Flavonoids from Haplophyllum pedicellatum, H. robustum AND H. glabrinum

Haplophyllum pedicellatum, H. robustum and H. glabrinum all yielded the known compound gossypetin 8,3′-dimethyl ether 3-rutinoside. In addition the first two species afforded isorhamnetin and its 3-rutinoside. A new glycoside, gossypetin 8,3′-dimethyl ether 3-glucoside was obtained from H. pedicellatum together with the 3-malonylrutinoside, 3-malonylglucoside and 3-galactoside of isorhamnetin plus kaempferol 3-malonylglucoside. H. robustum yielded isorhamnetin 7-glucoside and 3-glucoside and quercetin 3-galactoside, while H. glabrinum was found to contain gossypetin 8-methyl ether 3-malonylrutinoside in addition to kaempferol and isorhamnetin 3-glucoside.     

Differences in flavonoid constituents among the species ofFagonia sinaica complex (Zygophyllaceae)

Eight flavonol glycosides were detected in the three species of theFagonia sinaica complex. They were fully characterized as the 3-glucosides of kaempferol, quercetin and isorhamnetin, 3-rutinoside of quercetin and 3,7-diglucoside of quercetin and isorhamnetin. Two additional glycosides were partially characterized as a kaempferol 3,7-diglycoside and quercetin 3-diglycoside.     

Flavonol glycosides in the leaves ofTrillium apetalon Makino andT. kamtschaticum pallas

Seven flavonol glycosides were isolated from the leaves ofT. apetalon. They were identified chromatographically and spectrally to be: quercetin/kaempferol 3-O-α-arabinopyranosyl-(1→6)-β-galactopyranoside (TQ and TK), quercetin/kaempferol 3-O-[2‴-O-acetyl-α-arabinopyranosyl]-(1→6)-β-galactopyranoside (TAQ and TAK), quercetin 3-O-β-glucoside (ISQ), isorhamnetin 3-O-α-arabinopyranosyl-(1→6)-β-galactopyranoside (TI) and isorhamnetin 3-O-[2‴-O-acetyl-α-arabinopyranosyl]-(1→6)-β-galactopyranoside (TAI). TQ, TAQ, TI and TAI were major constituents. This is the first report on two new isorhamnetin-type glycosides, TI and TAI. The seven flavonol glycosides identical to those ofT. apetalon were isolated and identified in the leaves ofT. kamtschaticum; TQ and TAQ were also major components, but TI and TAI were only minor components. TI and TAI were not detected in the leaves ofT. tschonoskii. These leaf-flavonoid patterns were discussed from a chemosystematic point of view. Part 3 in the series “Studies of the flavonoids of the genusTrillium”. For Part 2 see Yoshitamaet al., (1997) J. Plant Res.110: 379–381.     

Phase change modifies anthocyanin synthesis in Acer palmatum Thunb. (Japanese maple) cultivars

The potential markers of juvenility (cyanidin 3-glucoside and cyanidin 3-rutinoside) in autumn leaves of seven Acer palmatum Thunb. cultivars were investigated. Three shoot positions were marked on each cultivar—crown shoot, middle shoot, and basal shoot—and the anthocyanins were analyzed using HPLC-MS. The results showed great differences in cyanidin 3-glucoside and cyanidin 3-rutinoside concentrations among seven cultivars; moreover, significant differences in cyanidin 3-glucoside content levels were also observed among three shoot positions regardless of the cultivar analyzed. The concentration decreased basipetally and reached levels up to 52 times higher in leaves obtained from crown shoots in comparison to basal shoot leaves. Therefore, the content level of cyanidin 3-glucoside can be defined as a quantitative marker of positional effect in all the Acer palmatum Thunb. cultivars analyzed. The content level of cyanidin 3-rutinoside did not express the same positional dependence.     

Flavonoide aus salix alba. Die struktur des Terniflorins und eines weiteren acylflavonoides

Eight flavonoids were isolated from the leaves of Salix alba. One, apigenin 7-O-(4-p-coumarylglucoside), is a new natural compound; another, terniflorin, the 6-isomer, is an artefact. The others are quercetin 3-O-glucoside, quercetin 3-O-rutinoside, isorhamnetin 3-O-glucoside, isorhamnetin 3-O-rutinoside and quercetin 7,′3-dimethylether 3-O-glucoside.     

Flavonoids in the leaves ofTrillium undulatum willdenow

Three flavonol glycosides were identified in the leaves ofTrillium undulatum. The main glycoside was kaempferol 3-O-α-rhamnosyl-(1→2)-O-[α-rhamnosyl-(1→6)]-β-glucoside; the glycosidic sugars and their linkage pattern were quite different from those of the leaf flavonoids ofT. tschonoskii, T. apetalon, T. Kamtschaticum, T. erectum andT. grandiflorum. Two minor compounds were kaempferol/quercetin 3-O-rutinoside. Part 2 in the series “Studies of the flavonoids of genusTrillium”. For Part 1, see Yoshitamaet al., (1992) Bot. Mag. Tokyo105: 555.     

A new petunidin tetraglycoside and tulipanin fromOphiopogon seeds

Blue seed-coats ofOphiopogon jaburan have been found to contain two kinds of anthocyanins. By means of paper chromatographic and spectral analyses, one present as a minor component was determined to be delphinidin 3-rutinoside, tulipanin, and the major component, a new anthocyanin, was identified as petunidin 3-O-β-(2^G-glucosylrutinoside)-5′-glucoside, which the authors have named “ophionin”. Both anthocyanins were also present in the blue seed-coasts ofO. japonicus andO. planiscapus.     

Properties and genetic control of anthocyanin 5-O-glucosyltransferase in flowers of Petunia hybrida

An anthocyanin 5-O-glucosyltransferase from flowers of Petunia hybrida was purified about 30-fold. Using uridine 5-diphosphoglucose as glucose donor (K_m 0.22 mM), the enzyme glucosylated the 3-(p-coumaroyl)-rutinoside derivatives of delphinidin and petunidin (K_m 3 M), isolated from pollen of Petunia. Delphinidin 3-rutinoside, cyanidin 3-rutinoside and delphinidin 3-glucoside did not serve as substrates. The glucosylation of petunidin 3-(p-coumaroyl)-rutinoside showed a pH-activity optimum at pH 8.3 and was neither stimulated by Mg²⁺ or Ca²⁺, nor inhibited by ethylenediaminetetraacetic acid. After separating the 5-O-glucosyltransferase from the anthocyanidin 3-O-glucosyltransferase by means of chromatofocusing, it was shown that both enzymes exhibit a high degree of positional specificity. The 5-O-glucosyltransferase activity was correlated with the gene An1, but not with the gene Gf.Abbreviations HPLC high performance liquid chromatography - 3GT 3-O-glucosyltransferase - 5GT 5-O-glucosyltransferase - 3RGac 3-(p-coumaroyl)-rutinoside - 3RGac5G 3-(p-coumaroyl)-rutinoside-5-glucoside - UDPGlc uridine 5-diphosphoglucose     

The flavonol glycosides in the fruit of Pyrus communis L. cultivar Bon Chrétien

1. Two new flavonol glycosides were isolated from the fruit of Pyrus communis L. cultivar Bon Chrétien. These were identified as isorhamnetin 3-rhamnogalactoside and a derivative of isorhamnetin 3-glucoside which was associated (possibly acylated) with an unknown aliphatic organic acid. 2. The melting point of isorhamnetin 3-glucoside isolated from Bon Chrétien pears is different from that of isorhamnetin 3-glucoside previously isolated from Argemone mexicana and Calendula officinalis. 3. Isorhamnetin 3-rhamnoglucoside was isolated from the fruit of Pyrus communis L. cultivar Bon Chrétien. This glycoside appears to be identical with narcissin, previously isolated from Narcissus tazetta and Lilium auratum. 4. Isoquercitrin, previously reported to be present in pear leaves, was isolated from the fruit of Bon Chrétien pears. 5. The isolated glycosides were present in the peels and flesh of the fruit, but were absent from the cores.     

Flavonoids from Brickellia chlorolepis and B. dentata

Eleven flavonoids including three new glycosides were isolated from Brickellia chlorolepis and one new and nine known flavonoids were obtained from B. dentata. The new glycosides from B. chlorolepis are 6-methoxykaempferol 3-rhamnoglucoside, spinacetin 3-rhamnogalactoside and veronicafolin 3-rhamnoglucoside. The known compounds identified from B. chlorolepis are patuletin, casticin, artemetin, eupatolitin 3-galactoside, quercetin 3-rhamnogalactoside, rutin, isorhamnetin 3-galactoside and eupatin 3-SO₃Ca_{$\text{1}\text{2}$}. B. dentata contains the new glycoside eupalitin 3-galactoside and nine known compounds: pectolinarigenin, salvigenin, eupafolin, cirsiliol, eupatorin, eupatolitin, eupatolitin 3-glucoside, eupatolitin 3-galactoside and eupatin.     

Flavonol glycosides of Limnanthes douglasii

Eighteen flavonol glycosides were isolated from petal and leaf-stem of Limnanthes douglasii. There were six aglycones: kaempferol, quercetin, isorhamnetin, myriectin, syringetin and a new flavonol, myricetin 3′-methyl ether. Each occurred as the 3-rutinoside, 3-rhamnosylrutinoside and 3-rutinoside-7-glucoside.     

Further flavonoid studies onAttalea species and some related cocosoid palms

In a flavonoid survey of direct and hydrolysed leaf extracts of sixteenAttalea, sevenScheelea and fourOrbignya species free tricin, tricin 7-glycosides, tricin 5-glucoside and flavone C-glycosides were the most frequent constituents; present in 100, 89, 70, and 81% of species, respectively. Luteolin, quercetin and isorhamnetin were each found in only 15% of the sample. The present results confirm the findings of a previous survey thatAttalea, Scheelea andOrbignya are chemically heterogeneous with as much variation between species as between genera. Furthermore, threeAttalea species,A. allenii, A. guaranitica andA. victoriana showed some infraspecific variation. On the other hand all three accessions ofA. ferruginea and six ofA. geraensis examined gave identical flavonoid profiles. The results support the view thatA. geraensis andA. guaranitica are closely related but do not support the suggested close relationship based on morphology betweenA. oleifera, A. burretiana andA. piassabossu.     

Flavonoid C- and O-glycosides from the Mongolian medicinal plant Dianthus versicolor Fisch

Eighteen flavonoids were identified from an aqueous extract of the aerial parts of Dianthus versicolor, a plant used in traditional Mongolian medicine against liver diseases. The flavonoid C- and O-glycosides isoorientin-7-O-rutinoside, isoorientin-7-O-rhamnosyl-galactoside, isovitexin-7-O-rutinoside, isovitexin-7-O-rhamnosyl-galactoside, isoscoparin-7-O-rutinoside, isoscoparin-7-O-rhamnosyl-galactoside, isoscoparin-7-O-galactoside, and isoorientin-7-O-galactoside were isolated and structurally elucidated. Their structures were established on the basis of extensive spectroscopic techniques including LC–UV–DAD, LC–MSⁿ, LC–HRMS, 1D and 2D NMR spectroscopy, and by GC–MS analysis after hydrolysis. Flavonoids with such a high glycosylation pattern are rare within the genus Dianthus. Furthermore, isovitexin-7-O-glucoside (saponarin), isovitexin-2″-O-rhamnoside, apigenin-6-glucoside (isovitexin), luteolin-7-O-glucoside, apigenin-7-O-glucoside, as well as the aglycons luteolin, apigenin, chrysoeriol, diosmetin, and acacetin were identified by TLC and LC–DAD–MSⁿ in comparison to reference substances or literature data. The NMR data of seven structures have not been reported in the literature to date.     

Acylated flavonol diglucosides from Lotus polyphyllos

Three acylated flavonol diglucosides, kaempferol 3-O-β-(6″-O-E-p-coumaroylglucoside)-7-O-β-glucoside; quercetin 3-O-β-(6″-O-E-p-coumaroylglucoside)-7-O-β-glucoside; isorhamnetin 3-O-β-(6″-O-E-p-coumaroylglucoside)-7-O-β-glucoside were isolated from the whole plant aqueous alcohol extract of Lotus polyphyllos. The known 3,7-di-O-glucosides of the aglycones kaempferol, quercetin and isorhamnetin were also characterized. All structures were established on the basis of chemical and spectral evidence.     

Flavonoid glycosides of Artemisia monosperma and A. herba-alba

Ten flavonoid glycosides were isolated and identified from Artemisia monosperma: vicenin-2, lucenin-2, acacetin 7-glucoside, acacetin 7-rutinoside, the 3-glucosides and 3-rutinosides of quercetin and patuletin, and the 5-glucosides of quercetin and isorhamnetin. From Artemisia herba-alba eight flavonoid glycosides were isolated and identified: isovitexin, vicenin-2, schaftoside, isoschaftoside and the 3-glucosides and 3-rutinosides of quercetin and patuletin.     

Negatively charged flavones and tricin as chemosystematic markers in the palmae

A survey of 125 species of the Palmae revealed a complex pattern of flavonoids in the leaf. C-Glycosylflavones, leucoanthocyanins and tricin, luteolin and quercetin glycosides were common, being present in 84, 66, 51, 30 and 24% of the species respectively. Apigenin and kaempferol were recorded in only a few species and isorhamnetin only once. Eighteen flavonoids were identified: the 7-glucoside, 7-diglucoside and 7-rutinoside of both luteolin and tricin, tricin 5-glucoside, apigenin 7-rutinoside, quercetin 3-rutinoside-7-galactoside, isorhamnetin 7-rutinoside, orientin, iso-orientin, vitexin, isovitexin and vitexin 7-O-glucoside. Many of the C- and O-flavonoid glycosides were present as the potassium bisulphate salts and negatively charged compounds were detected in 50% of the species. The distribution patterns are correlated with the taxonomy of the family in several ways. Thus, the Phoenicoideae and Caryotoideae have distinctive flavonoid patterns, there is evidence to support the separation of the subfamilies Phytelephantoideae and Nypoideae, and tricin is a useful marker at tribal level. At the generic level, Cocos is clearly separated from Butia, and other Cocoseae and Mascarena and Chamaedorea form well defined groups within the Arecoideae. A numerical analysis of these biochemical data, together with morphological characters, produces a new classification which suggests that the flavonoid data may have more systematic value than is indicated when they are applied to the traditional classification.     

Flavonoids in translucent bracts of the Himalayan<Emphasis Type="Italic"> Rheum nobile</Emphasis> (Polygonaceae) as ultraviolet shields

UV-absorbing substances were isolated from the translucent bracts of Rheum nobile, which grows in the alpine zone of the eastern Himalayas. Nine kinds of the UV-absorbing substances were found by high performance liquid chromatography (HPLC) and paper chromatography (PC) surveys. All of the five major compounds are flavonoids, and were identified as quercetin 3-O-glucoside, quercetin 3-O-galactoside, quercetin 3-O-rutinoside, quercetin 3-O-arabinoside and quercetin 3-O-[6-(3-hydroxy-3-methylglutaroyl)-glucoside] by UV, ¹H and ¹³C NMR, mass spectra, and acid hydrolysis of the original glycosides, and direct PC and HPLC comparisons with authentic specimens. The four minor compounds were characterised as quercetin itself, quercetin 7-O-glycoside, kaempferol glycoside and feruloyl ester. Of those compounds, quercetin 3-O-[6-(3-hydroxy-3-methylglutaroyl)-glucoside] was found in nature for the first time. The translucent bracts of R. nobile accumulate a substantial quantity of flavonoids (3.3–5 mg per g dry material for the major compounds). Moreover, it was clarified by quantitative HPLC survey that much more of the UV-absorbing substances is present in the bracts than in rosulate leaves. Although the flavonoid compounds have been presumed to be the important UV shields in higher plants, there has been little characterisation of these compounds. In this paper, the UV-absorbing substances of the Himalayan R. nobile were characterised as flavonol glycosides based on quercetin.     

Flavonoid chemistry ofBlennospermatinae, a trans-Pacific disjunct subtribe ofSenecioneae (Asteraceae)

The flavonoid profiles of seven species ofAbrotanella and one species ofIschnea have been shown to be based upon kaempferol 3- and quercetin 3-O-glycosides and a delphinidin glycoside. Glucosides, glucuronides, arabinosides, diglucosides, and rutinosides of the flavonols were identified. The profile ofIschnea consisted solely of quercetin 3-O-glucoside and 3-O-arabinoside whereas the profiles of theAbrotanella species were more varied. Although infraspecific variation was not investigated in this study, the flavonoid chemistry of the two genera is in accordance with the flavonoid variation described for other members ofSenecioneae which are primarily flavonol producers. Based on the known phylogeny and biogeography, the flavonoid distribution from the perspective of long-distance dispersals across the Pacific is discussed. Such events should lead to genetic bottle-neck situations and depauperate flavonoid profiles. A summary of current flavonoid knowledge in theSenecioneae is supplied.     

Flavonoid analysis of<Emphasis Type="Italic">Heloniopsis orientalis</Emphasis> (Thunb.) by high performance liquid chromatography

We have isolated and identified seven flavonoid compounds from the foliar extracts ofHeloniopsis orientalis, a member of Liliaceae, which is habituated at Namhansanseong and Maranggol (Jinburyung). All are glycosylated derivatives of the flavonols isorhamnetin, kaempferol, and quercetin. Among them, quercetin 3-O-galactoside is the major compound, while isorhamnetin 3-O-arabinosylgalactoside, isorhamnetin 3-O-digalactoside, kaempferol 3,7-O-galactoside, kaempferol 3-O-arabinosylgalactoside, kaempferol 3-O-glycoside, and quercetin 3-O-arabinosylgalactoside are present in smaller amounts. Although the two populations do not differ significantly in their overall flavonol profiles, their relative amounts indicate that flavonoid levels, especially for isorhamnetin, are geographically controlled and specifically depend on the origin of the individual population.     

Anthocyanins and flavonols from the flowers of Amherstia nobilis endemic to Myanmar

Three anthocyanins (1–3) and eight flavonols (4–11) were isolated from the flowers of Amherstia nobilis endemic to Myanmar. Anthocyanins were identified as cyanidin 3-O-glucoside (1), 3-O-xyloside (2), and peonidin 3-O-glucoside (3). On the other hand, flavonols were identified as isorhamnetin 3-O-glucoside (4), 7-O-glucoside (5), 3,7-di-O-glucoside (6) and 3-O-rutinoside (7), quercetin 3-O-rutinoside (8) and 3-O-glucoside (9), and kaempferol 3-O-rutinoside (10) and 3-O-glucoside (11). Although an anthocyanin, pelargonidin 3-O-pentoside, has been reported from the flowers of A. nobilis, it was not found in this survey. The presence of flavonols in A. nobilis was reported in this survey for the first time. Flavonoid composition of Amherstia was chemotaxonomically compared with those of phylogenetically related genera Cynometra and Brownea.