Four new terpenoids from the roots of Ligularia narynensis

Four new oplopane and guaiane type sesquiterpenoids (1-3), and a monoterpenoid (4) together with three known monoterpenoids (5-7), have been isolated from the roots of Ligularia narynensis. The structures of 1-4 were elucidated as 3beta,4-diacetoxy-8alpha-(2-methylbutyryloxy)-9alpha-(4-methylsenecioyloxy)-11alpha,12-epoxyoplop-10 (14)-ene (1), 3beta,4-diacetoxy-9alpha-(4-acetoxy-4-methylsenecioyloxy)-2beta,8alpha-di (2-methylbutyryloxy)-11alpha,12-epoxyoplop-10 (14)-ene (2), 2alpha-hydroxy-1betaH,7alphaH,10alphaH-guai-4,11 (12)-dien-3-one (3) and 1alpha,2beta,3alpha,6alpha-tetrahydroxy-p-menthane (4) by spectroscopic methods. 1 and 2 were evaluated for their in vitro cytotoxic activity against cultured SMMC-7721 (human hepatoma), L02 (human hepatocyte), and HL-60 (human promyelocytic leukaemia) cell lines.     

Bioactive terpenes from the roots of Chloranthus henryi

12,15-Epoxy-5alpha H,9beta H-labda-8(17),13-dien-19-oic acid (1) and 14-methoxy-15,16-dinor-5alpha H,9alpha H-labda-13(E),8(17)-dien-12-one (2), two new labdane-type diterpenes, and 1alpha-hydroxy-8,12-epoxyeudesma-4,7,11-triene-6,9-dione (3), one new eudesmane-type sesquiterpene, were isolated from Chloranthus henryi Hemsl, along with two known compounds, 8beta H-eudesma-4(14),7(11)-dien-12,8-olide (4) and 8beta-hydroxyeudesma-4(14),7(11)-dien-12,8-olide (5). Their structures were established by a combination of 1D- and 2D-NMR spectroscopic techniques. The new compounds 2, 3 and the known compound 4 exhibited antitumor activities against Hela and K562 human tumor cell lines.     

Cytotoxic constituents of the leaves of Ixeris sonchifolia

The ethyl acetate extract of the leaves of Ixeris sonchifolia afforded two new and two known sesquiterpene lactone glucosides of the guaiane-type, together with a known alkenol glucoside. The known compounds were identified as ixerin Z (1), ixerin Z-6'-p-hydroxyphenylacetate (2), and (Z)-3-hexen-1-ol-beta-D-glucopyranoside (3), respectively. The structures of the new compounds were elucidated as 11,13a-dihydroixerin Z [4, 3-hydroxy-2-oxo-guaia-1(10), 3-dien-5alpha,6beta,7alpha, 11betaH-12,6-olide-3-O-beta-D-glucopyranoside], and 3,10beta-dihydroxy-2-oxo-guaia-3,11(13)-dien-1alpha,5alpha,6alpha,7aH-12,6-olide-10-O-beta-D-glucopyranoside (5), respectively. The cytotoxicity of these compounds against human hepatocellular carcinoma cell (HepG2) and human melanoma cell (SK-MEL-2) was evaluated.     

Anti-platelet aggregation alkaloids and lignans from Hernandia nymphaeifolia

A new aporphine, N-(N-methylcarbamoyl)-O-methyl-bulbocapnine (1), together with seven known compounds, (-)-5'-methoxypodorhizol (2), a mixture of beta-sitosterone (3) and stigmasta-4,22-dien-3-one (4), a mixture of 3 beta-hydroxystigmast-5-en-7-one (5) and 3 beta-hydroxystigmasta-5,22-dien-7-one (6), and a mixture of 6 alpha-hydroxystigmast-4-en-3-one (7) and 6 alpha-hydroxystigmasta-4,22-dien-3-one (8), were isolated in continuing studies on the trunk bark of Formosan Hernandia nymphaeifolia. The structures of these compounds were determined through spectral analyses. In addition, the previously reported six alkaloids, laurotetanine, oxohernagine, thalicarpine, reticuline, (+)-vateamine-2'-beta-N-oxide, (+)-hernandaline and six lignans, (+)-epiaschantin, (+)-epimagnolin, (+)-epiyangambin, (-)-hernone, (-)-yatein, (-)-deoxypodophyllotoxin were demonstrated to have anti-platelet aggregation activity.     

New eremophilane-type sesquiterpenes from Ligularia hodgsonii

Four new eremophilanlides (1- 4) together with a known sesquiterpene were isolated from the roots and rhizomes of Ligularia hodgsonii. The structures of these new compounds were established as 6beta-(2'-methylbutanoyloxy)-10beta-acetoxy-3 beta, 8beta-dihydroxyeremophil-7(11)-en-8,12-olide (1), 6beta,10 beta-dihydroxyeremophil-7(11)-en-8alpha,12-olide (2), 3beta-acetoxy-6,9-dien-8-oxoeremophil-12-nor-11-ketone (3), and 3beta-acetoxy-6alpha, 8alpha-dihydroxyeremophil-7(11), 9-dien-8,12-olide (4) by means of mass, IR and NMR spectroscopy.     

Steroids from Harrisonia abyssinica

In addition to the known sterols and ketosteroids beta-sitosterol (24 alpha-ethylcholest-5-en-3 beta-ol), stigmasterol (24 alpha-ethylcholesta-5,22-dien-3 beta-ol), campesterol (24 alpha-methylcholest-5-en-3 beta-ol), beta-sitostenone (stigmast-4-en-3-one, 24 alpha-ethylcholest-4-en-3-one), stigmastenone (stigmasta-4,22-dien-3-one, 24 alpha-ethylcholesta-4,22-dien-3-one), campestenone (24 alpha-methylcholest-4-en-3-one), and stigmasta-3,5-dien-7-one (24 alpha-ethylcholesta-3,5-dien-7-one), the new steroids stigmasta-3,5,22-trien-7-one (24 alpha-ethylcholesta-3,5,22-trien-7-one), and campesta-3,5-dien-7-one (24 alpha-methylcholesta-3,5-dien-7-one) were isolated from the stem bark of Harrisonia abyssinica and identified by NMR and mass spectrometry.     

New sesquiterpenes from the roots of Ligularia dentata

Phytochemical investigation of the roots of Ligularia dentata has resulted in the isolation of three new bisabolane sesquiterpenes: 1alpha,3beta,10,11 -tetrahydroxy-2alpha,5alpha,8-triangeloyl-oxybisabola-(7)14-en-4-one, 1alpha,3beta,10-trihydroxy-11 -methoxy-2alpha,5alpha,8-triangeloyloxybisabola-7(14)-en-4-one, and lalpha, 3beta,10-trihydroxy-2alpha,5alpha,8-triangeloyloxybisabola-7(14),11(12)-dien-4-one. Their structures were elucidated with spectro-scopic methods and 2D-NMR techniques as well as chemical transformations. In addition, three known phenolic norsesquiterpenes, liguhodgsonal, ligujapone, and 2-hydroxy-platyphyllide have also been obtained.     

Cytotoxic diterpenoids from the roots of Euphorbia ebracteolata

Three new diterpenoids, yuexiandajisu D (1), E (2) and F were isolated from the roots of Euphorbia ebracteolata, along with eight known diterpenoids, jolkinolide B (4), jolkinolide A, ent-11alpha-hydroxyabieta-8(14),13(15)-dien-16,12alpha-olide (6), ent-(13S)-hydroxyatis-16-ene-3,14-dione, ent-3beta,(13S)-dihydroxyatis-16-en-14-one, ent-3-oxokaurane-16alpha,17-diol, ent-16alpha,17-dihydroxyatisan-3-one and ent-atisane-3beta,16alpha,17-triol. The structures of all compounds were deduced using spectroscopic methods and confirmed for 1 and 2 by single-crystal X-ray diffraction. A biogenetic pathway for the formation of 1 and 2 is proposed briefly. Cytotoxic activities were evaluated against ANA-1, B 16 and Jurkat tumor cells. Jolkinolide B (4) displayed modest activity on ANA-1, B 16 and Jurkat tumor cells with IC50 values 4.46 x 10(-2), 4.48 x 10(-2), 6.47 x 10(-2) microM, and ent-11alpha-hydroxyabieta-8(14),13(15)-dien-16,12alpha-olide (6) showed significant activity against ANA-1 and Jurkat cells with IC50 values 7.12 x 10(-3) and 1.79 x 10(-2) microM. Compound 1 was found to be slightly active against ANA-1 cells with an IC50 value 2.88 x 10(-1)microM. Structure-activity relationships of isolated compounds are also discussed.     

Anti-platelet aggregation and chemical constituents from the rhizome of Gynura japonica

A novel quinonoid terpenoid, (-)- alpha-tocospirone, a new chromanone, (-)-gynuraone, as well as three new steroids, (22 E,24 S)-7 alpha-hydroperoxystigmasta-5,22-dien-3 beta-ol, (22 E,24 S)-stigmasta-1,4,22-trien-3-one, and (24 R)-stigmasta-1,4-dien-3-one, together with 15 known components, were isolated from the rhizome of Formosan Gynura japonica. Structures of the new compounds were determined through spectral analyses and chemical evidence. Several of the isolated compounds, caryophyllene oxide, 6-acetyl-2,2-dimethylchroman-4-one, vanillin, 2,6-dimethoxy-1,4-benzoquinone, and benzoic acid exhibited significant anti-platelet aggregation activity in vitro.     

中国南海短指软珊瑚化学成分研究

目的研究短指软珊瑚Sinulariasp.的化学成分。方法利用硅胶色谱、Sephadex LH-20凝胶色谱、HPLC等手段对化学成分进行分离纯化;通过理化性质、波谱分析方法结合文献对照,鉴定化合物的结构。结果从短指软珊瑚甲醇提取物中,共分离鉴定了11个单体化合物:胆甾醇(1)、(22E)-麦角甾-5,22-二烯-3β-醇(2)、胆甾-5,20-二烯-3β-醇(3)、麦角甾-5,24(28)-二烯-3β-醇(4)、柳珊瑚甾醇(5)、3β-羟基胆甾-5-烯-7-酮(6)、3β-羟基麦角甾-5,24(28)-二烯-7-酮(7)、(22E)-3β-羟基麦角甾-5,22-二烯-7-酮(8)、3β-羟基麦角甾-5-烯-7-酮(9)、(22E)-3β-羟基胆甾-5,22-二烯-7-酮(10)、鲨肝醇(11)。结论化合物6～10为首次从该属软珊瑚中分离得到。化合物7在10μg.mL-1浓度水平,对K562肿瘤细胞株的抑制率为22.74%,对HeLa肿瘤细胞株的抑制率为9.98%。     

Anti-inflammatory ergostanes from the basidiomata of Antrodia salmonea

Three new anti-oxidative ergostanes, methyl antcinate L (1), antcin M (2), and methyl antcinate K (3), together with nine additional known compounds, 3-ketodehydrosulphurenic acid, sulphurenic acid, dehydrosulphurenic acid, 3beta,15alpha-dihydroxylanosta-7,9(11),24-trien-21-oic acid, zhankuic acid A, zhankuic acid B, zhankuic acid C, antcin C, and antcin K were isolated from the basidiomata of Antrodia salmonea, a newly identified species of Antrodia (Polyporaceae) in Taiwan. These three new compounds were identified as methyl 3alpha,7alpha,12alpha-trihydroxy-4alpha-methylergosta-8,24(29)-dien-11-on-26-oate (1), 3alpha,12alpha-dihydroxy-4alpha-methylergosta-8,24(29)-dien-11-on-26-oic acid (2), and methyl 3alpha,4beta,7beta-trihydroxy-4alpha-methylergosta-8,24(29)-dien-11-on-26-oate (3) by spectroscopic analysis. We studied their antioxidative potential on the production of reactive oxygen species and nitric oxide (NO) in neutrophils and microglial cells, respectively. Compounds 1-3 displayed potent antioxidative activity with IC50 values of around 2.0-8.8 microM that was partially due to inhibition (6-67%) of NADPH oxidase activity but not through direct radical-scavenging properties. Compounds 1-3 also inhibited NO production with IC50 values of around 1.7-16.5 microM and were more potent than a non-specific NOS inhibitor. We conclude that these three new compounds 1, 2, and 3 exhibit anti-inflammatory activities in activated inflammatory cells.     

Two new compounds and anti-HIV active constituents from Illicium verum

Two new compounds named illiverin A (1) and tashironin A (8) were isolated from the roots of Illicium verum, together with seven known compounds: 4-allyl-2-(3-methylbut-2-enyl)-1,6-methylenedioxybenzene-3-ol (2), illicinole (3), 3-hydroxy-4,5-methylenedioxyallyl-benzene (4), (-)-illicinone-A (5), 4-allyl-4-(3-methylbut-2-enyl)-1,2-methylenedioxycyclohexa-2,6-dien-5-one (6), 3,4-seco-(24 Z)- cycloart-4(28),24-diene-3,26-dioic acid, 26-methyl ester (7) and tashironin (9). Based on 1D- and 2D-NMR data (COSY, HMQC, HMBC), the structures of the new compounds were deduced to be (E)-1-[(3-methylbut-2-enyl)oxy]-2-methoxy-4-(prop-1-enyl)benzene (1) and 11-O-debenzoyl-11alpha-O-2-methylcyclopent-1-enecarboxyltashironin (8). Compounds 1-9 were screened for anti-HIV activity in vitro whereby compounds 5 and 7 possessed moderate anti-HIV activity with EC50 values of 16.0 and 5.1 microM with SI values of 18.2 and 15.6, respectively.     

Two new sesquiterpene lactones from Sarcandra glabra

Two new sesquiterpene lactones (1) and (2), along with three known sesquiterpenes, atractylenolide beta (3), chloranthalactone E (4), and ( - )-istanbulin A (5), were isolated from the whole plant of Sarcandra glabra. The structures of two new compounds were established as 8beta,9alpha-dihydroxyeudesman-4(15),7(11)-dien-8alpha,12-olide (1) and 8beta,9alpha-dihydroxylindan-4(5),7 (11)-dien-8alpha,12-olide (2) on the basis of spectroscopic analysis. Compound 3 was isolated from this genus for the first time.     

Eremophilane sesquiterpenes from Cacalia ainsliaeflora

Chemical investigation of Cacalia ainsliaeflora afforded four new eremophilane sesquiterpenes (1 - 3, 5) and a known sesquiterpene (4), which were identified as 3 beta-angeloyloxy-8 alpha-hydroxy-6 beta-methoxyeremophil-7(11),9(10)-dien-8,12-olide (1), 3 beta-angeloyloxy-6 beta,8 alpha-dihydroxyeremophil-7(11),9(10)-dien-8,12-olide (2), 3 beta-angeloyloxy-8 alpha-hydroxy-6 beta-ethoxyeremophil-7(11),9(10)-dien-8,12-olide (3), 3 beta-angeloyloxy-8-oxo-eremphila-6,9-dien-12-oic acid (4), and 3,8-oxo-eremophila-6,9-dien-12-oic acid (5) respectively. These compounds were assayed against Escherichia coli, Staphylococcus aureus and Bacillus subtilis, and compounds 1, 2, 4 and 5 showed weak antibacterial activity. The structures of the compounds were established by 1D and 2D NMR experiments.     

Cytotoxic triterpenoids and steroids from the bark of Melia azedarach

Two new triterpenoids (1, 2) and two new steroids (3, 4) along with twelve related known compounds (5-16) were isolated from the bark of Melia azedarach. The new structures were elucidated by means of spectroscopic methods and molecular modeling studies and found to be 21,24-cycloeupha-7-ene-3 β,16 β,21 α,25-tetrol (1), 3 β-acetoxy-12 β-hydroxy-eupha-7,24-dien-21,16 β-olide (2), 29-hydroperoxy-stigmasta-7,24(28) E-dien-3 β-ol (3), and 24 ξ-hydroperoxy-24-vinyl-lathosterol (4). All isolated compounds were tested for their cytotoxic activity against three human cancer cell lines (A549, H460, HGC27) using the CellTiter Glo? luminescent cell viability assay. Among them, compounds 2- 4, 24 ξ-hydroperoxy-24-vinyl-cholesterol (6), kulinone (7), meliastatin 3 ( 8), 3-oxo-olean-12-en-28-oic acid (10), and (22 E,24 S)-5 α,8 α-epidioxy-24-methyl-cholesta-6,22-dien-3 β-ol (12) were found to have cytotoxic effects, with IC?? values of 5.6-21.2?μg/mL.     

New monoterpenes from Mentha microphylla

Four new monoterpenes, (1 R*,2 S*)-1,2-dihydroxy- p-menth-4(8)-en-3-one ( 1), (4 S*)-4-hydroxy- p-mentha-1,8-dien-3-one ( 2), (4 S*)-4-methoxy- p-mentha-1,8-dien-3-one ( 3), and (3 R*,4 R*,6 S*)-3-acetoxy-6-hydroxy- p-mentha-1,8-diene ( 4) together with four known compounds have been isolated from the aerial parts of Mentha microphylla. The structures were determined using spectroscopic methods particularly high resolution (1)H-, (13)C-NMR as well as 2D (1)H- (1)H COSY, HMQC and HMBC analysis.     

中国南海木棘软珊瑚化学成分研究

目的研究木棘软珊瑚Dendrophthyasp.的化学成分。方法利用硅胶、Sephadex LH-20、ODS和HPLC等方法对化学成分进行分离纯化;根据波谱数据与文献对照鉴定化合物结构。结果从木棘软珊瑚Dendrophthyasp.的甲醇提取物中分离鉴定了12个化合物:胆甾-1,4,22-三烯-3-酮(1)、24-亚甲基-胆甾-1,4,22-三烯-3-酮(2)、胆甾-1,4-二烯-3-酮(3)、胆甾醇(4)、胆甾-5,22-二烯-3β-醇(5)、麦角甾-5,24(28)-二烯-3β-醇(6)、尿嘧啶(7)、胸腺嘧啶(8)、尿嘧啶-2’-脱氧核苷(9)、胸腺嘧啶-2’-脱氧核苷(10)、胸腺嘧啶核苷(11)、咖啡因(12)。结论化合物1～12均为首次从该种软珊瑚中分离得到。     

滇桂艾纳香化学成分的分离与鉴定（Ⅱ）

目的分离鉴定中药滇桂艾纳香的化学成分。方法利用硅胶柱色谱、Sephadex LH-20柱色谱等方法进行分离纯化,根据理化性质和波谱数据进行结构鉴定。结果分离得到10个化合物,分别鉴定为：环（亮-脯）二肽（1）（、24S）豆甾-4-烯-3-酮（2）（、24S）豆甾-4-22-二烯-3-酮（3）、二氢槲皮素-4′-甲醚（4）、丁香酸（5）、没食子酸（6）、香草酸（7）、呋喃甲酸（8）、水杨酸（9）、咖啡酸（10）。结论化合物1~10均为首次从该植物中分离得到。     

Biological Activities of the Chemical Constituents of<Emphasis Type="Italic">Erythrina stricta</Emphasis> and<Emphasis Type="Italic">Erythrina subumbrans</Emphasis>

Phytochemical investigation of the hexane and CH2Cl2 extracts of Erythrina stricta roots and E. subumbrans stems led to the isolation of six pterocarpans, one flavanone, one isoflavone, two alkaloids, five triterpenes, six steroids and alkyl trans-ferulates. The structures of all known compounds were determined on the basis of spectroscopic evidence. Sophoradiol (15), a mixture of stigmast-4-en-3-one (19) and stigmasta-4,22-dien-3-one (20), lupeol (21), cycloeucalenol (22), a mixture of 3beta-hydroxystigmast-5-en-7-one (23) and 3beta-hydroxystigmast-5,22-dien-7-one (24) and melilotigenin C (25) were first isolated from the genus Erythrina. The isolated compounds were evaluated for antiplasmodial activity, antimycobacterial activity and cytotoxicity. Among the tested compounds, 5-hydroxysophoranone (8) exhibited the highest antiplasmodial activity against Plasmodium falciparum (IC50 2.5 microg/mL). Compound 8, erystagallin A (5), erycristagallin (7) and erysubin F (10) showed the same level of antimycobacterial activity against Mycobacterium tuberculosis (MIC 12.5 microg/mL). For cytotoxicity, erybraedin A (2) showed the highest activity against the NCI-H187 and BC cells (IC50 2.1 and 2.9 microg/mL, respectively), whereas 10 exhibited the highest activity against the KB cells (IC50 4.5 microg/mL).     

A new isopimarane-type diterpene and a new natural atisane-type diterpene from Excoecaria agallocha

From the woods of Excoecaria agallocha, a new isopimarane-type diterpene, 3alpha,11beta-dihydroxy-ent-isopimara-8(14),15-dien-2-one and a new natural atisane-type diterpene, 16beta-hydroxy-ent-atisan-3-one were isolated together with three known compounds, ribenone, ent-labda-8(17),13E-diene-3beta,15-diol, and ent-3beta-hydroxybeyer-15-ene-2,12-dione. Their structures were determined by spectral data and x-ray crystallography evidence.