23-oic acid(11)、abiesadine C(12)、13β-epidioxy-8(14)-abieten-18-oic acid(13)、dehydroabietic acid(14)、15-hydroxydehydroabietic acid(15)、methyl 18-methoxydehydroabietate(16)、7β-hydroxy dehydroabietic acid(17)、dehydroabietan-18-ol(18)、centdaroic acid(19)、abietic acid(20)、6,8,11,13-abi-etatrien-18-oic acid(21)、abiesadine B(22)、abiesadine N(23)、12β-hydroxyabietic acid(24)。结论所有化合物均为首次从该植物中分离得到,其中化合物11为属内首次分离得到。     

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.     

Monoterpene glycosides and triterpene acids from Eriobotrya deflexa

A phytochemical study on a methanolic extract of leaves of Eriobotrya deflexa led to the isolation and characterization of nine terpenoid compounds. Four of these are new chemical entities, including two monoterpene glycosides, (3S)-O-alpha-L-rhamnopyranosyl-(1-->3)-[4-O-(E)-coumaroyl]-alpha-L-rhamnopyranosyl-(1-->6)-beta-D-glucopyranosyl-linalool (1) and (3S)-O-alpha-L-rhamnopyranosyl-(1-->3)-[4-O-(Z)-coumaroyl]-alpha-L-rhamnopyranosyl-(1-->6)-beta-D-glucopyranosyl-linalool (2), and two triterpene acids, 1beta,2alpha,19alpha-trihydroxy-3-oxo-12-ursen-28-oic acid (3) and 2alpha,3alpha,19alpha-trihydroxy-12-oleanen-28-oic acid (4). Their structures were elucidated on the basis of spectroscopic analysis. The activities of these isolates in an in vitro antiproliferation test were also determined.     

Scopadulciol, an inhibitor of gastric H+, K(+)-ATPase from Scoparia dulcis, and its structure-activity relationships.

A new tetracyclic diterpenoid, scopadulciol [3], together with 6-methoxybenzoxazolinone, glutinol, and acacetin, was isolated from the 70% EtOH extract of Scoparia dulcis collected in Taiwan. Its structure was elucidated to be 6 beta-benzoyl-12-methyl-13-oxo-9(12)a,9(12)b-dihomo-18-podocarpanol on the basis of spectral data. It mildly inhibited hog gastric H+, K(+)-ATPase. Examination of the inhibitory activities of derivatives of scopadulcic acid B [2], including 3, revealed that methylation of the carboxyl group and introduction of an acetyl group or oxime at C-13 or C-18 markedly enhanced the inhibitory activity, while debenzoylation reduced the activity. Among the 30 compounds tested, compound 12, a methyl ester of scopadulcic acid B [2], showed the most potent activity.     

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??OBJECTIVE To study the chemical constituents from the root bark of Celastrus monospermus Roxb. METHODS The compounds were isolate and purified by repeated column chromatography on silica gel, ODS and Sephadex LH-20, and the chemical structures of compounds were determined by spectral data analyses. RESULTS Twenty-three compounds were isolated from this plant, which were identified as ??-sitosterol palmitate (1), friedelan-3-one (2), 3??-hydroxyolean-12-en (3), 3??-hydroxylcholest-5,22-dien (4), ??-sitosterol (5), 3,22-dioxo-20-taraxastene (6), 3,12-dioxofriedelane (7), 3-oxo-28-hydroxyfriedelane (8), 3-oxo-11??-hydroxyfriedelane (9), 3-oxo-12??-hydroxyfriedelane (10), pristimerin(11), 3-oxo-30-hydroxyfriedelane (12), 3-oxo-29-friedelanoic acid (13), salaspermic acid (14), celastrol (15), 3??, 21??-dihydroxy-30-nor-friedelan-20(29)-en-27-oic acid (16), 3??, 22??-dihydroxy-olean-12-en-29-oic acid (17), wilforol A (18), orthosphenic acid (19), p-hydroxybenzoic acid (20), 3-oxo-2??-hydroxyfriedelan-29-oic acid (21), 21-oxo-2??,3??,22??-trihydroxy-29-nor-friedelan-24,2??-lactone (22)and daucosterol (23). CONCLUSION Compounds 1,6, 13-14,16-22 are obtained from this plant for the first time, and compounds 16, 20-22 are isolated from the genus Celastrus for the first time.     

Chemical investigation and anti-inflammatory activity of Vitex negundo seeds.

The CHCl3 extract of the defatted seeds of Vitex negundo exhibited anti-inflammatory activity and yielded four triterpenoids: 3 beta-acetoxyolean-12-en-27-oic acid [1], 2 alpha, 3 alpha-dihydroxyoleana-5,12-dien-28-oic acid [2], 2 beta,3 alpha-diacetoxyoleana-5,12-dien-28-oic acid [3], and 2 alpha,3 beta-diacetoxy-18-hydroxyoleana-5,12-dien-28-oic acid [5]. This is the first report of the isolation of compounds 2, 3, and 5 from a natural source.     

Antimycobacterial compounds from Piper sanctum

Bioassay-guided chromatographic separation of the antimycobacterial extract of the leaves of Piper sanctum afforded 14 new compounds, identified as 2-oxo-12-(3',4'-methylenedioxyphenyl)dodecane (1), 2-oxo-14-(3',4'-methylenedioxyphenyl)tetradecane (2), 2-oxo-16-(3',4'-methylenedioxyphenyl)hexadecane (3), 2-oxo-18-(3',4'-methylenedioxyphenyl)octadecane (4), 2-oxo-14-(3',4'-methylenedioxyphenyl)-trans-13-tetradecene (5), 2-oxo-16-(3',4'-methylenedioxyphenyl)-trans-15-hexadecene (6), 2-oxo-18-(3',4'-methylenedioxyphenyl)-trans-17-octadecene (7), 2-oxo-16-phenyl-trans-3-hexadecene (8), methyl [6-(10-phenyldecanyl)tetrahydropyran-2-yl]acetate (9), methyl 2-(6-tridecyltetrahydro-2H-pyran-2-yl)acetate (10), methyl 2-(5-tetradecyltetrahydro-2-furanyl)acetate (11), 2-oxo-14-(3',4'-methylenedioxyphenyl)-trans-3-tetradecene (12), 2-oxo-16-(3',4'-methylenedioxyphenyl)-trans-3-hexadecene (13), and 2-oxo-16-phenyl-3-hexadecane (14). In addition, p-eugenol (15), methyleugenol (16), Z-piperolide (17), demethoxyyangonin (18), 5,6-dehydro-7,8-dihydromethysticin (19), cepharanone B (20), piperolactam A (21), cepharadione B (22), N-trans-feruloyltyramine (23), and N-trans-(p-coumaroyl)tyramine (24) were obtained from the anti-TBC stem extract of the plant. GC-MS and HPLC analyses of the essential oils of the leaves and stem revealed that safrol (25) was the major component of the oils. Compounds 2, 3, 6, 18-21, and 24 inhibited the growth of Mycobacterium tuberculosis when tested by the MABA assay, with MIC values ranging from 4 to 64 microg/mL.     

Chemical constituents of the aerial parts of Schnabelia tetradonta

A phytochemical study on the ethanol extract of the aerial parts of Schnabelia tetradonta led to the isolation of five new compounds, 1-5, together with seven known compounds. The structures of the new compounds were elucidated on the basis of spectral data interpretation as 2alpha,3alpha,23,29-tetrahydroxyolean-12-en-28-oic acid (1), 3-O-beta-d-glucuronopyranosyl-2beta,3beta,16beta-trihydroxy-28-norolean-12-en-15-on-23-oic acid (2), 21-O-beta-d-glucopyranosyl-3beta,21alpha,30-trihydroxyolean-13(18)-en-24-oic acid (3), 6-C-beta-l-arabinopyranosyl-8-C-alpha-l-arabinopyranosylapigenin (4), and 4-acetylaminoethylphenyl 1-O-[6-O-(Z)-p-methoxycinnamoyl-beta-d-glucopyranosyl(1-->2)]-[beta-d-glucopyranosyl(1-->3)]-alpha-l-rhamnopyranoside (5), respectively.     

Plant anticancer agents, L. cytotoxic triterpenes from Sandoricum koetjape stems.

A new ring-A secotriterpene, koetjapic acid [1], and five known compounds, 3-oxo-olean-12-en-29-oic acid [2] (a novel natural product), katonic acid [3], (-)-alloaromadendrene, (-)-caryophyllene oxide, and (+)-spathulenol, have been isolated and characterized from a cytotoxic Et2O-soluble extract of Sandoricum koetjape stems. Of these compounds, 2 and 3 demonstrated significant cytotoxic activity against cultured P-388 cells (ED50 values of 0.61 and 0.11 microgram/ml, respectively). Significant, albeit less intense, cytotoxicity was also observed with a variety of cultured human cancer cells. The 13C-nmr chemical shifts of these triterpenes were assigned unambiguously using selective INEPT nmr experiments. Aside from compounds 2 and 3, these substances were not toxic with cultured cells.     

Bioactive 12-oleanene triterpene and secotriterpene acids from Maytenus undata

The aerial parts of Maytenus undata yielded four new 12-oleanene and 3,4-seco-12-oleanene triterpene acids, namely, 3-oxo-11alpha-methoxyolean-12-ene-30-oic acid (1), 3-oxo-11alpha-hydroxyolean-12-ene-30-oic acid (2), 3-oxo-olean-9(11), 12-diene-30-oic acid (3), and 3,4-seco-olean-4(23),12-diene-3, 29-dioic acid (20-epi-koetjapic acid) (5), together with the known 3, 11-dioxoolean-12-ene-30-oic acid (3-oxo-18beta-glycyrrhetinic acid) (4), koetjapic acid (6), and the 12-oleanene artifact 3-oxo-11alpha-ethoxyolean-12-ene-30-oic acid (7). Koetjapic acid (6) inhibited the growth of Staphylococcus aureus, methicillin-resistant S. aureus, and Pseudomonas aeruginosa, with an MIC range of 3.125-6.25 microg/mL. The new 3,4-secotriterpene acid 20-epi-koetjapic acid (5) potently inhibited rat neonatal brain microglia phorbol ester-stimulated thromboxane B(2) (IC(50) = 0.5 microM) and superoxide anion (IC(50) = 1.9 microM) generation.     

Triterpenoids from the resin of Styrax tonkinensis and their antiproliferative and differentiation effects in human leukemia HL-60 cells

Four new triterpenoids, 6beta-hydroxy-3-oxo-11alpha,12alpha-epoxyolean-28,13beta-olide (1), 3beta,6beta-dihydroxy-11alpha,12alpha-epoxyolean-28,13beta-olide (2), 3beta,6beta-dihydroxy-11-oxo-olean-12-en-28-oic acid (3), and 3beta-hydroxy-12-oxo-13Halpha-olean-28,19beta-olide (4), and five known triterpenes, 19alpha-hydroxy-3-oxo-olean-12-en-28-oic acid (5), 6beta-hydroxy-3-oxo-olean-12-en-28-oic acid (6), sumaresinolic acid (7), siaresinolic acid (8), and oleanolic acid (9), were isolated from the resin of Styrax tonkinensis. The structures of these triterpenoids were determined by physicochemical and spectroscopic methods. The configuration of compound 4 was confirmed by X-ray crystallographic analysis. All these triterpenoids inhibited HL-60 cell growth with IG(50) values ranging from 8.9 to 99.4 microM. Oleanolic acid (9) was the most effective antiproliferative agent, with an IG(50) value of 8.9 microM. While 3beta,6beta-dihydroxy-11-oxo-olean-12-en-28-oic acid (3) exhibited the least effective growth inhibition among these triterpenoids, it induced HL-60 cells to undergo differentiation as measured by an NBT reduction assay.     

紫菀正丁醇萃取液化学成分研究

目的：研究紫菀正丁醇萃取液的化学成分。方法：利用大孔树脂、硅胶柱层析以及制备液相分离化合物,并利用现代波谱技术进行结构鉴定。结果：从中药紫菀中正丁醇萃取部位分得9个化合物,其中紫菀皂苷类4个,分别为：3-O-[O-α-D-吡喃阿拉伯糖-（1→6）-β-D-吡喃葡萄糖基]-2β,3β,16α-三羟基齐墩果烷-12-烯-28-酸28-[O-β-D-吡喃木糖基-（1→3）-O-α-L-吡喃阿拉伯糖基-（1→4）-[O-β-D-呋喃芹菜糖基-（1→3）]-O-α-L-吡喃鼠李糖基-（1→2）-β-D-吡喃木糖基]酯（astersaponin A,1）、3-O-[O-α-L-吡喃阿拉伯糖基-（1→6）-β-D-吡喃葡萄糖基]-2β,3β,16α-三羟基齐墩果烷-12-烯-28酸8-[O-β-D-吡喃木糖基-（1→3）-O-α-L-吡喃阿拉伯糖基-（1→4）-[O-β-D-呋喃芹菜糖基-（1→3）-O-α-L-吡喃鼠李糖基-（1→2）-O-α-L-吡喃鼠李糖基-（1→3）]-β-D-吡喃木糖基]酯（astersaponin C,2）、3-O-[O-α-L-吡喃阿拉伯糖基-（1→6）-β-D-吡喃葡萄糖基]-2β,3β,16α-三羟基齐墩果烷-12-烯-28-酸28-[O-β-D-吡喃木糖基-（1→3）-O-α-L-吡喃阿拉伯糖基-（1→4）-O-α-L-吡喃鼠李糖基-（1→2）-β-D-吡喃木糖基]酯（astersaponin E,3）和3-O-[O-α-D-吡喃阿拉伯糖-（1→6）-β-D-吡喃葡萄糖基]-2β,3β,16α-三羟基齐墩果烷-12-烯-28-酸（4）,以及shionosides A（5）、epifriedelinol（6）、astin C（7）、二十四烷酸（8）和棕榈酸（9）。结论：化合物4为新的天然产物。     

Bioactive ent-clerodane diterpenoids from the aerial parts of Baccharis gaudichaudiana

Three new ent-clerodane diterpenes (1-3) were isolated from the aerial parts of Baccharis gaudichaudiana, and their structures were elucidated as 15,16-epoxy-15alpha-methoxy-ent-clerod-3-en-18-oic acid (1), 13-epi-15,16-epoxy-15alpha-methoxy-ent-clerod-3-en-18-oic acid (2), and 7-oxo-16-hydroxy-ent-clerod-3-en-15-oic acid methyl ester-18,19-olide (3), on the basis of spectroscopic data analysis. A known compound, 7-oxo-ent-clerod-3-en-15,16:18,19-diolide, was also identified. Compounds 1 and 2 showed enhancing activity of nerve growth factor (NGF)-induced neurite outgrowth in PC 12D cells.     

Bioactive diterpenes from the fruits of Detarium microcarpum

A fruit pulp extract of Detarium microcarpum showed inhibition of the growth of the plant pathogenic fungus Cladosporium cucumerinum and of the enzyme acetylcholinesterase, implicated in Alzheimer's disease. Fractionation of this extract led to the isolation of four new clerodane diterpenes, 3,4-epoxyclerodan-13E-en-15-oic acid (1), 5alpha,8alpha(2-oxokolavenic acid) (2), 3,4-dihydroxyclerodan-13E-en-15-oic acid (4), and 3,4-dihydroxyclerodan-13Z-en-15-oic acid (5). Also isolated were 2-oxokolavenic acid (3) and copalic acid (6). Structure elucidation of the compounds was carried out by spectroscopic data interpretation and by the X-ray crystallography of 2 and 4. Three of the new clerodane diterpenes (1, 2, and 5) showed both antifungal activity and inhibition of acetylcholinesterase, and 3 showed a slight inhibition of this enzyme.