Chemistry of toxic range plants. Highly oxygenated flavonol methyl ethers from Gutierrezia microcephala

The perennial American desert shrub, Gutierrezia microcephala, contains 20 flavonol methyl ethers displaying nine different oxygenation patterns. These include 11 new flavonols: 5,7-dihydroxy-3,6,8,3′,4′,5′-hexamethoxyflavone, 5,7,4′-trihydroxy-3,6,8,3′,5′-pentamethoxyflavone, 5,7,3′-trihydroxy-3,6,8,4′,5′-pentamethoxyflavone, 5,7,2′,4′-tetrahydroxy-3,6,8,5′-tetramethoxyflavone, 5,7,3′,4′-tetrahydroxy-3,6,8-trimethoxyflavone, 5,7,8,3′,4′-pentahydroxy-3,6-dimethoxyflavone, 3,5,7,3′,4′-pentahydroxy-6,8-dimethoxyflavone, 5,7,4′-trihydroxy-3,6,8-trimethoxyflavone, 5,7,8,4′-tetrahydroxy-3,3′-dimethoxyflavone, 5,7,8,3′,4′-pentahydroxy-3-methoxyflavone and 5,7,8,4′-tetrahydroxy-3-methoxyflavone. In addition, the following known flavonols were isolated: 5,7-dihydroxy-3,8,3′,4′,5′-pentamethoxyflavone, 5,7,4′-trihydroxy-3,8-dimethoxyflavone, 5,7,4′-trihydroxy-3,8,3′-trimethoxyflavone, 5,7,3′,4′-tetrahydroxy-3,8-dimethoxyflavone, 5,7,4′-trihydroxy-3,6,3′-trimethoxyflavone, 5,7,3′,4′-tetrahydroxy-3-methoxyflavone, 5,4′-dihydroxy-3,6,7,8,3′-pentamethoxyflavone, 5,7,4′-trihydroxy-3,6,8,3′-tetramethoxyflavone and 3,5,7,4′-tetrahydroxy-6,8,3′-trimethoxyflavone.     

Flavonoids from Artemisia ludoviciana var. ludoviciana

Nineteen flavonoids were isolated from Artemisia ludoviciana var. ludoviciana, including a new 2′- hydroxy- 6-methoxyflavone, 5,7,2′,4′-tetrahydroxy-6,5′-dimethoxyflavone. The known compounds include quercetagetin 3,6,3′,4′-tetramethyl ether, eupatilin, 5,7-dihydroxy-3,6,8,4′-tetramethoxyflavone, luteolin 3′,4′-dimethyl ether, jaceosidin, 5,7,4′-trihydroxy-3,6-dimethoxyflavone, tricin, hispidulin, chrysoeriol, kaempferol 3-methyl ether, apigenin, axillarin, eupafolin, selagin and luteolin together with three flavones which were previously isolated for the first time from Artemisia frigida: 5,7,4′-trihydroxy-6, 3′,5′-trimethoxyflavone, 5,7,3′-trihydroxy-6,4′,5′-trimethoxyflavone and 5,7,3′,4′-tetrahydroxy-6,5′- dimethoxyflavone.     

Flavonoids from Gutierrezia grandis

Thirteen flavonoids, including three new compounds, were isolated from Gutierrezia grandis. The structures of the new compounds were 3,5,7,3′,4′-pentahydroxy-6,8-dimethoxyflavone, 5,7,3′-trihydroxy-3,6,8,4′,5′-pentamethoxyflavone and 5,7,3′,5′-tetrahydroxy-3,6,8,4′-tetramethoxyflavone 3′-O-glucoside.     

Six 2′-hydroxyflavonols from Gutierrezia microcephala

Six 2′-hydroxyflavonols were isolated from Gutierrezia microcephala, including four new compounds, 5,7,2′-trihydroxy-3,6,4′,5′-tetramethoxyflavone, 5,7,2′-trihydroxy-3,6,8,4′,5′-pentamethoxyflavone, 5,2′-dihydroxy-3,6,7,8,4′,5′-hexamethoxyflavone and 5,7,2′,4′-tetrahydroxy-3,8,5′-trimethxoyflavone and two known compounds, 5,7,2′,5′-tetrahydroxy-3,6,8,4′-tetramethoxyflavone and 5,7,2′,4′-tetrahydroxy-3,6,8,5′-tetramethoxyflavone.     

5-Methyl ether flavone glucosides from the leaves of Bruguiera gymnorrhiza

Two new 5-methyl ether flavone glucosides (7,4′,5′-trihydroxy-5,3′-dimethoxyflavone 7-O-β-D-glucopyranoside and 7,4′-dihydroxy-5-methoxyflavone 7-O-β-D-glucopyranoside) were isolated from the leaves of Thai mangrove Bruguiera gymnorrhiza together with 7,3′,4′,5′-tetrahydroxy-5-methoxyflavone, 7,4′,5′-trihydroxy-5,3′-dimethoxyflavone, luteolin 5-methyl ether 7-O-β-D-glucopyranoside, 7,4′-dihydroxy-5,3′-dimethoxyflavone 7-O-β-D-glucopyranoside, quercetin 3-O-β-D-glucopyranoside, rutin, kaempferol 3-O-rutinoside, myricetin 3-O-rutinoside and an aryl-tetralin lignan rhamnoside. The structure of a lignan rhamnoside was found to be related to racemiside, an isolated compound from Cotoneaster racemiflora, and also discussed. Structure determinations were based on analyses of physical and spectroscopic data including 1D- and 2D-NMR.     

艾纳香化学成分的研究

从艾纳香(Blumea balsamifera DC.)中分离得到12个化合物,通过理化性质和波谱数据分析分别鉴定为;商路素(1),花椒油素(2),2,4-二羟基-6-甲氧基苯乙酮(3),5,7-二羟基色原酮(4),金丝桃苷(5),异槲皮苷(6),3′,4′,5,7-四羟基-3-甲氧基黄酮(7),槲皮素(8),槲皮素-3′-甲氧基-3-O-β-D-半乳吡喃糖苷(9),4′,5,7-三羟基-3,3′-二甲氧基黄酮(10),3,5,7-三羟基-3′,4′-二甲氧基黄酮(11),木犀草素(12).其中,化合物3-7和9- 11为首次从该属植物中分离得到.     

Flavonoids of Chrysosplenium tetrandrum

Chrysosplenium tetrandrum, from northern British Columbia, accumulates a variety of flavonoid glycosides. Several kaempferol and quercetin mono- and diglycosides were identified. The major flavonoid fraction consisted of O-methylated compounds having an hydroxyl or methoxyl substituent at position-6. Aglycones identified were 5,4′-dihydroxy-3,6,7-trimethoxyflavone, 5,6,7,3′,4′-pentahydroxy-3-methoxyflavone, 5,6,3′,4′-tetrahydroxy-3,7-dimethoxyflavone, 5,6,4′-trihydroxy-3,7,3′-trimethoxyflavone, 5,3′,4′-trihydroxy-3,6,7-trimethoxyflavone, and 5,4′-dihydroxy-3,6,7,3′-tetramethoxyflavone. All occurred as glucosides. The occurrence of 6-substitution and the preponderance of O-methylated flavonoids supports removal of Chrysosplenium from Engler's Saxifraginae.     

Flavonoids in the black rhizomes of Boesenbergia panduta

5-Hydroxy-7-methoxyflavanone, 5,7-dimethoxyflavanone, 5-hydroxy-7-methoxyflavone 5-hydroxy-7,4′-dimethoxyflavone, 5,7-dimethoxyfiavone, 5,7,4′-trimethoxyflavone, 5,7,3′,4′-tetramethoxyflavone, 5-hydroxy-3,7-dimethoxyflavone, 5-hydroxy-3,7,4′-trimethoxyflavone, 3,5,7-trimethoxyflavone and 5-hydroxy-3,7,3′,4′-tetramethoxyflavone have been isolated from the black rhizomes of Boesenbergia pandurata.     

Labdane derivatives and flavones from Gutierrezia dracunculoides

An investigation of the aerial parts of Gutierrezia dracunculoides afforded, in addition to known compounds, three new labdane derivatives, all related to lambertianic acid, 17-hydroxy- and 17-acetoxylambertianic acid and 7α- hydroxylambertianic acid, two esterified and three highly oxygenated flavones, 5,7,4′-trihydroxy-3,3′-dimethoxy- flavone-4′-O- [2-methylbutyrate] and isovalerate, 3′,5′-dihydroxy-3,5,6,7,8,4′-hexamethoxyflavone, 5,3′,5′-trihydroxy- 3,6,7,8,4′-pentamethoxyflavone and 5,7,3′,5′-tetrahydroxy-3,6,8,4′-tetramethoxyflavone. The structures were elucidated by spectroscopic methods and a few chemical transformations.     

Flavonoids from Millettia pulchra

Chemical examination of Millettia pulchra yielded (?)-maackiain, (?)-pterocarpin, (?)-sophoranone and the new compounds (6S, 6aS, 11aR)-6α-methoxypterocarpin, (6S, 6aS,11aR)-6α-methoxyhomopterocarpin, (2S)5,7,4′-trihydroxy-8,3′,5′-triprenylflavanone, (2R,3R)7,4′-dihydroxy-8,3′,5′-triprenyldihydroflavanol, 5,7,2′,4′-tetrahydroxy-6,3′-diprenylisoflavone and 5,7,4′-trihydroxy-2′-methoxy-6,3′-diprenylisoflavone.     

5,7,3′-Trihydroxy-4′,5′-dimethoxyflavone and other phenolics from Poa huecu

Whole plants of Poa huecu have yielded a new flavone characterized as 5,7,3′-trihydroxy-4′,5′-dimethoxyflavone as well as tricin, selagin, umbelliferone and scopoletin.     

Flavonoids of geigeria

Chromatographic separation of the ethanol extract of Geigeria burkei resulted in the isolation and characterization of two known flavonoids, 5,7,3′,4′-tetrahydroxy-6-methoxyflavone and 5,7,4'-trihydroxy-6 methoxyflavone. ¹³CNMR data, as well as the respiratory inhibition and uncoupling of oxidative phosphorylation, is reported for the first time.     

A chalcone and an isoflavone from Millettia pachycarpa seeds

Chemical examination of the seeds of Millettia pachycarpa has yielded a new prenylated isoflavone and a new prenylated chalcone in addition to the previously reported isoflavones 5-hydroxy-4′-methoxy-6″,6″-dimethylpyrano (2″,3″:7,8)isoflavone, 5,7,4′-trihydroxy-6,8-diprenylisoflavone, 5,7,3′,4′-tetrahydroxy-6,8-diprenyl-isoflavone and pomiferin.     

New isoflavonoids related to kievitone from Phaseolus vulgaris

The new isoflavonoids 5,7,2′,4′-tetrahydroxy-8-(3,3-dimethylallyl)isoflavone (2,3-dehydrokievitone) and 7,2′,4′-trihydroxy-8-(3,3-dimethylallyl)isoflavanone (5-deoxykievitone) have been isolated from fungus-inoculated Phaseolus vulgaris pod tissue and from the inoculation droplets. A third isoflavonoid was tentatively identified as 1″,2″-dehydrocyclokievitone and appears to be a metabolite of the phytoalexin kievitone.     

Chemical constituents of the root bark of Erythrina droogmansiana

Two new compounds namely 7,4′-dihydroxy-2′-methoxy-3′-(3-methylbut-2-enyl)isoflavanone (1) and 5,7,3′-trihydroxy-8-(3-methylbut-2-enyl)-[6′′,6′′-dimethylpyrano(2′′,3′′:4′,5′)]isoflavone (4) were isolated from the root bark of Erythrina droogmansiana together with eight known compounds. Their structures were elucidated on the basis of spectroscopic analyses (1D- and 2D-NMR and ESI-HRMS) and by comparison with literature data. In addition, the correct ¹³C NMR of 5,7,2′,4′-tertahydroxy-8,5′-di-(3-metylbut-2-enyl)isoflavone (6) was assigned. The DPPH free radical scavenging properties of the isolated compounds were evaluated. Compounds 4–7 showed weak to moderate DPPH free radical scavenging activities.     

New water soluble flavone and xanthone glycosides from Hypericum canariense L.

The water soluble portion of the aerial parts of Hypericum canariense L. yielded after acetylation the 5,7,3′4′-tetra- and 7,3′4′-triacetates of a new flavonoid 5,7,3′,4′-tetrahydroxy-3-O-β-d-(methyl 2,3,4-triacetoxypyranuronyl)-quercetin, the 3′-acetate of a new flavonoid 3′-hydroxy-5,7,4′-trimethoxy-3-O-β-d-(methyl 2,3,4-triacetoxypyranuronyl)-quercetin, the 3′-acetate and the 3′5′-diacetate of the new flavonoid 5,3′dihydroxy-7,4′-dimethoxy-3-β-d-(methyl 2,3,4-triacetoxypyranuronyl)-quercetin, the xanthone derivative mangiferin 2′,3′,4′,6′-tetraacetate and the latter's new 1,3,6,7′-tetramethoxy, 1,3,6-trimethoxy-4-acetoxy and 1,7-diacetoxy-3,6-dimethoxy analogs.     

Flavonols of parthenium section bolophytum

Casticin (V), 5,7,3′,4′-tetrahydroxy-3,6-dimethoxyflavone-7-glycoside (I), 5,7,4′-trihydroxy-6-methoxyflavone-7-glycoside (hispidulin 7-glycoside) (IV), 5,4′-dihydroxy-3,6,7,3′-tetramethoxyflavone (VII) and 5,7-dihydroxy-3,6,3′,4′-tetramethoxyflavone (XII) were found, with the coumarin scopoletin (IX), in various combinations in the three species of Parthenium section Bolophytum. No infraspecific variation was detected in these calciphilic relicts.     

New prenylated isoflavones and a prenylated dihydroflavonol from Millettia pachycarpa

Extraction of Millettia pachycarpa Benth. gave 5,7,4′-trihydroxy-6,8-diprenylisoflavone (1a), 5,7,4′-trihydroxy-6,3′-diprenylisoflavone (2a), 5,7,3′,4′-tetrahydroxy-6,8-diprenylisoflavone (3a) and (2R, 3R)-5,4′-dihydroxy-8-prenyl-6″,6″-dimethylpyrano[2″,3″: 7,6]-dihydroflavonol (4a) whose structures were established by chemical transformations and spectroscopic means. Pectolinarigenin and salvigenin were isolated from Buddleia macrostachya Benth.     

Two methylated flavones from Artemisia frigida

Two new highly oxygenated flavones were isolated from Artemisia frigida. Their structures were determined by spectroscopic methods as 5,7,4′-trihydroxy-6,3′,5′-trimethoxyflavone and 5,7,3′-trihydroxy-6,4′,5′-trimethoxyflavone.     

Two new antioxidant flavones from the twigs of Eriosema robustum (Fabaceae)

Phytochemical study of the ethanol extract of the twigs of Eriosema robustum, a Cameroonian medicinal plant resulted to the isolation of two new flavones, 2′,3′,5′,5,7-pentahydroxy-3,4′-dimethoxyflavone (1) and 2′,3,5′,5,7-pentahydroxy-4′-methoxyflavone (2), along with five known compounds: 6-prenylpinocembrin (3), 1-O-heptatriacontanoyl glycerol (4), β-sitosterol (5), stigmasterol (6) and 3-O-β-d-glucopyranoside of sitosterol (7). The structure of the isolated compounds were elucidated on the basis of their NMR, UV and MS data, and by comparison with those reported in the literature. The ethanol crude extract, fractions and some isolated compounds (1–4) were evaluated for their radical scavenging capacity using 2,2-diphenyl-1-picryhydrazyl (DPPH). The crude extract, fraction II, the new compounds namely robusflavones A (1) and B (2) exhibited significant antioxidant activity.