Flavonol glycosides and a naphthopyranone glycoside from Paepalanthus macropodus (Eriocaulaceae) (original) (raw)

Naphthopyranone glycosides from Paepalanthus bromelioides

Phytochemistry, 1998

Two new naphthoð1\2!CŁpyran!0!one glycosides\ paepalantine!8!O!b!D!glucopyranoside and pae! palantine!8!O!b!D!allopyranosyl"0 : 5#glucopyranoside\ were isolated from an ethanolic extract of capitula from Paepalanthus bromelioides and identi_ed from their spectrometric data[ Þ 0887 Elsevier Science Ltd[ All rights reserved

Naphthopyranone Glycosides from Paepalanthus m icrophyllus

Journal of Natural Products, 2001

New Flavonol Tetraglycosides from Astragalus caprinus

Chemical and Pharmaceutical Bulletin, 2002

Astragalus caprinus MAIRE (Fabaceae) is an endemic of North Africa, the leaves of which are used as an antihaemorrhoidal in Tunisian folk medicine. Our previous paper describing the structure of a new 3-O-tetraglycoside of kaempferol from this plant was the first phytochemical report on this species. 1) Here we report the isolation and structural elucidation of five new flavonol glycosides. Results and Discussion The methanolic extract of dried leaves from A. caprinus, once prepurified, was fractionated by repeated column and preparative thin-layer chromatography to give 1-5. Analysis of the 1 Hand 13 C-NMR spectra of compound 1 (Table 1; all assignments based on heteronuclear single quantum coherence-total correlation spectroscopy (HSQC-TOCSY) and heteronuclear multiple bond correlation (HMBC) experiments) showed the presence of one aromatic system and four sugar moieties. The 1 H-NMR resonances of two metacoupled doublets at d 6.19 and 6.38 ppm (1H, Jϭ1.9 Hz), correlated with the carbons at 99.8 and 94.7 ppm, respectively, in the HSQC spectrum, characterized the 6-and 8-protons of a flavonoid 5,7 dihydroxy A-ring. 2) Ring B was assigned as a 1,4-substituted benzene ring (d H 8.07, d, 2H, Jϭ8.8 Hz; 6.89, d, 2H, Jϭ8.8 Hz) from a HMBC experiment. Thus, the aglycone of 1 was identified as 3,5,7,4Ј-tetrahydroxyflavone (kaempferol), as suggested by its UV spectral properties. A HSQC-TOCSY experiment was performed to identify the spin systems of sugar units, starting from anomeric protons at d 5.57 (d, Jϭ7.8 Hz), 5.22 (s), 4.52 (s) and 4.32 (d, Jϭ7.4 Hz); on the basis of the chemical shifts, multiplicity of the signals and values of the coupling constants, the sugars were identified as b-galactopyranosyl (Gal), a-rhamnopyranosyls (Rha a and Rha b) and b-xylopyranosyl (Xyl). 3) The common D-configuration for Gal and Xyl, and the L-configuration for Rha were assumed according to those most often encountered among the plant glycosides. HMBC experiments showed long-range correlations between Gal H-1 (d 5.57) and Kaempferol C-3 (d 134.5), Rha a H-1/C-1 (d 5.22/102.6) and Gal C-2/H-2 (d 77.5/3.93), Rha b H-1/C-1 (d 4.52/101.8) and Gal C-6/H-6 (d 67.5/3.68), Xyl H-1/C-1 (d 4.32/106.4) and Rha b C-3/H-3 (d 82.3/3.55). Thus, compound 1 was identified as kaempferol-3-O-{[b-Dxylopyranosyl(1→3)-a-L-rhamnopyranosyl(1→6)][a-Lrhamnopyranosyl(1→2)]}-b-D-galactopyranoside. This identification was corroborated by electrospray ionization mass July 2002 Notes Chem. Pharm. Bull. 50(7) 981-984 (2002) 981

Two New Acylated Flavanone Glycosides from the Leaves and Branches of Phyllanthus emblica

CHEMICAL & PHARMACEUTICAL BULLETIN, 2002

Phyllanthus emblica L. (Euphorbiaceae) is a shrub or tree native to subtropical and tropical areas of China, India, Indonesia and the Malay Peninsula. The fruit has been widely used for antiinflammatory and antipyretic treatment. The root, leaves and bark are also used for the treatment of indigestion, diarrhea or dysentery, eczema and wart. As a continuation of investigation on the constituents of this plant, 1-5) we chemically examined its leaves and branches, and two new acylated flavanone glycosides, a new phenolic glycoside, and 22 known compounds were isolated. This paper describes the isolation and structural elucidation of these compounds.

Flavonoids and a Naphthopyranone from Eriocaulon ligulatum and Their Mutagenic Activity

CHEMICAL & PHARMACEUTICAL BULLETIN, 2007

Eriocaulon ligulatum (VELL.) L. B. SMITH. (the pipewort family, Eriocaulaceae), called "botão-dourado" (golden bud), is exported to Europe, Japan and North America as an ornamental flower, representing an important source of income to the population of Minas Gerais State, Brazil. Scientific research on Eriocaulon is scarce and very little is known about its chemical constituents. The flavonols quercetagetin (8-hydroxyquercetin) and patuletin (6-methoxyquercetin) were identified in the leaves of E. septangulare (common pipewort), E. brownianum, E. nilagirense, E. decangulare, E. sexangulare, E. wightianum. 1) Four flavonoids, including (2S)-3Ј,4Ј-methylenedioxy-5,7-dimethoxyflavan and hispidulin [7-(6-E-p-coumaroyl-b-D-glucopyranoside)], as well as tocopherol, have been identified in the capitulae of E. buergerianum KOERN. 2) Other derived flavones and glycosylated naphthopyranones were isolated from the capitulae of Eriocaulon. 3) Taxonomic studies to delimit the genus, about which there is still some confusion, and the biological investigation into the isolated molecules of Eriocaulaceae are of great importance because several molecules possess antioxidant, 4) cytotoxic, mutagenic, 5,6) and antiulcerogenic activity. 7,8) We report here the isolation of taxonomically relevant flavonoids and a naphthopyranone dimer isolated from methanol and dichloromethane extracts from capitulae of E. ligulatum, respectively, and also the mutagenic activity of methanol and dichloromethane extracts assayed using the Ames test. Results and Discussion Chromatographic fractionation of the extracts of E. ligulatum afforded the substances presented in Figs. 1-3. When revealed with Natural Product/Polyethylenoglycol Reagent (NP/PEG Reagent), compounds 1-3 showed yellow spots, characteristic of flavonoids. 9) Compounds 1-4 were determined to be 6-methoxyapigenin-7-O-b-D-glucopyranoside (1), 6-methoxyapigenin-7-O-b-D-allopyranoside (2), 6,4Јdimethoxyquercetin-3-O-b-D-6Љ[3,4,5-trihydroxy (E)-cin-namoyl]glucopyranoside (3) and eriocauline (4). Compounds 3 and 4 were identified using spectroscopic methods (IR, UV, HR-ESI-MS and NMR 1-D and 2-D). Compound 3 was obtained as a pale yellow amorphous solid. The IR spectrum presented bands at 3387 cm Ϫ1 (n O-H), 1637 cm Ϫ1 (n CϭO) and 1604 cm Ϫ1 (n CϭC). The UV spectra showed absorption bands at 240 and 336 nm. The positive HR-ESI-MS mass spectrum gave the pseudomolecular ion [MϩH] ϩ at m/z 687.1561 corresponding to the molecular formula C 32 H 30 O 17. The adduct with sodium [MϩNa] ϩ appeared at m/z 693.1434 and the adduct with potassium [MϩK] ϩ appeared at m/z 725.2463. The 13 C-NMR and DEPT spectra of 3 showed 32 signals, 6 of which could be assigned to a glucopyranosyl moiety (Table 1). Sixteen other signals were similar to those of 6-methoxyquercetin. 10) The remaining 7 signals are compatible with a 3,4,5-trihydroxycinnamoyl moiety. 10) The 1 H-NMR of 3 clearly indicated a

Polyphenols Isolated from Pterocaulon purpurascens, I. 6-Hydroxyflavonoids

Journal of Natural Products, 1987

The genus Ptnocawlon is widely distributed in northeastern Argentina, southern Brazil, and Paraguay. Various species are used in folk medicine for various applications, as an insecticide and as an agent against snake bites (14). In previous papers we described the caffeoylquinic acid content from Ptcmurrh virgatnm DC. ( 5 ) and Ptcroclurlapwpnraaw W (6) and the isolation of coumarins (7) and flavonoids (8,9) from P. virgatnm. Continuing ow study of the Argentine G m p i c a e with medicinal uses, we now report the isolation and identification of flavonoids from the CH,CI, extract of P. pnrpnrusm. Six flavonoids were isolated and identified as quercetin, isorhamnetin, and the quercetagetin methyl ethers: quercetagetin-3,7,4'-trimethyl ether (lo), quercetagetin-3,7diethyl ether (1 I), quercetagetin-3,3'dimethyl ether (12), and quercetagetin-3,7dimethyl ether (1 1). We give further infonnation of the mass spectra which is not detailed in the current literature. EXPERIMENTAL PLANT m n m . -A e r i a l pam ofP. pwpnrascm were collected from Chaco, Argentina, in 1983. The herbarium specimens are deposited at the Museo de Bothica "Juan A. Domingua," Facultad de Farmacia y Bioquimica, U.B.A. (Schultz 1024).

α-d-Glucopyranosyl-(1→2)-[6-O-(l-tryptophanyl)-β-d-fructofuranoside]

Molbank

The Mycobacterium sp. BRS2A-AR2 is an endophyte of the mangrove plant Rhizophora racemosa G. Mey., which grows along the banks of the River Butre, in the Western Region of Ghana. Chemical profiling using 1H-NMR and HRESI-LC-MS of fermentation extracts produced by the strain led to the isolation of the new compound, α-d-Glucopyranosyl-(1→2)-[6-O-(l-tryptophanyl)-β-d–fructofuranoside] or simply tortomycoglycoside (1). Compound 1 is an aminoglycoside consisting of a tryptophan moiety esterified to a disaccharide made up of β-d-fructofuranose and α-d-glucopyranose sugars. The full structure of 1 was determined using UV, IR, 1D, 2D-NMR and HRESI-LC-MS data. When tested against Trypanosoma brucei subsp. brucei, the parasite responsible for Human African Trypanosomiasis in sub-Saharan Africa, 1 (IC50 11.25 µM) was just as effective as Coptis japonica (Thunb.) Makino. (IC50 8.20 µM). The extract of Coptis japonica (Thunb.) Makino. is routinely used as laboratory standard due to its powerful...

Isoflavone Tetraglycosides from Sophora japonica Leaves §

Journal of Natural Products, 2008

Two new isoflavone tetraglycosides (1 and 2) and six known compounds were isolated from the leaves of Sophora japonica. The new glycosides are genistein 7-O-D-glucopyranoside-4′-O-(6′′′-OR -L-rhamnopyranosyl)-sophoroside (1) and genistein 7-OR -L-rhamnopyranoside-4′-O-(6′′′-OR -L-rhamnopyranosyl)-sophoroside (2). The structures of compounds 1 and 2 were established primarily by NMR experiments and chemical methods, and they are the first reported naturally occurring isoflavone glycosides with four attached sugar residues. The genus Sophora, family Leguminosae, is a rich source of flavonoids, 1 alkaloids, 2 and saponins. 3 Sophora japonica L. (Leguminosae) is widely distributed throughout China. Its buds and fruits have been used as a hemostatic agent in traditional Chinese medicine, and flavonoids were discovered as hemostatic constituents from the buds of S. japonica. 1b Triterpenes, phospholipids, alkaloids, amino acids, polysaccharides, and fatty acids have also been reported from its seeds. 4,5 Recently we systematically investigated the chemical constituents in the pericarps 1c and seeds 1d of S. japonica and isolated and identified many compounds including flavonols, isoflavones, and their glycosides. To our knowledge, no phytochemical investigation on the leaves of this species has been reported. The current report describes the isolation and structure elucidation of two new isoflavone glycosides, genistein 7-O-Dglucopyranoside-4′-O-(6′′′-OR -L-rhamnopyranosyl)-sophoroside (1) and genistein 7-OR -L-rhamnopyranoside-4′-O-(6′′′-OR -L-rhamnopyranosyl)-sophoroside (2), from the leaves of S. japonica, together with six known compounds. The structures of 1 and 2 have been determined on the basis of the spectroscopic data including 2D NMR spectra and chemical evidence. The known compounds were identified as genistein 7-O-D-glucopyranoside-4′-O-D-glucopyranoside, sophorabioside, genistin, rutin, quercetin 3-O-D-glucopyranoside, and kaemgferol 3-O-D-glucopyranoside by comparison of their spectroscopic data with those reported 6,7 and by comparison with authentic samples. Compounds 1 and 2 are the first reported naturally occurring isoflavone glycosides having four sugar residues. Compound 1 was isolated as a colorless, amorphous powder. The molecular formula was established as C 39 H 49 O 24 on the basis of the HRFABMS data. The exact mass of the [M-H]ion at m/z 901.2582 matched well with the expected molecular formula of C 39 H 49 O 24 (calcd 901.2598). The IR spectrum of compound 1 showed strong absorption bands at 3415 (OH), 1652 (R,unsaturated CdO), 1612, 1582, 1495 (CdO, aromatic), and a broad band at 1160-1000 cm-1 , indicating its glycosidic nature. The UV spectrum (λ max 260 nm) of compound 1 was typical of compounds having an isoflavone skeleton. 6 A characteristic resonance for H-2 of an isoflavone was observed at δ H 8.48 (1H, s, δ C 155.2) in the 1 H NMR spectrum. 6,8 This assignment was confirmed by longrange correlation with δ C 180.4 (C-4), 157.2 (C-9), and 122.2 (C-1′) in the corresponding HMBC spectrum. Upon acid hydrolysis of 1, genistein, glucose, and rhamnose were identified by TLC. Genistein was also identified by UV and 1 H NMR spectroscopy. 7

Erratum to ?Three acylated flavone glycosides from Aytac and Aksoy? [Phytochemistry 65 (2004) 2095?2099]

Phytochemistry, 2005

Additionally, one of the new compounds, chrysoeriol 7-O-[2 000 -O-p-coumaroyl-6 000 -b-O-acetyl-D D-glucopyranosyl-(1 ! 2)-b-D D-glucopyranoside], was written incorrectly in the abstract and should be chrysoeriol 7-O-[2 000 -O-p-coumaroyl-6 000 -O-acetyl-b-D D-glucopyranosyl-(1 ! 2)-b-D D-glucopyranoside]. Additionally, one of the new compounds, chrysoeriol 7-O-[2 000 -O-p-coumaroyl-6 000 -b-O-acetyl-D D-glucopyranosyl-(1 ! 2)-b-D D-glucopyranoside], was written incorrectly in the abstract and should be chrysoeriol 7-O-[2 000 -O-p-coumaroyl-6 000 -O-acetyl-b-D D-glucopyranosyl-(1 ! 2)-b-D D-glucopyranoside]. Abstract From the aerial parts of Sideritis ozturkii, three new flavonoids, chrysoeriol 7-O-[2 000 -O-caffeoyl-6 000 -O-acetyl-b-D D -glucopyranosyl-ð1 ! 2Þ-b-D D -glucopyranoside], chrysoeriol 7-O-[2 000 -O-caffeoyl-b-D D -glucopyranosyl-(1! 2)-b-D D -glucopyranoside] and chrysoeriol 7-O-[2 000 -O-p-coumaroyl-6 000 -b-O-acetyl-D D -glucopyranosyl-ð1 ! 2Þ-b-D D -glucopyranoside] named as ozturkosides A, B and C, respectively, were isolated, along with three known phenylethanoid glycosides, verbascoside, leucoseptoside A, martynoside and five known diterpenoids, 7-epicandicandiol, linearol, sidol, sideroxol, epoxyisolinearol. The structures were elucidated mainly by spectroscopic methods.

Flavonol glycosides and a naphthopyranone glycoside from Paepalanthus macropodus (Eriocaulaceae) (original) (raw)

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