Flavonoids and phenol glycosides from Boerhavia diffusa

Four new compounds were isolated from Boerhavia diffusa namely eupalitin 3-O-beta-D-galactopyranosyl-(1' --> 2')-O-beta-D-galactopyranoside (1), 3,3',5-trihydroxy-7-methoxyflavone (4), 4',7-dihydroxy-3'-methylflavone (5) and 3,4-dimethoxyphenyl-1-O-beta-D-apiofuranosyl-(1' --> 3')-O-beta-D-glucopyranoside (7) along with eight known compounds. The structures were elucidated by analysis of their spectroscopic data.     

Molecular interactions of new pregnenedione derivatives

The in vitro inhibitory activity of five new progesterone derivatives: 17alpha-hydroxy-16beta-methylpregna-1,4,6-triene-3,20-dione 1; 16beta-methyl-17alpha-toluoyloxypregna-1,4,6-triene-3,20-dione 2; 17alpha-hydroxy-6-methylenepregn-4-ene-3,20-dione 3; 6-methylene-17alpha-toluoyloxypregn-4ene-3,20-dione 4 and 17alpha-(p-bromobenzoyloxy)-6-methylenepregn-4-ene-3,20-dione 5 was determined. These compounds were evaluated as 5alpha-reductase inhibitors as well as antagonists for the androgen receptor. Compounds 1, 2, 3, 4 and 5 showed the following inhibitory activity for the 5alpha-reductase enzyme with IC(50) values of: 1 (1.65 microM), 2 (10 microM), 3 (19 nM), 4 (100 nM) and 5 (100 nM). The results of this study also showed the effect of increasing concentrations of the novel steroids upon [(3)H]dihydrotestosterone binding to androgen receptors from male hamster prostate. The K(i) values for compounds 1, 2, 3, 4, 5 and dihydrotestosterone showed the following order of affinity for the androgen receptor: 4>5>dihydrotestosterone>2>3>1. The overall data indicated that all synthesized compounds 1, 2, 3, 4 and 5 are inhibitors of the 5alpha-reductase enzyme present in the hamster prostate. In addition compounds 1, 2, 3, 4 and 5 also presented an affinity for the androgen receptor.     

宽叶秦岭藤根部的化学成分

通过正相和反相硅胶柱层析从宽叶秦岭藤根部乙醇提取物中分离纯化得到19个化合物,经波谱分析并结合化学方法鉴定了其结构,其中4个为新化合物,它们分别是3,5-二羟基二十烷酸羽扇豆醇酯(3),2-羟甲基-5-甲氧基苯基-O-β-D-吡喃葡萄糖甙(11),Δ5-孕甾烯-3β,20(S)-二醇-20-O-β-D-吡喃葡萄糖基(1→6)-β-D-吡喃葡萄糖甙(18,秦岭藤甙C)和Δ5-孕甾烯-3β,20(S)-二醇-3-O-β-D-吡喃葡萄糖基-20-O-β-D-吡喃葡萄糖基(1→6)-β-D-吡喃葡萄糖甙(19,秦岭藤甙D).     

Five new phenylethanoid glycosides from the whole plants of Lamium purpureum L

Five new phenylethanoid glycosides, lamiusides A (1), B (2), C (3), D (4) and E (5), were isolated from the whole plants of Lamium purpureum L. (Labiatae) together with seven known compounds (6-12). On the basis of chemical and spectral analyses, the structures of the new compounds were elucidated to be 2-(3,4-dihydroxyphenyl)ethyl-O-beta-D-galactopyranosyl-(1-->2)-alpha-L-rhamnopyranosyl-(1-->3)-(4-O-trans-caffeoyl)-beta-D-glucopyranoside (1), 2-(3,4-dihydroxyphenyl)ethyl-O-beta-D-galactopyranosyl-(1-->2)-alpha-L-rhamnopyranosyl-(1-->3)-(4-O-trans-feruloyl)-beta-D-glucopyranoside (2), 2-(3,4-dihydroxyphenyl)ethyl-O-beta-D-galactopyranosyl-(1-->2)-alpha-L-rhamnopyranosyl-(1-->3)-(6-O-trans-caffeoyl)-beta-D-glucopyranoside (3), 2-(3,4-dihydroxyphenyl)-R,S-methoxy-ethyl-O-beta-D-galactopyranosyl-(1-->2)-alpha-L-rhamnopyranosyl-(1-->3)-(4-O-trans-caffeoyl)-beta-D-glucopyranoside (4) and 2-(3-hydroxy-4-methoxyphenyl)ethyl-O-alpha-L-rhamnopyranosyl-(1-->3)-beta-D-glucopyranosyl-(1-->6)-(4-O-cis-feruloyl)-beta-D-glucopyranoside (5). In addition, the radical-scavenging activities of compounds 1-4 on 1,1-diphenyl-2-picrylhydrazyl radical were examined.     

Synthesis and characterization of novel 2-(1-benzyl-3-[4-fluorophenyl]-1H-pyrazol-4-yl)-7-fluoro-4H-chromen-4-one derivatives

Novel 1-benzyl-3-(4-fluorophenyl)-1H-pyrazole-4-carbaldehydes 3a to 3e were synthesized via Vilsmeier-Haack reaction of the appropriate 1-benzyl-2-(1-(4-fluorophenyl)ethylidene)hydrazines, derived from 4-fluoroacetophenone 1 with substituted 2-benzylhydrazines 2a to 2e . The base catalyzed condensation of 1-benzyl-3-(4-fluorophenyl)-1H-pyrazole-4-carbaldehydes 3a to 3e with 1-(4-fluoro-2-hydroxyphenyl)ethanone 4 gave (E)-3-(1-benzyl-3-(4-fluorophenyl)-1H-pyrazol-4-yl)-1-(4-fluoro-2-hydroxyphenyl)prop-2-en-1-ones 5a to 5e . On cyclization with dimethyl sulfoxide (DMSO)/I₂, compounds 5a to 5e gave 2-(1-benzyl-3-(4-fluorophenyl)-1H-pyrazol-4-yl)-7-fluoro-4H-chromen-4-ones 6a to 6e . Structures of all novel compounds were confirmed by infrared (IR), proton nuclear magnetic resonance (¹H NMR), carbon nuclear magnetic resonance (¹³C NMR), and mass spectral data. All the synthesized compounds were screened for their antibacterial activities.     

Chemical Constituents of a Formosan Soft Coral Sinularia sp.

A new marine sterol 7β-hydroperoxy-24-methylenecholesterol ( 1 ) along with five known compounds sarcophytol A ( 2 ), (Z)-N-[2-(4-hydroxyphenyl)ethyl]-3-methyldodec-2-enamide ( 3 ), 5α,7αH-eduesm-11(13)en-4α-ol ( 4 ), 24-methylenecholesterol ( 5 ) and 1β-hydroxy-α-cyperone ( 6 ) have been isolated from a Formosan soft coral Sinularia sp. The structures of the above compounds were determined by spectral analyses. Cytotoxicity of compounds 1–6 toward various cancer cell lines also is reported.     

New benzoyl glucosides and cytotoxic pterosin sesquiterpenes from Pteris ensiformis Burm

Three new compounds: 2R,3R-pterosin L 3-O-beta-D-glucopyranoside (1), beta-D-xylopyranosyl(1-->2)-7-O-benzoyl-beta-D-glucopyranoside (2) and 4-O-benzoyl-beta-D-xylo-pyranosyl(1-->2)-7-O-benzoyl-beta-D-glucopyranoside (3), together with nine known compounds, were isolated from the ethyl acetate extract of Pteris ensiformis. 5-[2-Hydroxyethylidene]-2(5H)-furanone (4), which had been synthesized, was isolated from natural sources for the first time. The structures of all isolated compounds were determined on the basis of mass and spectroscopic evidence. Compound 1 and pterosin B (5) show cytotoxicity against HL 60 cells (human leukemia) with the IC(50) values of 3.7 and 8.7 microg/mL, respectively.     

Bioactive Components from the Mycelium of Antrodia Salmonea

Three new compounds, 2,4‐dimethoxy‐6‐methylbenzene‐1,3‐diol ( 1 ), salmoquinone ( 2 ), and 3‐(4‐hydroxyphenyl)‐4‐isobutyl‐1H‐pyrrole‐2,5‐dione ( 3 ), together with six known compounds, 2‐methoxy‐6‐methyl‐p‐benzoquinone ( 4 ), 2,3‐dimethoxy‐5‐methyl‐p‐benzoquinone ( 5 ), 2‐hydroxy‐5‐methoxy‐3‐methyl‐p‐benzoquinone ( 6 ), eburcoic acid ( 7 ), fomefficinic acid C ( 8 ), and a pyrroledione ( 9 ), were isolated from the mycelium of Antrodia salmonea. The structures of these compounds were elucidated by spectrometric analyses including IR, NMR, and MS. Among these compounds, 4 and 5 exhibited cytotoxicity against KB, HepG2, and H2058 cell lines.     

Carboxylic Acids from <Emphasis Type="Italic">Phyllanthus urinaria</Emphasis>

Five compounds, terephthalic acid mono-[2-(4-carboxy-phenoxycarbonyl)-vinyl] ester (1), (E)-3-(5′-hydroperoxy-2,2′-dihydroxy[1,1′-biphenyl]-4-yl)-2-propenoic acid (2), 3,4,5-trihydroxybenzoic acid (3), succinic acid (or butanedioic acid) (4), and 2,3,4,5,6-pentahydroxybenzoic acid (5), were isolated from Phyllanthus urinaria. The structures of these compounds were elucidated by means of spectral techniques including IR, MS, and 1D/2D NMR. 1 and 2 are new compounds.__________Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 14–17, January–February, 2005.     

Strontium Nitriminotetrazolates – Suitable Colorants in Smokeless Pyrotechnic Compositions

The new compounds strontium 5‐nitriminotetrazolate dihydrate ( 1 ), strontium bis(1‐hydro‐5‐nitriminotetrazolate) tetrahydrate ( 2 ), strontium bis(1‐methyl‐5‐nitriminotetrazolate) monohydrate ( 3 ) and strontium bis(2‐methyl‐5‐nitraminotetrazolate)·x H₂O (x = 2–4) ( 4 ) were synthesized by the reactions of strontium hydroxide octahydrate and 5‐nitriminotetrazole ( 5 ), 1‐methyl‐5‐nitriminotetrazole ( 6 ) and 2‐methyl‐5‐nitraminotetrazole ( 7 ), respectively. The compounds were characterized using multinuclear NMR spectroscopy, vibrational (IR and Raman) spectroscopy, elemental analysis and differential scanning calorimetry. The solid state structures of 1 , 2 , 3 and 4 were determined using low temperature X‐ray diffraction. In addition, the sensitivities (impact, friction, electrical discharge) of 1 – 4 were investigated and their use as red colorants in pyrotechnic compositions was tested.     

Highly efficient total synthesis of the marine natural products (+)-avarone, (+)-avarol, (-)-neoavarone, (-)-neoavarol and (+)-aureol

Biologically important and structurally unique marine natural products avarone (1), avarol (2), neoavarone (3), neoavarol (4) and aureol (5), were efficiently synthesized in a unified manner starting from (+)-5-methyl-Wieland-Miescher ketone 10. The synthesis involved the following crucial steps: i) Sequential BF(3)Et(2)O-induced rearrangement/cyclization reaction of 2 and 4 to produce 5 with complete stereoselectivity in high yield (2 --> 5 and 4 --> 5); ii) strategic salcomine oxidation of the phenolic compounds 6 and 8 to derive the corresponding quinones 1 and 3 (6 --> 1 and 8 --> 3); and iii) Birch reductive alkylation of 10 with bromide 11 to construct the requisite carbon framework 12 (10 + 11 --> 12). An in vitro cytotoxicity assay of compounds 1-5 against human histiocytic lymphoma cells U937 determined the order of cytotoxic potency (3 > 1 > 5 > 2 > 4) and some novel aspects of structure-activity relationships.     

Three New Phenyl Ether Derivatives from Aspergillus carneus HQ889708

Three new phenyl ether derivatives, 3‐hydroxy‐5‐(3‐hydroxy‐5‐methylphenoxy)benzoic acid ( 1 ), 3,4‐dihydroxy‐5‐(3‐hydroxy‐5‐methylphenoxy)benzoic acid ( 2 ), 3‐[3‐hydroxy‐5‐(hydroxymethyl)phenoxy]‐5‐methylphenol ( 3 ), and three known compounds 4 – 6 were obtained from the fermentation broth of Aspergillus carneus HQ889708, which was isolated from sea water from South China Sea. The structures of compounds 1 – 3 were established on the basis of spectroscopic methods including ESI‐MS and NMR. Compounds 4 – 6 were reported before as synthesized products, herein, they are reported from nature for the first time.     

含肟醚的新型四唑啉酮衍生物的合成及除草活性研究

1-(4-氯苯基)-1,4-二氢-四唑-5-酮(1)与氯丙酮反应生成1-(4-氯苯基)-4-(2-氧代丙基)-1,4-二氢-四唑-5-酮(2). 中间体2、盐酸羟胺和卤化物通过三组分一锅法合成了目标化合物3. 初步生物活性测试结果表明: 目标化合物3具有较好的除草活性.     

New taxane diterpenoids from the roots of Taiwanese Taxus mairei

Five new taxane diterpenoids, taxumairols G (1), H (2), I (3), J (4), and L (5) were isolated from extracts of the roots of Taiwanese Taxus mairei (LEMEE & LEVL.) S. Y. Hu. Compounds 1-4 belong to the new 11(15-->1)-abeo-taxene system, having a tetrahydrofuran ring along carbons C-2, C-3, C-4 and C-20. Compounds 3 and 4 contain an isopropenyl group at C-1 while compounds 1 and 2 are attached with a benzoxyl group at C-15. The structures of compounds 1-5 were determined on the basis of two-dimensional (2D)-NMR techniques including correlation spectroscopy (COSY), heteronuclear single quantum coherence (HSQC), heteronuclear multiple bond correlation (HMBC), and nuclear Overhauser effect spectroscopy (NOESY) experiments.     

A series of (6,6)-connected porous lanthanide−organic framework enantiomers with high thermostability and exposed metal sites: scalable syntheses, structures, and sorption properties

A series of microporous lanthanide-organic framework enantiomers, Ln(BTC)(H(2)O)·(DMF)(1.1) (Ln = Y 1a, 1b; Tb 2a, 2b; Dy 3a, 3b; Er 4a, 4b; Yb 5a, 5b, BTC = 1,3,5-benzenetricarboxylate; DMF = N,N-dimethylformamide) with unprecedented (6,6)-connected topology have been prepared and characterized. All these compounds exhibit very high thermal stability of over 450 °C. The pore characteristics and gas sorption properties of these compounds were investigated at cryogenic temperatures by experimentally measuring nitrogen, argon, and hydrogen adsorption/desorption isotherms. The studies show that all these compounds are highly porous with surface areas of 1080 (1), 786 (2), 757 (3), 676 (4), and 774 m(2)/g (5). The amounts of the hydrogen uptakes, 1.79 (1), 1.45 (2), 1.40 (3), 1.51 (4), and 1.41 wt % (5) at 77 K (1 atm), show their promising H(2) storage performances. These porous materials with considerable surface areas, high voids of 44.5% (1), 44.8% (2), 47.7% (3), 44.2% (4), and 45.7% (5), free windows of 6-7 ?, available exposed metal sites and very high thermal stability can be easily prepared on a large scale, which make them excellent candidates in many functional applications, such as, gas storage, catalysis, and so on.     

Neuroprotective Activities of Boophone haemanthoides (Amaryllidaceae) Extract and Its Chemical Constituents

Parkinson’s disease (PD) is a neurodegenerative condition that progresses as age increases, and some of its major symptoms include tremor and postural and movement-related difficulties. To date, the treatment of PD remains a challenge because available drugs only treat the symptoms of the disease or possess serious side effects. In light of this, new treatment options are needed; hence, this study investigates the neuroprotective effects of an organic Boophone haemanthoides extract (BHE) and its bioactive compounds using an in vitro model of PD involving the toxin 1-methyl-4-phenylpyridinium (MPP⁺) and SH-SY5Y neuroblastoma cells. A total of seven compounds were isolated from BHE, viz distichamine (1), 1α,3α-diacetylnerbowdine (2), hippadine (3), stigmast-4-ene-3,6-dione (4), cholest-4-en-3-one (5), tyrosol (6), and 3-hydroxy-1-(4′-hydroxyphenyl)-1-propanone (7). Six compounds (1, 2, 4, 5, 6 and 7) were investigated, and five showed neuroprotection alongside the BHE. This study gives insight into the bioactivity of the non-alkaloidal constituents of Amaryllidaceae, since the isolated compounds and the BHE showed improved cell viability, increased ATP generation in the cells as well as inhibition of MPP⁺-induced apoptosis. Together, these findings support the claim that the Amaryllidaceae plant family could be a potential reserve of bioactive compounds for the discovery of neuroprotective agents.     

An Unexpected and Green Synthetic Protocol for Ethyl 1‐Aroyl/Aroylmethyl‐5‐methyl‐3‐methylthiopyrazole‐4‐carboxylates: High Regioselectivity in Alkylation and Acylation Reactions between N‐1 and N‐2 of a Pyrazole Ring

Two series, totaling twelve, of new compounds, ethyl 1‐aroyl/(aroylmethyl)‐5‐methyl‐3‐methylthiopyrazole‐4‐carboxylates ( 5 / 6 ), have been synthesized via highly regioselectively acylation and alkylation reactions of ethyl 3‐methyl‐5‐methylthio‐1 H‐pyrazole‐4‐carboxylate ( 2a ) with aroyl chloride ( 3 ) and eco‐friendly reagents alpha‐tosyloxysubstituted acetophenones ( 4 ), respectively, and a green protocol has been developed. The acylation reactions were carried out under ultrasound irradiation, and the alkylation reactions were under microwave irradiation and ultrasound irradiation, respectively. Conventional reaction conditions, as well as the use of alpha‐bromosubstituted acetophenone ( 4 ′) have also been applied in the synthesis of some randomly selected compounds in both series and have generated identical compounds correspondingly. Unexpected structures of compounds were unambiguously determined by X‐ray crystallographic analysis.     

New Helvolic Acid Derivatives with Antibacterial Activities from Sarocladium oryzae DX-THL3, an Endophytic Fungus from Dongxiang Wild Rice (Oryza rufipogon Griff.)

Three new helvolic acid derivatives (named sarocladilactone A (1), sarocladilactone B (2) and sarocladic acid A (3a)), together with five known compounds (6,16-diacetoxy-25-hy- droxy-3,7-dioxy-29-nordammara-1,17(20)-dien-21-oic acid (3b), helvolic acid (4), helvolinic acid (5), 6-desacetoxy-helvolic acid (6) and 1,2-dihydrohelvolic acid (7)), were isolated from the endophytic fungus DX-THL3, obtained from the leaf of Dongxiang wild rice (Oryza rufipogon Griff.). The structures of the new compounds were elucidated via HR-MS, extensive 1D and 2D NMR analysis and comparison with reported data. Compounds 1, 2, 4, 5, 6 and 7 exhibited potent antibacterial activities. In particular, sarocladilactone B (2), helvolinic acid (5) and 6-desacetoxy-helvolic acid (6) exhibited strongly Staphylococcus aureus inhibitory activity with minimum inhibitory concentration (MIC) values of 4, 1 and 4 μg/mL, respectively. The structure–activity relationship (SAR) of these compounds was primarily summarized.     

Pregnane glycosides and steroid saponins from Smilax bockii Warb. and their NGF-potentiating activity

The chemical constituents of the roots of Smilax bockii Warb. were investigated and two pregnane glycosides and three steroid saponins were isolated. Their structures were established as 3beta-hydroxypregna-5,16-dien-20-one-3-O-alpha-L-rhamnopyranosyl(1 --> 4)-alpha-L-rhamnopyranosyl(1 --> 4)-[alpha-L-rhamnopyranosyl(1 --> 2)]-beta-D-glucopyranoside (1), 3beta-hydroxypregna-5,16-dien-20-one-3-O-alpha-L-rhamnopyranosyl(1 --> 2)-[alpha-L-rhamnopyranosyl(1 --> 4)]-beta-D-glucopyranoside (2), dioscin (3), methyl protodioscin (4), 26-O-beta-D-glucopyranosyl-22alpha-methoxyl-(25R)-furost-5-en-3beta, 26-diol 3-O-alpha-L-rhamnopyranosyl(1 --> 4)-alpha-L-rhamnopyranosyl(1 --> 4)-[alpha-L-rhamnopyranosyl(1 --> 2)]-beta-D-glucopyranoside (5) on the basis of spectral analysis and chemical methods. Compound 1 is a new natural product and compounds 2, 5 were first isolated from the genus Smilax. Compound 5 showed enhancing activity of nerve growth factor (NGF)-induced neurite outgrowth in PC 12D cells.     

Isolation of toxic compounds from wild Phaeocystis globosa

Two new compounds, namely taenialactam C and globorin A (1 and 2), as well as six known compounds, cornoside (3), 2-phenylethyl-b-D-glucoside (4), 3-isopropyl-5-acetoxycyclohexene-2-one-1 (5), 4-methyl-phenol (6), 5-[(2S)-2-aminobutyl]-2-methyl-phenol (7), and 1-(4-methylphenyl)-1-propanone (8) were isolated from wild Phaeocystis globosa. The structures of the new compounds were established by detailed spectroscopic analysis and by comparison with spectral data of related known compounds. The structures of the known compounds were identified by comparing their spectroscopic data with those reported in the literature. This paper also reports toxicity properties of the eight compounds against the brine shrimp Artemia salina and juvenile Epinephelus akaara fish. Some of these compounds showed significant lethality on the brine shrimp A. salina and the juvenile E. akaara fish.