Acylated cyanidin 3-sambubioside-5-glucosides from the purple-violet flowers of Matthiola longipetala subsp. bicornis (Sm) P. W. Ball. (Brassicaceae)

A novel acylated cyanidin 3-sambubioside-5-glucoside was isolated from the purple-violet flowers of Matthiola longipetala subsp. bicornis (Sm) P. W. Ball. (family: Brassicaceae), and determined to be cyanidin 3-O-[2-O-(2-O-(trans-feruloyl)-β-xylopyranosyl)-6-O-(trans-feruloyl)-β-glucopyranoside]-5-O-[6-O-(malonyl)-β-glucopyranoside] by chemical and spectroscopic methods. In addition, two known acylated cyanidin 3-sambubioside-5-glucosides, cyanidin 3-O-[2-O-(2-O-(trans-sinapoyl)-β-xylopyranosyl)-6-O-(trans-feruloyl)-β-glucopyranoside]-5-O-[6-O-(malonyl)-β-glucopyranoside] and cyanidin 3-O-[2-O-(β-xylopyranosyl)-6-O-(trans-feruloyl)-β-glucopyranoside]-5-O-[6-O-(malonyl)-β-glucopyranoside] were identified in the flowers.     

A tetra-acylated cyanidin 3-sophoroside-5-glucoside from the purple-violet flowers of Moricandia arvensis (L.) DC. (Brassicaceae)

A novel tetra-acylated cyanidin 3-sophoroside-5-glucoside was isolated from the purple-violet flowers of Moricandia arvensis (L.) DC. (Family: Brassicaceae), and determined to be cyanidin 3-O-[2-O-(2-O-(4-O-(6-O-(4-O-(β-glucopyranosyl)-trans-caffeoyl)-β-glucopyranosyl)-trans-caffeoyl)-β-glucopyranosyl)-6-O-(trans-caffeoyl)-β-glucopyranoside]-5-O-[6-O-(malonyl)-β-glucopyranoside] by chemical and spectroscopic methods.     

Unique flavonoid glycosides from the new zealand white pine, Dacrycarpus dacrydioides

A number of new flavonoid glycosides have been isolated from foliage of the New Zealand white pine, Dacrycarpus dacrydioides. These include tricetin 3′,5′-di-O-β-glucopyranoside; the 3′-O-β-xylopyranoside, 7-O-α-rhamnopyranoside and 7-O-α-rhamnopyranoside-3′-O-β-xylopyranoside of 3-O-methylmyricetin; the 3′-O-β-xylopyranoside, 7-O-α-rhamnopyranoside and 7-O-α-rhamnopyranoside-3′-O-β-xylopyranoside of 3-O-methyl-quercetin, and the 3′-O-β-xylopyranoside and 7-O-α-rhamnopyranoside-3′-O-β-xylopyranoside of 3,4′-di-O-methylmyricetin. The accumulation of 3-methoxyflavones and B-ring trioxygenated flavonoids appears to distinguish D. dacrydioides from all other New Zealand members of the classical genus Podocarpus. Support for De Laubenfels' proposed separation of Dacrycarpus from this genus is seen in the present work.     

Isolation from a softwood xylan of oligosaccharides containing two 4-O-methyl-d-glucuronic acid residues

Partial hydrolysis of a larch arabino(4-O-methylglucurono)xylan afforded two series of oligouronides composed of 4-O-methyl- d-glucuronic acid and d-xylose residues. The first series included aldouronic acids up to the aldopentaouronic acid. Methylation analysis indicated that the aldopentao- and aldotetrao-uronic acids were mixtures of isomers. One aldotetraouronic acid was isolated and identified as O-β-d-Xylp-(1 → 4)-O-β-d-Xylp-(1 → 4)-O-(4-O-Me-α-d-GlcAp)-(1 → 2)-d-Xyl. The two isomeric aldotriouronic acids were separated from each other. The acids of the second series, which were composed of two uronic acids and 2-4 d-xylose residues, were identified as follows: O-β-d-Xylp-(1 → 4)-O-(4-O-Me-α-d-GlcAp)-(1 → 2)-O-β-d-Xylp-(1 → 4)-O(4-O-Me-α-d-GlcAp)-(1 → 2)-O-β-d-Xylp-(1 → 4)-d-Xyl, O-(4-O-Me-α-d-GlcAp)-(1 → 2)-O-β-d-Xylp-(1 → 4)-O-(4-O-Me-α-d-GlcAp)-(1 → 2)-O-β-d-Xylp-(1 → 4)-O-β-d -Xylp-(1 → 4)-D-Xyl, O-(4-O-Me-α-d-GlcAp)-(1 → 2)-O-β-d-Xylp-(1 → 4)-O-(4-O-Mec-α-d-GlcAp)-(1 → 2)-O-β-d-Xylp-(1 → 4)-D-Xyl, and O-(4-O-Me-α-d-GlcAp)-(1 → 2)-O-β-d-Xylp-(1 → 4)-O-(4-O-Me-α-d-GlcAp)-(1 → 2)-D-Xyl. The first three compounds were new acidic oligosaccharides. The 4-O-methyl-d-glucuronic acid in the second series was present in a larger proportion than in the first series, indicating that a large proportion of the uronic acid side-chains were located on two contiguous D-xylose residues in the backbone of the softwood xylan.     

Anthocyanins in Caprifoliaceae

The qualitative and relative quantitative anthocyanin content of 19 species belonging to the genera Sambucus, Lonicera and Viburnum in the family Caprifoliaceae has been determined. Altogether 12 anthocyanins were identified; the 3-O-glucoside (2), 3-O-galactoside (5), 3-O-(6″-O-arabinosylglucoside) (7), 3-O-(6″-O-rhamnosylglucoside) (9), 3-O-(2″-O-xylosyl-6″-O-rhamnosylglucoside) (10), 3-O-(2″-O-xylosylgalactoside) (11), 3-O-(2″-O-xylosylglucoside) (12), 3-O-(2″-O-xylosylglucoside)-5-O-glucoside (14), 3-O-(2″-O-xylosyl-6″-O-Z-p-coumaroylglucoside)-5-O-glucoside (15) and 3-O-(2″-O-xylosyl-6″-O-E-p-coumaroylglucoside)-5-O-glucoside (16) of cyanidin, in addition to the 3-O-glucosides of pelargonidin and delphinidin (1 and 3). Pigment 7 is the first complete identification of the disaccharide vicianose, 6″-O-α-arabinopyranosyl-β-glucopyranose, linked to an anthocyanidin.     

Synthesis of a branched d-mannopentaoside and a branched d-mannohexaoside: Models of the inner core of cell-wall glycoproteins of Saccharomyces cerevisiae

Synthetic routes are discussed to the branched d-mannopentaoside methyl 6-O-(2,6-di-O-α-d-mannopyranosyl-α-d-mannopyranosyl)-3-O-α-d-mannopyranosyl-α-d-mannopyranoside and d-mannohexaoside methyl 6-O-(2,6-di-O-α-d-mannopyranosyl-α-d-mannopyranosyl)-3-O-(2-O-α-d-mannopyranosyl-α-d-mannopyranosyl)- α-d-mannopyranoside, employing the properly benzylated d-mannobioside methyl 2,4-di-O-benzyl-6-O-(3,4-di-O-benzyl-α-d-mannopyranosyl)-α-d-mannopyranoside and d-mannotrioside methyl 2,4-di-O-benzyl-6-O-(3,4-di-O-benzyl-α-d-mannopyranosyl)-3-O-(3,4,6-tri-O-benzyl-α-d-mannopyranosyl)-α-d- mannopyranoside as key intermediates.     

A synthesis of psi-cytidine

2-O-Benzoyl-3,6-di-O-benzyl-4-O-(chloroacetyl)-, 4-O-acetyl-2-O-benzoyl-3,6-di-O-benzyl-, and 2-O-benzoyl-3,4,6-tri-O-benzyl-α-d-galactopyranosyl chloride were converted into the corresponding 2,2,2-trifluoroethanesulfonates, and these were treated with allyl 2-O-benzoyl-3,6-di-O-benzyl-α-d-galactopyranoside, to give allyl 2-O-benzoyl-4-O-[2-O-benzoyl-3,6-di-O-benzyl-4-O-(chloroacetyl)-β-d-galactopyranosyl]-3,6-di-O-benzyl- α-d-galactopyranoside (26; 41% yield), allyl 4-O-(4-O-acetyl-2-O-benzoyl-3,6-di-O-benzyl-β-d-galactopyranosyl)-2-O-benzoyl-3,6-di-O-benzyl- α-d-galactopyranoside (27; 62% yield), and allyl 2-O-benzoyl-4-O-(2-O-benzoyl-3,4,6-tri-O-benzyl-β-d-galactopyranosyl)-3,6-di-O-benzyl-α-d-galactopyranoside (28; 65% yield). All disaccharides were free from their α anomers. Disaccharides 26 and 27 were found to be base-sensitive, and were de-esterified by KCN in aqueous ethanol, and debenzylated with H₂-Pd. Attempts to produce (1→4)-β-d-galactopyranosides from the coupling of a number of fully esterified d-galactopyranosyl sulfonates to allyl 2,3,6-tri-O-benzoyl-α-d-galactopyranoside were unsuccessful.     

Sulphated polysaccharides of the grateloupiaceae family : Part VII. Investigation of the acetolysis products of a partially desulphated sample of the polysaccharide of pachymenia carnosa

Investigation of the acetolysis products of a partially desulphated sample of the polysaccharide isolated from Pachymenia carnosa led to the isolation and characterization of the following oligosaccharides: 3-O-α-D-galactopyranosyl-D-galactose (1), 4-O-β-D-galactopyranosyl-D-galactose (2), 3-O-(2-O-methyl-α-D-galactopyranosyl)-D-galactose (3), a 4-O-galactopyranosyl-2-O-methylgalactose (4), 3-O-α-D-galactopyranosyl-6-O-methyl-D-galactose (5), 4-O-β-D-galactopyranosyl-2-O-methyl-D-galactose (6), 2-O-methyl-4-O-(6-O-methyl-β-D-galactopyranosyl)-D-galactose (14), O-β-D-galactopyranosyl-(1→4)-O-α-D-galactopyranosyl-(1→3)-D-galactose (8), O-α-D-galactopyranosyl-(1→3)-O-β-D-galactopyranosyl-(1→4)-D-galactose (9), O-β-D-galactopyranosyl-(1→4)-O-α-(2-O-methyl-D-galactopyranosyl)-(1→3)-D-galactose (11), O-α-(2-O-methyl-D-galactopyranosyl)-(1→3)-O-β-D-galactopyranosyl-(1→4)-D-galactose (12), O-α-D-galactopyranosyl-(1→3)-O-β-D-galactopyranosyl-(1→4)-2-O-methyl-D-galactose (13), O-α-(2-O-methyl-D-galactopyranosyl)-(1→3)-O-β-D-galactopyranosyl-(1→4)-2-O-methyl-D-galactose (16), and O-β-D-galactopyranosyl-(1→4)-O-α-D-galactopyranosyl-(1→3)-O-β-D-galactopyranosyl-(1→4)-D-galactose (10). In addition, evidence was obtained for the presence of 4-O-(6-O-methyl-β-D-galactopyranosyl)-D-galactose (7) and O-β-D-galactopyranosyl-(1→4)-O-α-D-galactopyranosyl-(1→3)-6-O-methyl-D-galactose (15).     

Synthesis of the tetrasaccharide repeating-unit of the O-specific polysaccharide from Salmonella senftenberg

The oligosaccharide β-d-Man-(1 → 4)-α-l-Rha (1 → 3)-d-Gal-(6 ← 1)-α-d-Glc, which is the repeating unit of the O-specific polysaccharide chain of the lipopolysaccharide from Salmonella senftenberg, was obtained by glycosylation of benzyl 2,4-di-O-benzyl-6-O-(2,3,4-tri-O-benzyl-6-O-p-nitrobenzoyl-α-d-glucopyranosyl)-β-d-galactopyranoside or benzyl 2-O-acetyl-6-O-(2,3,4-tri-O-benzyl-6-O-p-nitrobenzoyl-α-d-glucopyranosyl)-β-d-galactopyranoside with 3-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-d-mannopyranosyl)-β-l-rhamnopyranose 1,2-(methyl orthoacetate) followed by removal of protecting groups.     

Synthesis of a branched d-mannopentaoside and a branched d-mannohexaoside: Models of the outer chain of the glycan of soybean agglutinin

Synthetic routes are described to the d-mannopentaoside methyl 3-O-(3,6-di-O-α-d-mannopyranosyl-α-d-mannopyranosyl)-6-O-α-d-mannopyranosyl-α-d-mannopyranoside, and the d-mannohexaoside methyl 3-O-(3,6-di-O-α-d-mannopyranosyl-α-d-mannopyranosyl)-6-O-(2-O-α-d-mannopyranosyl-α-d-mannopyranosyl)-α- d-mannopyranoside, formed in a regio- and stereo-controlled way by employing the properly protected d-mannobioside methyl 2,4-di-O-benzyl-3-O-(2,4-di-O-benzyl-α-d-mannopyranosyl)-α-d-mannopyranoside and d-mannotrioside methyl 2,4-di-O-benzyl-3-O-(2,4-di-O-benzyl-α-d-mannopyranosyl)-6-O-(3,4,6-tri-O-benzyl-α-d- mannopyranosyl)-α-d-mannopyranoside as key intermediates.     

Flavonoids from the flowers of Adenium obesum (Forssk.) Roem. & Schult., Mandevilla sanderi (Hemsl.) Woodson,and Nerium oleander L. (Apocynaceae)

Twenty-two ornamental flowers from different Adenium obesum, Mandevilla sanderi, and Nerium oleander cultivars/seedlings were analyzed for the presence of anthocyanins, flavonols, and chlorogenic acid using nuclear magnetic resonance (NMR) and mass spectrometry (MS). Cyanidin 3-O-[6-O-(rhamnosyl)-galactoside] and cyanidin 3-O-(galactoside) were identified as the major and minor anthocyanins, respectively, in three A. obesum seedlings that had red and red-purple flowers.Cyanidin 3-O-[2-O-(xylosyl)-galactoside] was identified as the major anthocyanin, whereas cyanidin 3-O-[6-O-(rhamnosyl)-galactoside] and cyanidin 3-O-(galactoside) were identified as the minor anthocyanins in 8 M. sanderi cultivars that had red and red-purple flowers. Cyanidin 3-O-[6-O-(rhamnosyl)-galactoside] and cyanidin 3-O-(galactoside) were identified as the major anthocyanins, whereas cyanidin 3-O-[2-O-(xylosyl)-galactoside] was identified as the minor anthocyanin in 8 N. oleander cultivars with red and red-purple flowers. Low levels of anthocyanins were detected in the N. oleander and M. sanderi cultivars that had white flowers, and there were no anthocyanins detected in the N. oleander cultivars with yellow flowers. Chlorogenic acid and four flavonols, quercetin 3-O-[6-O-(rhamnosyl)-galactoside], quercetin 3-O-[6-O-(rhamnosyl)-glucoside], kaempferol 3-O-(galactoside), and kaempferol 3-O-[6-O-(rhamnosyl)-galactoside], were identified in the flowers from all 22 cultivars/seedlings investigated.     

New trans- and cis-p-coumaroyl flavonol tetraglycosides from the leaves of Mitragyna rotundifolia

Two new flavonol tetraglycosides, quercetin 3-O-(4-O-trans-p-coumaroyl)-α-l-rhamnopyranosyl (1→2) [α-l-rhamnopyranosyl (1→6)]-β-d-glucopyranoside-7-O-α-l-rhamnopyranoside (krathummuoside A) and quercetin 3-O-(4-O-cis-p-coumaroyl)-α-l-rhamnopyranosyl (1→2) [α-l-rhamnopyranosyl (1→6)]-β-d-glucopyranoside-7-O-α-l-rhamnopyranoside (krathummuoside B) were isolated from the leaves of Mitragyna rotundifolia in addition to eight known compounds, quercetin 3-O-α-l-rhamnopuranosyl (1→2) [α-l-rhamnopyranosyl (1→6)]-β-d-glucopyranoside-7-O-α-l-rhamnopyranoside, rutin, (−)-epi-catechin, 3,4,5-trimethoxyphenyl β-d-glucopyranoside, (6S, 9R)-roseoside, 3-O-β-d-glucopyranosyl quinovic acid 28-O-β-d-glucopyranosyl ester, (+)-lyoniresinol 3α-O-β-d-glucopyranoside, and (+)-syringaresinol-4-O-β-d-glucopyranoside. The structure elucidation of these compounds was based on analyses of spectroscopic data including 1D- and 2D-NMR.     

7-O-methyl-(2R:3R)-dihydroquercetin 5-O-β-D-glucoside and other flavonoids from Podocarpus nivalis

In the course of a chemotaxonomic survey of New Zealand Podocarpus species, a number of new flavonoid glycosides have been isolated from P. nivalis. These are: luteolin 3′-O-β-D-xyloside, luteolin 7-O-β-D-glucoside-3′-O-β-D-xyloside, dihydroquercetin 7-O-β-D-glucoside, 7-O-methyl-(2R:3R)-dihydrokaempferol 5-O-β-D-glucopyranoside, 7-O-methyl-(2R:3R)-dihydroquercetin 5-O-β-D-glucopyranoside, 7-O-methylkaempferol 5-O-β-D-glucopyranoside and 7-O-methylquercetin 5-O-β-D-glucopyranoside. Diagnostically useful physical techniques for distinguishing substitution patterns in dihydroflavonols are discussed and summarized. Glucosylation of the 5-hydroxyl group in (+)-dihydroflavonols is shown to reverse the sign of rotation at 589 nm.     

Anthocyanins from red flowers of Camellia cultivar 'Dalicha'

Five anthocyanins, cyanidin 3-O-(2-O-β-xylopyranosyl-6-O-(Z)-p-coumaroyl)-β-galactopyranoside (2), cyanidin 3-O-(2-O-β-xylopyranosyl-6-O-(E)-p-coumaroyl)-β-galactopyranoside (3), cyanidin 3-O-(2-O-β-xylopyranosyl-6-O-(E)-caffeoyl)-β-galactopyranoside (4), cyanidin 3-O-(2-O-β-xylopyranosyl-6-O-acetyl)-β-galactopyranoside (5), and cyanidin 3-O-(2-O-β-xylopyranosyl-6-O-acetyl)-β-glucopyranoside (6), together with the known cyanidin 3-O-(2-O-β-xylopyranosyl)-β-galactopyranoside (1), were isolated from red flowers of Camellia cultivar ‘Dalicha’ (Camellia reticulata) by chromatography using open columns. Their structures were subsequently determined on the basis of spectroscopic analyses, i.e., ¹H NMR, ¹³C NMR, HMQC, HMBC, HR ESI-MS and UV-vis.     

Synthesis of 3- and 2′-fucosyl-lactose and 3,2′-difucosyl-lactose from partially benzylated lactose derivatives

O-β-d-Galactopyranosyl-(1→4)-O-[α-l-fucopyranosyl-(1→3)]-d-glucose has been synthesised by reaction of benzyl 2,6-di-O-benzyl-4-O-(2,3,4,6-tetra-O-benzyl-β-d-galactopyranosyl)-β-d-glucopyranoside with 2,3,4-tri-O-benzyl-α-l-fucopyranosyl bromide in the presence of mercuric bromide, followed by hydrogenolysis. Benzylation of benzyl 3′,4′-O-isopropylidene-β-lactoside, via tributylstannylation, in the presence of tetrabutylammonium bromide or N-methylimidazole, gave benzyl 2,6-di-O-benzyl-4-O-(6-O-benzyl-3,4-O-isopropylidene-β-d-galactopyranosyl)-β-d-glucopyranoside (6). α-Fucosylation of 6 in the presence of tetraethylammonium bromide provided either benzyl 2,6-di-O-benzyl-4-O-[6-O-benzyl-3,4-O-isopropylidene-2-O-(2,3,4-tri-O-benzyl-α-l-fucopyransoyl)-β-d- galactopyranosyl]-β-d-glucopyranoside (13, 73%) or a mixture of 13 (42%) and benzyl 2,6-di-O-benzyl-4-O-[6-O-benzyl-3,4,-O-isopropylidene-2-O-(2,3,4-tri-O-benzyl-α-l-fucopyranosyl)-β-d- galactopyranosyl-3-O-(2,3,4-tri-O-benzyl-α-l-fucopyranosyl)-β-d-glucopyranoside (16, 34%). α-Fucosylation of 13 in the presence of mercuric bromide and 2,6-di-tert-butyl-4-methylpyridine gave 16 (73%). Hydrogenolysis and acid hydrolysis of 13 and 16 afforded O-α-l-fucopyranosyl-(1→2)-O-β-d-galactopyranosyl-(1→4)-d-glucose and O-α-l-fucopyranosyl-(1→2)-O-β-d-galactopyranosyl-(1→4)-O-[α-l-fucopyranosyl-(1→3)]-d-glucose, respectively.     

Flavonoid glycosides from needles of Pinus massoniana

Seven flavonoids have been isolated from Pinus massoniana needles and identified as taxifolin and its 3′-O-β-D-glucopyranoside, (+)-catechin, naringenin-7-O-β-D-glucopyranoside and three new flavonoid glycosides, 6-C-methylaromadendrin 7-O-β-D-glucopyranoside, taxifolin 3′-O-β-D-(6″-O-phenylacetyl)-glucopyranoside and eriodictyol 3′-O-β-D-glucopyranoside.     

Pyruvic acid-containing mono- and oligo-saccharides from rhizobium trifolii bart A

After partial, acid hydrolysis of the extracellular, acid polysaccharide from Rh. trifolii Bart A, the following products were isolated and characterized: 3,4-O-(1-carboxyethylidene)-d-galactose, 4,6-O-(1-carboxyethylidene)-d-galactose, 3-O-[3,4-O-(1-carboxyethylidene)-β-d)-galactopyranosyl]-d-glucose, 3-O-[4,6-O-(1-carboxyethylidene)-β-d-galactopyranosyl]-d-glucose, O-[3,4-O-(1-carboxyethylidene)-β-d-galactopyranosyl ]-(1→3)-O-d-glucopyranosyl-(1→4)-d-glucose, and O-[4,6-O-(1- carboxyethylidene)-β-d-galactopyranosyl]-(1→3)-O-β-d-glucopyranosyl-(1→4)-d-glucose. The presence of pyruvic acid linked either to O-3 and O-4 or to O-4 and O-6 of the d-galactopyranosyl group of these saccharides indicates that both structures may be present in the original polysaccharide.     

Synthesis of di-, tri-, and tetra-saccharides corresponding to receptor structures recognised by Streptococcus pneumoniae

Syntheses are described for methyl 2-acetamido-2-deoxy-4-O-β-d-galactopyranosyl-α-d-glucopyranoside, methyl 2-acetamido-2-deoxy-4-O-β-d-galactopyranosyl-β-d-glucopyranoside, methyl 3-O-(2-acetamido-2-deoxy-β-d-glucopyranosyl-β-d-galactopyranoside, methyl 3-O-(2-acetamido-2-deoxy-4-O-β-d-galactopyranosyl-β-d-glucopyranosyl)-β-d-galactopyranoside, and methyl 4-O-[3-O-(2-acetamido-2-deoxy-4-O-β-d-galactopyranosyl-β-d-glucopyranosyl)-β-d-galactopyranosyl]- β-d-glucopyranoside.     

Phenolic glucoside gallates from quercus mongolica and q. acutissima

Six phenolic glucoside gallates: D-threo-guaiacylglycerol 8-O-, L-threo-guaiacylglycerol 8-O-, 3-methoxy-4-hydroxyphenol 1-O-, gentisic acid 5-O-, 3,5- dimethoxy-4-hydroxyphenol 1-O- and cis-coniferyl alcohol 4-O-β-D-(6′-O-galloyl)glucopyranosides were isolated from Quercus mongolica and Q. acutissima.     

Acetylated allose-containing flavonoid glucosides from Stachys anisochila

In continuation of our chemosystematic study of Stachys (Labiatae) we have isolated the previously reported isoscutellarein 7-O-[6″'-O-acetyl-β-D-allopyranosyl-(1 → 2)-β-D-glucopyranoside] (1) and 3′-hydroxy-4′-O-methylisoscutellarein 7-O-[6″'-O-acetyl-β-D-allopyranosyl-(1 → 2)-β-D-glucopyranoside] (4) and four new allose-containing flavonoid glycosides from S. anisochila. The new glycosides are hypolaetin 7-O-[6″'-O-acetyl-β-D-allopyranosyl-(1 → 2)-β-D-glucopyranside] (6) as well as the three corresponding diacetyl analogues of 1, 4 and 6, isoscutellarein 7-O-[6″'-O-acetyl-β-D-allopyranosyl-(1 → 2)-6″-O-acetyl-β-D-glucopyranoside], 3′-hydroxy-4′-O-methylisoscutellarein 7-O-[6″'-O-acetyl-β-D-allopyranosyl-(1 → 2)-6″-O-acetyl-β-D-glucopyranoside] and hypolaetin 7-O-[6″'-O-acetyl-β-D-allopyranosyl-(1 → 2)-6″-O-acetyl-β-D-glucopyranoside]. Extensive two-dimensional NMR studies (proton-carbon correlations, COSY experiments) allowed assignment of all ¹H NMR sugar signals and a correction of the ¹³C NMR signal assignments for C-2 and C-3 of the allose.