Glycosides of marine invertegrates. XI. Two new triterpene glycosides from holothurians of the familyStichopadidae

By repeated column chromatography on silica gel new glycosides have been isolated from the holothuriansAstichopus multifidus andStichopus chloronotus — astichoposide C and stichoposide C (I and II, respectively). Their structures have been studied with the aid of chemical and physicochemical methods. The complete structures of the glycosides have been established as 23(S)-acetoxy-3β-{4′-O-[O-(3-O-methyl-β-D-glucopyranosyl)-(1→3)-β-D-glucopyranosyl]-2′-O-[O-(3-O-methyl-β-D-glucopyranosyl)-(1→3)-O-β-D-xylopyranosyl-(1→4)-β-D-quinovopyranosyl]-β-D-xylopyranosyloxy}holosta-7,25-diene and -holost-7-ene.     

Three new flavonol C-glycosides from Sida cordifolia Linn

Three new flavonol C-glycosides: 3′-(3″,7″-dimethyl-2″,6″-octadiene)-8-C-β-D-glucosyl-kaempferol 3-O-β-D-glucoside (1), 3′-(3″,7″-dimethyl-2″,6″-octadiene)-8-C-β-D-glucosyl-kaempferol 3-O-β-D-glucosyl [1→4]-α-D-glucoside (2) and 6-(3″-methyl-2″-butene)-3′-methoxyl-8-C-β-D-glucosyl-kaempferol 3-O-β-D-glucosyl [1→4]-β-D-glucoside (3) have been isolated from 80% ethanolic extract of the aerial parts of Sida cordifolia Linn followed by partitioning with ethyl acetate. Structures were established by chemical and spectroscopic methods.     

Glycosides of marine invertebrates. XII. Structure of a new triterpene oligoglycoside from holothurians of familyStichopodidae

From an ethanolic extract of the holothuriansStichopus chloronotus by column chromatography on silica gel a new triterpene oligoside has been isolated the structure of which has been established as 23(S)-acetoxy-3β-{4′-O-[O-(3-O-methyl-β-D-glucopyranosyl)-(1→3)-β-D-glucopyranosyl]-2′-O-[O-(3-O-methyl-β-D-glucopyranosyl(-(1→3)-O-β-D-xylopyranosyl-(1→4)-β-D-glucopyranosyl]-β-D-xylopyranosyloxy}holost-7-ene. A hypothesis has been put forward concerning the biosynthesis of the carbohydrate chains in the glycosides of holothurians of the orderAspidochirota from bioside blocks.     

Glycosides of cinnamyl alcohol from the rhizomes ofRhodiola rosea

Three new cinnamyl alcohol glycosides have been isolated for the first time from the rhizomes of roseroot stonecropRhodiola rosea L. (Sedum rosea). On the basis of chemical transformations and the results of UV, IR, PMR, and mass spectroscopy the following structures are proposed for the compounds isolated: rozin — trans-cinnamyl O-β-D-glucopyranoside; rozavin — transcinnamyl O-(6′-O-α-L-arabinopyranosyl-β-D-glucopyranoside); and rozarin — trans-cinnamyl O-(6′-O-α-L-arabinofuranosyl-β-glucopyranoside).     

Versicoside — A new lignan glycoside fromHaplophyllum versicolor

A new lignin glyocoside has been isolated fromHaplophyllum versicolor and has been called versicoside. It has been established by chemical and spectral methods that verscioside is (+)-epipinoresinol 4′-O-[O-α-L-rhamnopyranosyl-(1 → 6)-β-D-glucopyranoside].     

Flavonoids of the rhizomes ofRhodiola rosea. I. Tricin glucosides

Gallic acid and the flavonoid tricin (4′,5,7-trihydroxy-3′,5′-dimethoxyflavone) and its 7- and 5-O glucosides have been isolated for the first time from the rhizomes ofRhodiola rosea L. Identification was made on the basis of UV, IR, PMR, and mass spectra of the initial substances and the products of their acid hydrolysis and acetylation. The physicochemical constants, not previously given in the literature, of the 5-O-β-D-glucopyranoside have been determined.     

Tomatoside a from the seeds ofLycopersicum esculentum

Results are given which confirm the structure of the furostanol glycoside from tomato seeds forming wastes of the preserving industry. From a butanolic extract of the seeds ofLycopersicum esculentum Mill. we have isolated the furostanol glycoside tomatoside A (I) the structure of which has been established as 25(S)-5α-furostan-3β,22α,26-triol 26-O-β-D-glucopyranoside 3-O-[O-β-D-glucopyranosyl-(1→2)-O-β-D-glucopyranosyl-(1→4)-β-D-galactopyranoside]. At the same time, by enzymatic and chemical transformations three new spirostanol glycosides of neotigogenin have been obtained: tomatoside B (III), which is 25(S)-5α-spirostan-3β-ol 3-O-[O-β-D-glucopyranosyl-(1→2)-β-D-galactopyranoside], 25(S)-5α-spirostan-3β-ol 3-O-[O-β-D-glucopyranosyl-(1→4)-β-D-galactopyranoside] (V), and 25(S)-5α-spirostan-3β-ol 3-O-β-D-galactopyranoside (IV).     

Steroid saponins and sapogenins ofAllium. XVI. Turoside C fromAllium turcomanicum

From a methanolic extract of the bulbs ofAllium turcomanicum Rgl. we have isolated a new furostanol glycoside, turoside C (I). An acid hydrolysate was found to contain the aglycone — neoagigenin (II) — and the sugars D-xylose, D-glucose, and D-galactose in a ratio of 1:4:1. The structure of the furostanol (I) has been established by methylation, enzymatic hydrolysis, and oxidative cleavage, and also by the oxidative cleavage of (II), as (25S)-5α-furostan-2α,3β,6β,22α,26-pentaol 26-O-β-D-glucopyranoside 3-O-{[O-β-D-xylopyranosyl-(1→3)]-[O-β-D-glucopyranosyl-(1→2)-O-β-D-glucopyranosyl-(1→2)]-O-β-D-glucopyranosyl-(1→4)-β-D-galacto-pyranoside}.     

Acetylspectabiflaside fromStachys atherocalyx

From the herbage ofStachys atherocalyx C. Koch, a new flavonoid glycoside has been isolated — acetylspectabiflaside, with mp 237–242°C. On the basis of acetylation, the formation of a hydroxamic acid, alkaline, and enzymatic hydrolysis, and oxidative degradation, and also the results of UV, IR, and PMR spectroscopy, the structure of 4′,5,7,8-tetrahydroxy-3′-methoxyflavone 7-O-{acetyl-[O-β-D-glucopyranosyl-(1→2)-β-D-mannopyranoside]} has been proposed for acetylspectrabiflaside.     

Tripenoid glycosides of alfalfa. VII. Medicosides E and F

Two hederagenin glycosides — medicosides E and F — have been isolated from the roots ofMedicago sativa L. (Leguminosae). Medicoside E has the structure of hederagenin 28-O-β-D-glucopyranoside 3-O-[O-β-G-glucopyranosyl-(1→3)-β-D-xylopyranoside]. Medicoside F has the structure of hederagenin 28-O-β-D-glucopyranoside 3-O-[O-β-D-glucopyranosyl-(1→2)-α-L-arabinopyranoside].     

Triterpene glycosides ofHedera helix II. Determination of the structure of glycoside L-6d from common ivy leaves

A new hederagenin pentaoside — glycoside L-6d — has been isolated from the leaves of common ivyHedera helix L., fam. Araliaceae, and its structure has been determined by using various NMR-spectroscopic methods. Glycoside L-6d is hederagenin 3-O-[O-α-L-rhamnopyranosyl-(1→4)-O-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl-(1→4)-O-α-L-rhamnopyranosyl-(1→2)-α-L-arabinopyranoside.     

Contribution à la phytochimie du genre Gentian,XI Identification de nouveaux dérivés de l'iso-orientine extraits des feuilles de Gentiana burseri Lapeyr

Two new derivates of iso-orientin have been isolated and identified from the leaves of Gentiana burseri, LAPEYR. The structure of the new compounds were established as: trans-cafeoyl-2″-iso-orientin (1) and p-β-D-glucosyl-trans-cafeoyl-2″-iso-orientin-4′-O-β-D-glucoside (2).     

Steroid saponins and sapogenins ofAllium. XV. Eruboside B fromAllium erubescens

A new steroid glycoside of the spirostan series — eruboside B (I) — has been isolated from an ethanolic extract of the bulbs ofAllium erubescens C. Koh. In an acid hydrolysate, the aglycone β-chlorogenin (II) and the sugars D-glucose and D-galactose in a ratio of 3:1 have been found. By methylation, partial hydrolysis, and oxidation the structure of the spirostanol (I) has been established as (25R)-5α-spirostan-3β,6β-diol 3-O-{[O-β-D-glucopyranosyl-(1→3)]-[O-β-D-glucopyranosyl-(1→2)]-O-β-D-glucopyranosyl-(1→4)-β-D-galactopyranoside}.     

Steroid glycosides ofNicotiana tabacum seeds I. The structures of nicotianosides A,B, and E

Two steroid glycosides of the spirostan series — nicotianosides A and B — and one glycoside of the furostan series — nicotianoside E — have been isolated from the seeds ofNicotiana tabacum L. Nicotianoside A is (25S)-5α-spirostan-3β-ol 3-O-β-D-glucopyranoside, nicotianoside B is (25S)-5β-spirostan-3β-ol 3-O-[O-α-L-rhamnopyranosyl-(1→2)-gb-D-glucopyranoside], and nicotianoside E is (25S)-5α-furostan-3β,22α,26-triol 26-O-β-glucopyranoside 3-O-[O-α-L-rhamnopyranosyl-(1→2)-β-D-glucopyranoside].     

Coumarins ofHapolophyllum obtusifolium. Structures of two new coumarin glycosides

Two coumarin glycosides have been isolated from an aqueous ethanolic extract of the epigeal part ofHaplophyllum obtusifolium: (I) — C₁₆H₁₆O₁₀, mp 164–166°C, [α]_D ?52.4° (dimethylformamide); and (II) — C₂₆H₂₆O₁₂, mp 206–208°C, [α]_D ?110.5° (pyridine). It has been established on the basis of chemical transformations and spectral characteristics that (I) has the structure of fraxetin 7-O-β-D-glucopyranoside and (II) that of scopoletin 7-O-(6′-O-feruloyl-β-D-glucopyranoside).     

中药普乐安片质量标准研究

建立中药普乐安片的质量标准.采用TLC法对普乐安片中主要有效成分山奈酚-3-O-β-D-(2-O-β-D-葡萄糖基)吡喃葡萄糖苷(KMP)进行定性鉴别.采用HPLC法对普乐安片中主要有效成分山奈酚-3,4′-双-O-β-D-葡萄糖苷(KMG)和山奈酚-3-O-β-D-(2-O-β-D-葡萄糖基)吡喃葡萄糖苷进行含量测定...     

Steroid glycosides of the leaves of Yucca aloifolia

Two new steroid glycosides have been isolated from the leaves of aloe yucca and their structures have been established. Glycosides B and C are tigogenin penta-and hexaosides. Glycoside B, which we have called yuccaloeside B is (25R)-5α-spirostan-3β-ol 3-{[O-β-D-glucopyranosyl-(1→2)]-[O-α-L-rhamnopyranosyl-(1→4)-O-β-D-glucopyranosyl-(1→3)]-O-β-D-glucopyranosyl-(1→4)-β-D-galactopyranoside}, and glycoside C, which we have called yuccaloeside C is (25R)-5α-spirostan-3β-ol 3-{[(O-β-D-glucopyranosyl-(1→3)-O-β-D-glucopyranosyl-(1→2)]-[O-α-L-rhamnopyranosyl-(1→4)-O-β-D-glucopyranosyl-(1→3)]-O-β-D-glucopyranosyl-(1→4)-β-D-galactopyranoside}.     

Synthesis of mono-, di- and trisulfated Lewis x trisaccharides

3′-Sulfated and 3′,6′-disulfated Lewis x trisaccharides have been prepared through selective sulfation of methyl 2-acetamido-6-O-benzyl-2-deoxy-4-O-β-D-galactopyranosyl-3-O-(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-β-D-glucopyranoside, followed by catalytic hydrogenolysis. In a similar manner, 3′,6-disulfated and 3′,6,6′-trisulfated Lewis x trisaccharides have been selectively obtained from methyl 2-acetamido-2-deoxy-4-O-β-D-galactopyranosyl-3-O-(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-β-D-glucopyranoside.     

Structure d'un nouvel heteroside d'isoflavone: le sarothamnoside

The structure of sarothamnoside (genistein 7,4′-di-O-[4-O-β-D-glucopyranosyl-β-D-apiofuranoside]), a new isoflavone glycoside from $\text{Sarothamnus scoparius}$ and $\text{S}$, patens, has been established by spectral analysis, mainly ₁₃C NMR.     

Cucumarioside G4 — A new triterpenglycoside from the holothurian Eupentacta fraudatrix

A minor glycoside — cucumarioside G₄ (I) — has been isolated from the total triterpeneglycosides of the holothurianEupentacta fraudatrix, and its structure has been determined by physical and chemical methods as 16β-acetoxyholosta-7,23E-diene-3β, 25-diol 3-O-(3-O-methyl-β-D-xylopyranosyl)-(1→3)-O-β-D-glucopyranosyl-(1→4)-O-β-D-quinovopyransoyl-(1→2)-(4-O-(sodium sulfato)-β-D-xylopyranoside)].