A novel sesquiterpenoid from the leaves of <Emphasis Type="Italic">Cinnamomum subavenium</Emphasis>

A novel sesquiterpenoid, subamol ((3-methoxy-5H-9,10-dihydroxybenzo[3,4]cyclohepta[1,2-f])inden-7-yl)methanol)) (1), along with six compounds, including one ionone: (+)-abscisic acid (2); and five benzenoids: syringaldehyde (3), trans-coumaric acid (4), cis-coumaric acid (5), vanillic acid (6), and p-hydroxybenzoic acid (7), were isolated from the leaves of Cinnamomum subavenium Miq (Lauraceae). These compounds were identified and characterized by physical and spectral evidence.     

Secondary metabolites isolated from the fungus <Emphasis Type="Italic">Biscogniauxia cylindrospora</Emphasis> BCRC 33717

One new dihydroisocoumarin, (3S)-5-hydroxy-8-O-methylmellein (1), as well as nine known compounds, 5-formylmellein (2), mellein-5-carboxylic acid (3), 5-hydroxymethylmellein (4), 3β-hydroxystigmast-5- en-7-one (5), N-trans-feruloyltyramine (6), N-cis-feruloyltyramine (7), vanillic acid (8), methyl paraben (9), and syringaldehyde (10), were isolated from the n-BuOH-soluble fraction of the 70% EtOH extract of rice fermented with the endophytic fungus Biscogniauxia cylindrospora (BCRC 33717). Their structures were elucidated by 1D and 2D NMR spectroscopy together with HR-ESI-MS analysis and comparison of the spectroscopic data with those reported for structurally related compounds.     

An isoindole alkaloid from Portulaca oleracea L.

A novel isoindole alkaloid named oleraisoindole (1), together with six known compounds, 7′-ethoxy-trans-feruloyltyramine (2), N-trans-feruloyltyramine (3), N-trans-feruloyl-3-methoxytyramine (4), N-trans-p-coumaroyltyramine (5) aurantiamide (6) and ferulic acid methyl ester (7) were isolated from Portulaca oleracea L. Compounds 2 and 7 were isolated for the first time from this plant. Compound 1 was identified using spectroscopic methods including HR-ESI-TOF-MS, 1D-NMR, 2D-NMR. It was tested in a nitric oxide (NO) inhibition assay and was shown to inhibit NO production in RAW 264.7 cells induced by LPS.     

Annelation of drotaverine by <Emphasis Type="Italic">p</Emphasis>-quinones to form hydroxyindolo- and hydroxybenzindoloisoquinoline derivatives

1-(3, 4-Diethoxybenzyl)-6, 7-diethoxy-3, 4-dihydroisoquinoline (drotaverine, 1a) reacts with p-benzoquinone (2) and p-naphthoquinone (3) in nitromethane or during fusion to give 5-(3, 4-diethoxyphenyl)-7, 8-diethoxy-3-hydroxy-5a, 10, 11, 12-tetrahydroindolo[2, 1-a]isoquinoline (4) and 7-(3, 4-diethoxyphenyl)-9, 10-diethoxy-5-hydroxy-7a, 12, 13, 14-tetrahydrobenz[g]indolo[2, 1-a]isoquinoline (5), respectively. Compounds 4 and 5 are smoothly alkylated at the oxygen atom in the presence of bases. The structure of one alkylation product, viz., 3-allyloxy-5-(3, 4-diethoxyphenyl)-7, 8-diethoxy-5a, 10, 11, 12-tetrahydroindolo[2, 1-a]isoquinoline, was established by X-ray diffraction analysis.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 761–769, March, 2005.     

A new lactam alkaloid from Portulaca oleracea L. and its cytotoxity

A new lactam alkaloid named oleraciamide D (1), indentified as (5R)-4-(3-methoxy-4-hydroxyphenyl)-5-(4-hydroxyphenyl)-5,6-dihydropyridin-2(1H)-one, together with five known compounds, indole-3-aldehyde (2), portulacatone (3), N-trans-feruloyloctopamine (4), N-trans-feruloyl-3′-O-methyldopamine (5) and N-trans-feruloyltyramine (6) were isolated from Potulaca oleracea L. Among them, indole-3-aldehyde (2) was isolated from the medicine for the first time. The structure of the new alkaloid was elucidated via UHPLC-ESI-Q-TOF/MS, 1D NMR and 2D NMR. The five known compounds were established by comparing the ¹H-NMR and ¹³C NMR with the reported literature. Oleraciamide D (1) showed cytotoxicity against SH-SY5Y cells when concentration at 50 uM by CCK-8 method.     

New C20-gibberellin diterpene from the leaves of Schefflera sessiliflora De P. V.

From the leaves of Schefflera sessiliflora De P. V., one new C₂₀-gibberellin diterpene 2β,12β-dihydroxygibberellin (12β-hydroxy-GA₁₁₀ or 2β-hydroxy-GA₁₁₂) (1), together with three known compounds, trans-tiliroside (2), kaempferol 3-O-β-d-glucuronopyranoside (3), 5-p-trans-coumaroylquinic acid (4), was isolated for the first time from the genus Schefflera by various chromatography methods. Their structures were elucidated by IR, UV, HR-ESI-MS, NMR 1D and 2D experiments and comparison with previous reported data. The α-glucosidase inhibitory activity of all compounds was measured. The isolates (2, 3) showed better α-glucosidase inhibitory activity (IC₅₀ = 134.60, 147.10 μM, respectively) than the standard drug acarbose (IC₅₀ = 214.50 μM).     

Two new quercetin glycoside derivatives from the fruits of Gardenia jasminoides var. radicans

Two new quercetin glycoside derivatives named quercetin-3-O-[2-O-trans-caffeoyl-α-l-rhamnopyranosyl-(1 → 6)-β-d-glucopyranoside] (1) and quercetin-3-O-[2-O-trans-caffeoyl-β-l-rhamnopyranosyl-(1 → 6)-β-d-glucopyranoside] (2) along with three known flavonoids, 5-hydroxy-6,7,3′,4′,5′-pentamethoxyflavone (3), 5,7-dihydroxy-8-methoxyflavone (4) and kaempferol 3-O-β-d-glucopyranoside (5), were isolated from the fruits of Gardenia jasminoides var. radicans. The structures of the new compounds were determined by means of extensive spectroscopic analysis (1D, 2D NMR and HR-ESI-MS), glycoside hydrolysis and sugar HPLC analysis after derivatisation. This is the first report on the isolation of a pair of compounds with α or β-l-rhamnopyranosyl configuration from plant and the first detail assignment of their NMR data.     

A new cerebrogalactoside from <Emphasis Type="Italic">Juglans mandshurica</Emphasis>

A new cerebrogalactoside, Juglans cerebroside A (1), together with five known compounds, quercetin-3-O-β-D-galactopyranoside (2), myricetin-3-O-β-D-galactopyranoside (3), 2″E-quercetin-3-O-β-D-(6″″-O-[3″(4′″-hydroxyphenyl) propylene acyl]) glucopyranoside (4), gallic acid (5), and 2-methyl-1-hexadecanol (6) were isolated from the leaves of Juglans mandshurica Maxim. The structures of these compounds were determined by 1D, 2D NMR, and MS techniques.     

Feruloyl,caffeoyl, and flavonol glucosides from <Emphasis Type="Italic">Equisetum hyemale</Emphasis>

Feruloyl, caffeoyl, and flavonol glucosides were isolated from the stems of Equisetum hyemale L. The structures of the compounds were elucidated as trans-feruloyl-4-β-glucoside (1), cis-feruloyl-4-β-glucoside (2), trans-caffeoyl-3-β-glucoside (3), kaempferol-3-sophoroside (4), kaempferol-3-sophoroside-7-β-glucoside (5), and herbacetin-3-sophoroside-8-β-glucoside (6) based on the spectral evidence.     

Two new diacetylene glycosides: bhutkesoside A and B from the roots of Ligusticopsis wallichiana

Two new diacetylene glycosides: bhutkesoside A (1) and B (2), along with 10 known compounds, i.e. falcarindiol (3), chlorogenic acid (4), 5-O-p-coumaroyl-quinic acid (5), 3,5-di-O-caffeoyl-quinic acid (6), 4-hydroxy-7-methoxy-phenylethanol (7), ferulic acid (8), dehydrodiconiferyl alcohol-4-O-β-d-glucopyranoside (9), 5,7-dihydroxy-2-methylchromone-7-O-rutinoside (10), schumanniofioside B (11) and marmesinin (12) were isolated from the roots of Ligusticopsis wallichiana (DC) Pimenov & Kljuykov (Apiaceae), commonly known as ‘Bhutkesh’ in Nepal. The structures were determined on the basis of spectroscopic data. Compounds 4 and 6 showed potent antioxidant activity on DPPH free radical scavenging assay.     

Phenolic compounds from the aerial parts of Clematis viticella L. and their in vitro anti-inflammatory activities*

Phytochemical investigations on the EtOH extract of Clematis viticella led to the isolation of six flavonoid glycosides, isoorientin (1), isoorientin 3′-O-methyl ether (2), quercetin 7-O-α-L-rhamnopyranoside (3), quercetin 3,7-di-O-α-L-rhamnopyranoside (4), manghaslin (5) and chrysoeriol 7-O-β-D-glucopyranoside (6), one phenylethanol derivative, hydroxytyrosol (7), along with three phenolic acids, caffeic acid (8), (E)-p-coumaric acid (9) and p-hydroxybenzoic acid (10). The structures of the isolates were elucidated on the basis of NMR and HR-MS data. All compounds were isolated from C. viticella for the first time. Compounds 7 and 8 showed significant anti-inflammatory activity at 100 μM by reducing the release of NO in LPS-stimulated macrophages comparable to positive control indomethacin. Compounds 3 and 7 exhibited anti-inflammatory activity through lowering the levels of TNF-α while 1, 3 and 5 decreased the levels of neopterin better than the positive controls.     

Phenolics from Castanea sativa leaves and their effects on UVB-induced damage

The phytochemical investigation of the methanol extract of the leaves of Castanea sativa Mill., source of the Italian PGI (Protected Geographical Indication) product ‘Marrone di Roccadaspide’ (Campania region) afforded as main compounds crenatin (1), chestanin (2), gallic acid (3), cretanin (4), 5-O-p-coumaroylquinic acid (5), p-methylgallic acid (6) and quercetin-3-O-glucoside (7). To quantify the isolated compounds a LC-ESI(QqQ)MS method working with a very sensitive and selective mass tandem experiment called Multiple Reaction Monitoring (MRM) has been developed. Moreover the antioxidant capacity by TEAC assay and the ability of compounds 1–7 to protect HaCaT human keratinocytes from UVB-induced damage has been investigated.     

Inhibition effect of phenyl compounds from the Oryza sativa roots on melanin production in murine B16-F10 melanoma cells

Five phenyl compounds, vanillin (1), methyl trans-ferulate (2), trans-p-coumaric acid methyl ester (3), N-benzoyltryptamine (4), and N-(trans-cinnamoyl)tryptamine (5), were isolated from the roots of Oryza sativa L. and identified on the basis of spectroscopic data. Compounds 3 and 5 showed strong inhibition effect on melanin production in murine B16-F10 melanoma cells and tyrosinase activity. Also, the quantitative analysis of the compounds was carried out using LC/MS/MS experiment. Compounds 3 and 5 could be used as skin-whitening agents.     

A new 9,10-dihydrophenanthrene from Dendrobium moniliforme

A new 9,10-dihydrophenanthrene,1,5-dihydroxy-3,4,7-trimethoxy-9,10-dihydrophenanthrene (1) was isolated and identified from the whole plants of Dendrobium moniliforme, as well as 24 known compounds including hircinol (2), (2R^*,3S^*)-3-hydroxymethyl-9-methoxy-2-(4′-hydroxy-3′,5′-dimethoxyphenyl)-2,3,6,7-tetrahydro-phenanthro[4,3-b]furan-5,11-diol (3), diospyrosin (4), aloifol I (5), moscatilin (6), 3,4′-dihydroxy-3′,4,5-trimethoxybibenzyl (7), gigantol (8), 3,3′-dihydroxy-4,5-dimethoxybibenzyl (9), longicornuol A (10), N-trans-cinnamoyltyramine (11), paprazine (12), N-trans-feruloyl 3′-O-methyldopamine (13), moupinamide (14), dihydroconiferyl dihydro-p-coumarate (15), dihydrosinapyl dihydro-p-coumarate (16), 3-isopropyl-5-acetoxycyclohexene-2-one-1 (17), p-hydroxybenzaldehyde (18), vanillin (19), p-hydroxyphenylpropionic acid (20), vanillic acid (21), protocatechuic acid (22), (+)-syringaresinol (23), β-sitosterol (24) and daucosterol (25). Compounds 3, 4, 13, 16, 17 and 20 were isolated from the Dendrobium genus for the first time, and compounds 2, 5, 7, 9–12, 14, 15, 18, 21 and 22 were originally obtained from D. moniliforme.     

含噁二唑肟醚取代的均三唑水杨醛席夫碱的合成及抗菌活性

4-氨基-5-(4-甲氧苯基)-3-巯基-均三唑(2)在无水乙酸钠作用下与β-氯苯丙酮(3)缩合得氨基三唑硫代苯丙酮(4). 化合物4与盐酸羟胺肟化得羰基肟化物5, 接着与水杨醛缩合得到席夫碱肟6, 用氯甲基噁二唑7a～7e对化合物6的肟羟基醚化得到目标物均三唑噁二唑肟醚1a～1e. 所合成的新化合物结构由元素分析和光谱数据表征, 体外抗菌活性也被试验.     

Phenolic constituents from the stems of <Emphasis Type="Italic">Acanthopanax senticosus</Emphasis>

A new phenolic glycoside was isolated from the stems of Acanthopanax senticosus together with sixteen known compounds. The structure of the new compound was determined to be 2,6-dimethoxy-4-[(1E)-3,3-dimethoxy-1-propenyl]phenyl β-D-glucopyranoside (1) by means of physical, chemical, and spectroscopic methods. Of the known compounds, salvadoraside (7), (7R,8S)-dihydrodehydrodiconiferyl alcohol 4,9′-di-O-β-D-glucopyranoside (8), 3-(4-O-β-D-glucopyranosylferuloyl)quinic acid (15), rel-5-(1R,5S-dimethyl-3R,4R,8S-trihydroxy-7-oxa-6-oxobicyclo[3,2,1]oct-8-yl)-3-methyl-2Z,4E-pentadienoic acid (16), and lycoperodine-l (17) were first reported from the title plant. The inhibitory activities of the isolated compounds against α-glucosidase from rat intestine were also reported.     

New thiazinediones and other components from Xanthium strumarium

Two new thiazinediones along with five known compounds were isolated from the fruits of Xanthium strumarium L. The structures of the two new compounds were determined to be 7-hydroxymethyl-8,8-dimethyl-4,8-dihydrobenzol[1,4]thiazine-3,5-dione-11-O-β-D-glucopyranoside (1) and 2-hydroxy-7-hydroxymethyl-8,8-dimethyl-4,8-dihydrobenzol[1,4]thiazine-3,5-dione-11-O-β-D-glucopyranoside (2). The five known compounds were identified as xanthiazone (3), chlorogenic acid (4), ferulic acid (5), formononetin (6), and ononin (7), respectively. Published in Khimiya Prirodnykh Soedinenii, No. 5, pp. 456–458, September–October, 2006.     

New chalcanonol glycoside from the seeds of saw palmetto: antiproliferative and antioxidant effects

A new chalcanonol glycoside dimer, bis-O-[(I-4′) → (II-6′)]-α-hydroxyphloretin-2′-O-β-glucoside (1), in addition to six known compounds, namely ( ? )-epicatechin (2) and ( ? )-epiafzelechin (3), 4-hydroxybenzoic acid (4), protocatechuic acid (5), methylgallate (6), β-sitosterol (7) and β-sitosterol-3-O-glucoside (8), was isolated from the seeds of saw palmetto. The structures of the isolated compounds were established from the analysis of their MS and 1D and 2D NMR spectroscopic data. The antiproliferative activities of the isolated compounds towards PC3, the human prostate cancer cells were investigated. Amongst the isolated compounds, the new compound and the sterolic derivatives showed antiproliferative effects. Screening of the antioxidant effects of the isolated compounds by 2,2′-azino-bis-(3-ethylbenzthiazoline-6-sulfonic acid radical assay revealed that the isolated phenolics were active free radical scavengers.     

Synthesis and transformations of (±)-trans-4aβ(H), saα(H)-octahydro-4α,7β-dimethyl-2H-1-benzopyran-2-one

Hydrogenation of 4,7-dimethylcoumarin ( 1 ) in alkaline medium has been shown to furnish a mixture of (±)-trans-4aβ(H),8aα(H)-octahydro-4α,7β-dimethyl-2H-1-benzopyran-2-one ( 2 ), (±)-trans-4aβ(H),8aα(H)-octahydro-4α,7α-dimethyl-2H-1-benzopyran-2-one ( 3 ) and (±)-cis-4aα(H),8aα(H)-octahydro-4α,7α-dimethyl-2H-1-benzopyran-2-one ( 4 ) in 40:25:35:ratio, respectively. The stereochemistry of the major hydrogenation product 2 , has been established by transforming it to p-menthane derivatives e.g. (±)-2 (R)-[2′(R)hydroxy-4′(R) methylcyclohex-(1′S)-yl]propan-1-ol ( 20 ) and (±)-trans-3α,6β-dimethyl-3aβ(H),7aα(H)-octahydrobenzofuran ( 12 ). Starting from a mixture of lactones 2, 3 and 4 , lactone 3 has been obtained in pure state employing a sequence of reactions.     

A new alternariol glucoside from fungus Alternaria alternate cib-137

A new secondary metabolite, 2-O-methylalternariol 4-O-β-[4-methoxyl-glucopyranoside] (1), together with four known compounds alternariol methyl ether (2), altenuene (3), isoaltenuene (4) and 2-(2′S-hydroxypropyl)-5-methyl-7-hydroxychromone (5), was isolated from the fungus Alternaria alternate cib-137. Its structure was elucidated on the basis of spectroscopic data. Compounds 3 and 4 demonstrated moderate activity against Staphylococcus aureus.