大萼香茶菜挥发油化学成分的气相色谱/质谱法分析

采用常规水蒸气蒸馏法提取出大萼香香茶菜挥发油，经气相色谱－质谱联机分析，分离出116个峰，确认了其中60种成分，所鉴定的组分占总峰面积的75．77％。     

皱叶香茶菜化学成分的研究

从采自西藏的皱叶香茶菜中分离鉴定了3对B-闭联对映贝壳杉烯型二萜化合物:二萜化合物皱叶香茶菜素(Ⅰ)和二氢皱叶香茶菜素(Ⅱ);isodocarpin(Ⅲ)和dihydroisodocarpin(Ⅳ)及Carpalasionin(Ⅴ)和dihydrocarpalasionin(Ⅵ)。(Ⅰ)、(Ⅲ)和(Ⅴ)分别与对应的二氢化合物(Ⅱ)、(Ⅳ)和(Ⅵ)以混合物的形式被分离和鉴定。化合物(Ⅱ)为新化合物,(Ⅰ)、(Ⅳ)和(Ⅵ)首次在自然界发现,(Ⅲ)和(Ⅴ)为已知化合物。     

二维核磁共振波谱和分子力学方法计算香茶菜醛溶液中的…

采用二维核磁共振波谱完全归属了天然有机化合物香茶菜醛的＾１Ｈ和＾１３Ｃ ＮＭＲ化学位移，测定了部分质子的偶合常数，并用孤立自旋对近似方法质量处理香茶菜醛的相敏ＮＯＳＥＹ谱，根据１／γ＾６ｉｊ∝Ａｉｊ计算出相应的质子间距离。其溶液中的三维空间结构采用以ＮＭＲ结构参数为初始数据的ＷＵＰＨ计算程序和分子力学能量优化（ＭＭ２）完成计算。计算结果表明，得到的香茶菜醛在溶液中的三维空间结构反映了该化合物在溶液     

高效液相色谱法同时测定蓝萼香茶菜中蓝萼甲素和蓝萼乙素的含量

提出了高效液相色谱法测定蓝萼香茶菜中蓝萼甲素和蓝萼乙素的含量。样品采用甲醇超声提取后,经0.45μm滤膜过滤,滤液供高效液相色谱仪测定。采用Hypersil ODS C18色谱柱(4.6mm×200mm,5μm)分离,用甲醇-水(55+45)溶液为流动相洗脱,用二极管阵列检测器在波长231nm处测定。蓝萼甲素和蓝萼乙素的质量浓度分别在0.018～0.575g.L-1和0.009～0.298g.L-1范围内与峰面积呈线性关系。方法用于蓝萼香茶菜样品的分析,蓝萼甲素和蓝萼乙素的回收率分别为102%和103%,测定值的相对标准偏差(n=6)分别为0.084%和0.071%。     

LongikaurinB的晶体结构分析

长管香茶菜B（LongikaurinB）分子的化学计量式为C22H30O7，Mr=406．47，用X射线衍射法确定其晶体结构，该结晶是无色透明柱状，属单斜晶系，空间和群为P21，晶胞参数：a=11．893（2），b=6.380（2），c=13．205（2）A，β=99．39（2）°，Z=2，V=988．5（4）A3，Dc＝1．366g／cm3，F（000）＝436，u＝0．9cm-1。应用直接法解析分子结构，以最小二乘法修正结构参数。最终可靠因子R=0.042，Ra=0.043。结果表明，该化合物为长管香茶菜B，属7，20-氧桥-对映-贝壳杉烯型工花化合物。结构与功能关系研究表明LongikaurinB化合物可能具有抗肿瘤生物活性。     

二维核磁共振波谱和分子力学方法计算香茶菜醛溶液中的三维空间结构

采用二维核磁共振波谱完全归属了天然有机化合物香茶菜醛的~1H和~(13)C NMR化学位移,测定了部分质子的偶合常数,并用孤立自旋对近似方法定量处理香茶菜醛的相敏NOESY谱,根据1/r_(ij)~8∝A_(ij)计算出相应的质子间距离.其溶液中的三维空间结构采用以NMR结构参数为初始数据的WUPH计算程序和分子力学能量优化(MM2)完成计算.计算结果表明,得到的香茶菜醛在溶液中的三维空间结构反映了该化合物在溶液中的真实空间结构.     

龙胜香茶菜的成分: 新二萜龙胜香茶菜素的结构

从广西桂林产龙胜香茶菜叶中分得一种新的对映-贝壳杉烯型二萜化合物, 命名为龙胜香茶菜素, 经光谱和化学方法证明了其结构.     

三种西藏香茶菜挥发油化学成分的研究

唇形科植物香茶菜广泛分布于全国各地,民间一直用作抗菌消炎药使用,近年来发现,香茶菜属植物有抑制肿瘤和抗癌活性,其活性成分是二萜。我们对采自西藏的3种香茶菜的挥发油进行了GC/MS分析。从小叶香茶菜[Rabdosia Parrifolia(Batal)Hara; Litte leaf Rabdosia]油中分出84个峰,鉴定了27个,占总面积的60％;从川藏香茶菜(Rabbosia Pseudo-irrarata C.Y.Wu,Szechwan-Tibet Rabdosia)油中分出72个峰,鉴定了39个,占总面积的82.5％;从皱叶香茶菜[Rabdosia rugosa(Wcll.)Hara,Wrinkted leaf Rabdosia]中分出了90个峰,鉴定了39个,占总面积的62.1％。3种香茶菜的分析尚未见报道。     

Crystal Structure of Macrocalyxin J

The title compound,(1α,6β,11β,14α)-1,7:6,20-diepoxy-6,11-dihydroxy-6,7-seco-ent-kaur-16-ene-7,15-dione-14-acetate (macrocalyxin J),is a diterpenoid which was isolated from the leaves of Rabdosia macrocalyx and characterized by single-crystal X-ray diffraction. It cry-stallizes in orthorhombic,space group P212121 with a=9.3608(8),b=14.9787(12),c=15.5750(13) ,Z=4,V=2183.8(3) 3,C22H30O9,Mr=438.46,Dc=1.334 g/m3,μ(MoKα)=0.103 mm1,F(000)=936,the final R=0.0532 and wR=0.1262 for 2252 observed reflections (I > 2σ(I)). In the molecule,three six-membered rings adopt chair,boat and slightly distorted boat conformations,respectively,while both five-membered rings have approximate envelope conformations.     

一个新的对映-贝壳杉烷型二萜化合物,白叶甲素

一个新的对映－贝壳杉烷型二萜化合物，白叶甲素陈绍农１林中文２陈耀祖１，３＊孙汉董２＊（１兰州大学国家应用有机重点实验室７３００００２中国科学院昆明植物研究所植物化学开放实验室６５０２０４３浙江大学化学系３１００２７）关键词白叶香茶菜唇形科对映－贝壳杉...     

线叶旋复花化学成份的研究

Xian-Ye-Xuan-Fu-Hua, the flowers of Inula linariaefolia Turcz (Compositae), is a commonly known Chinese medicinal herb and used as expectorant as well as for the treatment of some malignant tumors. The chemical investigation of its active principles by our early work in 1964 resulted in the isolation of a new sesquiterpene lactone (m.p. 190-192`C, (α)D-24 in CHCl3), which possesses significant inhibitory action against Hela cells and fungi in vitro. Besides, it also shows some expectorant activity in preliminary pharmacological tests. Analyses of the spectral data (IR, UV, ^1H NMR, 13C NMR, MS) and our early results of chemical reactions suggested that the compound is the same as britanin 1 (m.p. 192-194`C, (α)D-26 in CHCl3) studied Chugunov in 1971. However its stereochemistry remained unsolved. On careful examination of the 360 MHZ 1H NMR data (in CDCl3 and in C6D6) and the Cotton effects of ORD spectra of its saturated lactone and cyclopentanone derivatives, we considered that britanin must be ambros-11(13)-en-2β, 4β, 6α, 8α-tetraol-12-oic-(12,8)- lactone, 2, 6-diacetate (7). Since the large values for J6,7, J7,8, J8,9, J9,10 and J1,10 indicate the existence of successive a-a trans coupling in all vicinal protons form C6 to C1, the cofnformation of the cycloheptane ring must be in chair from. The other constitutent isolated from the same plant has been identified as taraxasteryl palmitate.     

Structure of a new sterol from the South China sponge Dysidea fragilis

A new sterol, 5a-cholesta-8(14),24(25)-diene-3/β, 6a-diol (1) and a known sterol (24Z)-24-ethyl-cholesta-7(8),24(28)-diene-3β,5a,6β-triol (2) have been isolated from the South China Seasponge Dysidea fragilis. The structure and relative stereochemistry of 1 were established by spectralanalysis, including 2D NMR experiments.     

Synthesis,structure, and acylation of dihydroquinopimaric acid hydroxy derivatives

Reduction conditions of methyl dihydroquinopimarate with sodium borohydride and lithium aluminum hydride were established. As a result of the reduction 14β-hydroxy, 17α-hydroxy, 14β,17α-dihydroxy, and 14β,17α,21α-trihydroxy derivatives were obtained. The structure of methyl esters of 14β-acetoxy- and 17α-hydroxydihydroquinopimaric acid was established by XRD and NMR methods. Mono-, di-, and triacylates were obtained from the diterpene alcohols.     

Two New Daucane Sesquiterpenoids from <em>Daphne aurantiaca</em>

Two new daucane sesquiterpenoids 1β,2β-epoxy-10(H)α-dauca-11(12)-ene-7α,14-diol (1) and 1α,2α-epoxy-10(H)α-dauca-11(12)-ene-7α,14-diol (2) were isolated from the plateau medicinal plant Daphne aurantiaca Diels. (Thymelaeceae). Their structures were elucidated by 1D and 2D NMR spectroscopy, as well as HR-ESI-MS data.     

Structure Studies of the Extracellular Polysaccharide from <Emphasis Type="Italic">Trichoderma</Emphasis> sp. KK19L1 and Its Antitumor Effect via Cell Cycle Arrest and Apoptosis

An extracellular polysaccharide TP1A was purified from the fermented broth of Trichoderma sp. KK19L1 by combination of Q Sepharose fast flow and Sephacryl S-300 chromatography. TP1A was composed of Man, Gal, and Glc in a molar ratio of about 3.0:5.1:8.1. The molar mass of TP1A was about 40.0 kDa. Methylation and NMR analysis indicated that the probable structure of TP1A was [→4,6)-α-D-Glcp(1→6)-β-D-Galf(1→6)-β-D-Galf(1→2,6)-β-D-Galf(1→2,6)-β-D-Galf(1→2,6)-β-D-Galf(1→2,6)-α-D-Manp(1→2,6)-α-D-Manp(1→] with [α-D-Glcp(1→] and [α-D-Manp(1→6)-α-D-Glcp(1→6)-α-D-Glcp(1→] as branches. The antitumor study showed that TP1A was able to inhibit the cell viability of HeLa and MCF-7 cells. TP1A could arrest HeLa cells in G2/M phase and induce HeLa cell apoptosis. These findings suggest that fungal polysaccharides could be a potential source for antitumor agents.     

Withanolides from Withania adpressa

From the leaves of Withania adpressa, a plant endemic to Sahara of Morocco and Algeria, the novel steroidal lactone (22R)‐14α,15α,17β,20β‐tetrahydroxy‐1‐oxowitha‐2,5,24‐trien‐26,22‐olide (= (15S,17S)‐14,15,17,20‐tetrahydroxy‐22,26‐epoxyergosta‐2,5,24‐triene‐1,26‐dione; 1 ), was isolated, along with three known compounds, withanolides F ( 2 ), J ( 3 ), and oleanolic acid. Their structures were mainly solved by in‐depth 1D‐ and 2D‐NMR (including ADEQUATE) experiments, as well as by HR‐MS analyses and chemical evidence.     

Isolation ofΔ9(11)-sterols from the sea cucumber psolusfabricii. Implications for holothurin biosynthesis

- 14α-Methyl-5α-cholest-9(11)-en-3β-ol ($\text{2}$) and 4α,14α-dimethyl-5α-cholest-9(11)-en-3β-ol ($\text{3}$) have been isolated from the sea cucumber $\text{Psolus}$$\text{fabricii}$ and characterised by ¹H NMR, ¹³C NMR and mass spectrometry. Lanost-9(11)-en-3β-ol ($\text{4}$) has also been tentatively identified. The relevance of this series of Δ⁹⁽¹¹⁾-sterols to holothurin biosynthesis is briefly discussed.     

8β-hydroxyeremophil-7(11)-ene-12,8α(4β,6α)-diolide分子的晶体结构

8β-hydroxyeremophil-7(11)-ene-12,8α(4β,6α)-diolide was isolated from the Ligularia intermedia and char- acterized by MS, multi NMR and X-ray single crystal diffraction. Its crystal structure was determined as in a orthorhombic type, with space group P212121 with a=6.8519(5), b=10.7191(8), c=18.5942(14) oA, V =1365.67(18) oA3, Z=4, and the calculated density is 1.354 mg/m3. F(000)=592, μ=0.101 mm-1.     

Cardenolide and pregnane derivatives from the roots of Trachycalymma fimbriatum (Weimark) Bullock. Glycosides and aglycones. 322

The roots of Trachycalymma fimbriatum (WEIMARCK ) BULLOCK contain both cardenolide and pregnaneglycosides. Elimination of 2-deoxysugars by mild acid hydrolysis gave a mixture from which some anhydroderivatives and the following compounds could be isolated: uzarigenin ( l ), ascleposide = 3-O-(6-deoxy-β-D -allopyranosyl)-uzarigenin ( 4 ), coroglaucigenin ( 6 ) and two pregnane derivatives (H and J). Compound H could be identified as 3β,14β-dihydroxy5α, 17α-pregnan-20-one ( 10 ). Compound J is probably a new substance, for which we tentatively assign structure 18 , i.e. 3β8β,14β-trihydroxy-5α,17α-pregnan-20-one. We suspect H and J to be artefacts produced from the corresponding 17b-derivatives during acid hydrolysis. 17-iso-H is probably a precursor in the biosynthesis of uzarigenin. The cardenolides of Trachycalymma fimbriatum are the same as found in Asclepias glaucophylla, a closely related species, while the pregnane derivatives of the latter are distinctly higher hydroxylated.