A new stilbene glycoside from the <Emphasis Type="Italic">n</Emphasis>-butanol fraction of <Emphasis Type="Italic">Veratrum dahuricum</Emphasis>

A new stilbene glycoside, 5-methylresveratrol-3,4′-O-β-D-diglucopyranoside (1), was isolated from the n-butanol fraction of the rhizomes of Veratrum dahuricum, together with five known stilbenoids: resveratrol-3-O-β-D-glycoside (2), 4′-methylresveratrol-3-O-β-D-glycoside (3), oxyresveratrol-4′-O-β-D-glycoside (4), oxyresveratrol-3-O-β-D-glycoside (5), and oxyresveratrol-3,4′-O-β-D-diglycoside (6), and found for the first time in the investigated plant. The structures of six isolates were identified on the basis of 1D and 2D NMR data. Compounds 1–6 showed platelet aggregation inhibition, and compound 1 had an IC₅₀ value of 383.6 μM against platelet aggregation induced by AA. Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 279–282, May–June, 2009.     

Cardiac glycosides from Strophanthus kombe

Twelve cardiac glycosides and aglycons were isolated from Strophanthus kombe seeds. Of these, eight were identified as cymarin, K-strophanthin-β, K-strophanthoside, periplocymarin, 17α-strophadogenin, erysimin (= helveticoside), erysimoside, and neoglucoerysimoside. Four glycosides, preliminarily designated Sk-x, Sk-y, Sk-z, and Sk-20, were new. Their chemical structures were established as 3β-O-β-D-glucopyranosyl-5β,14β,16β-trihydroxy-19-oxo-17α-card-20(22)enolide (17α-strophadogenin-3-O-β-D-glucoside), 3β-O-β-D-cymaropyranosyl-5β,14β,16β-trihydroxy-19-oxo-17α-card-20(22)enolide (17α-strophadogenin-3-O-β-D-cymaroside), 3β-O-β-D-cymaropyranosyl-4′-O-β-D-glucopyranosyl-6″-O-β-D-glucopyranosyl-5β, 14β,16β-trihydroxy-19-oxo-17α-card-20(22)enolide (17α-strophadogenin-3-O-strophanthotrioside), and 3-O-β-D-digitoxopyranosyl-4′-O-β-D-glucopyranosyl-6″-O-β-D-glucopyranosyl-5β,14β, 19-trihydroxy-card-20(22)enolide (strophanthidol-3-O-gentiobiosyldigitoxoside), respectively. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 156–159, March–April, 2006.     

Two new coumarin biosides from Angelica dahurica

Two new coumarin biosides, tert-O-β-D-apiofuranosyl-(1→6)-O-β-D-glucopyranosyl-byakangelicin (1) and 2′-O-β-D-apiofuranosyl-(1→6)-β-D-glucopyranosyl-peucedanol (2), were isolated from the fresh roots of Angelica dahurica. The structures of the new compounds were elucidated on the basis of spectral analysis. Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 561–563, November–December, 2008.     

Flavonoids from the aerial part of <Emphasis Type="Italic">Vicia subvillosa</Emphasis>

The new flavone glucoside viscioside, luteolin-4′-O-β-D-galactopyranoside, in addition to the known flavonoids apigenin, luteolin, quercetin, cinaroside, luteolin-4′-O-β-D-glucoside, and isoquercitrin were isolated from the aerial part of Vicia subvillosa. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 30–31, January–February, 2007.     

Isoflavone glycosides from the bark of Amorpha fruticosa

Four known isoflavone glucosides have been isolated from the bark of Amorpha fruticosa, which is a traditional remedy plant, for the first time. They were elucidated as 3′-hydroxy-4′-methoxyisoflavone-7-O-β-D-glucopyranoside (1), 4′,6-dimethoxyisoflavone-7-O-β-D-glucopyranoside (2), 4′-methoxyisoflavone-7-O-β-D-glucopyranoside (3), and 3′,5-dihydroxy-4′-methoxyisoflavone-7-O-β-D-glucopyranoside (4), based on the UV, FT-IR, EIMS, FABMS, HREIMS, and NMR (¹H and ¹³C, DEPT, COSY, NOESY, HMQC, and HMBC) data. Published in Khimiya Prirodnykh Soedinenii, No. 4, pp. 336–338, July–August, 2006.     

Two new benzoyl esters of glucose from Lagotis yunnanensis

Two new benzoyl esters of glucose 1-O-(E)-4′-methoxybenzoyl-β-D-glucopyranose (1) and 1-O-(E)-4′-methoxybenzoyl-β-D-gluconic acid (2) were isolated from Lagotis yunnanensis, together with six previously known iridoid glucosides. The structures of these compounds were elucidated on the basis of spectral analysis, including 2D NMR spectroscopy. Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 529–530, November–December, 2006.     

Synthesis of 20S-protopanaxadiol 20-O-β-D-glucopyranoside, a metabolite of Panax ginseng glycosides, and compounds related to it

A preparative semi-synthetic method was developed to prepare 20S-protopanaxadiol 20-O-β-Dglucopyranoside (1), a metabolite of Panax ginseng glycosides. The 20-O-•-D-glucopyranosides of 20S-hydroxydammar-24-en-3,12-dione, 3β,20S-dihydroxydammar-24-en-12-one, and 3β,12α, 20S-trihydroxydammar-24-ene were synthesized for the first time. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 364–369, July–August, 2006.     

Two new isoflavonoid monogalactosides from <Emphasis Type="Italic">Trifolium pratense</Emphasis> roots

Formononetin and the new isoflavonoid glycosides formononetin-7-O-β-D-galactopyranoside and inermin-3-O-β-D-galactopyranoside were isolated from Trifolium pratense L. roots. The structures of the isolated compounds were proved using chemical transformations and UV, PMR, and ¹³C NMR spectra. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 21–23, January–February, 2008.     

New glycosidic and other constituents from hulls of <Emphasis Type="Italic">Oryza sativa</Emphasis>

Three new compounds, 4-hydroxymethylene-7-(9,9,13-trimethylcyclohexyl)-heptanyl-3′,7′,7′-trimethylcyclohexa-2′,4′-dien-1′-oate (1), 1-(n-hexadec-7-enoxy)-6-(n-octadecanoxy)-β-D-glucopyranoside (2), and (Z)-12-hydroxy-9-octadecenoic acid-12-β-D-glucopyranoside (3), along with the known compound hexacosanoic acid (4), were isolated and identified from the rice hulls of Oryza sativa. Their structures were elucidated by 1D and 2D NMR spectroscopic techniques (¹H-¹H COSY, ¹H-¹³C HETCOR, DEPT) aided by EIMS, FABMS, HRFABMS, and IR spectra. Published in Khimiya Prirodnykh Soedinenii, No. 4, pp. 344–347, July–August, 2007.     

Alkylation of salts ofN-(β-hydroxyalkyl)-N′-hydroxydiazeneN-oxides with alkyl halides and dimethyl sulfate

Salts ofN-(β-hydroxyalkyl)-N′-hydroxydiazeneN-oxides, RCH(OH)CH₂N(O)=NO⁻ M⁺ (R=Me, Prⁱ, or Bu^t; and M=Li, Na, K, Ag, NH₄, or Me₄N), were prepared. Their alkylation with alkyl halides R′X (X=Cl, Br, or I) and dimethyl sulfate was studied. Generally, alkylation afforded mixtures ofN-(β-hydroxyalkyl)-N′-alkoxydiazeneN-oxides RCH(OH)CH₂N(O)=NOR′ andO-alkyl-N-(β-hydroxyalkyl)-N-nitrosohydroxylamines RCH(OH)CH₂N(NO)OR′. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1996–2001, October, 1998.     

Triterpenoids from plants of the genus Tamarix

The taraxeran-14-ene-type triterpenoids methyl 3-β-al-D-fridoolean-14-en-28-oate (1), 3-α-[3″,4′-dihydroxytrans-cinnamoyl]-oxy-D-fridoolean-14-en-28-oic acid (2), and β-sitosterol (3) were isolated from the aerial part of plants from the genus Tamarix (T. laxa, T. elongata) (Tamaricaceae). The structures of the triterpenoids were proved using spectral data (IR, UV, PMR, ¹³C NMR, 2D NMR ¹H-¹H COSY, HMQC, HMBC, mass). Compound 1 is new and not previously described in the literature. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 271–273, May–June, 2006.     

Study on the Inclusion Compounds of Eugenol with α-, β-, γ- and Heptakis (2,6-di-O-methyl)-β-cyclodextrins

Several host–guest inclusion compounds of eugenol as a guest molecule and cyclodextrins (α-,β-,γ-CD) and heptakis (2,6-di-O-methyl)-β-cyclodextrin (DMβ-CD) as hosts were investigated in the solid state and in aqueous solution. The one-to-one solid inclusion compounds of eugenol and β-CD or γ-CD were prepared, but those of eugenol with α- or DMβ-CD were not obtained under the same condition. However, the UV-visible absorption spectroscopy data indicated that the liquid guest could form a 1:1 inclusion compound with all four hosts respectively in aqueous solution. The two solid inclusion compounds were characterized by powder X-ray diffraction (XRD), infrared spectroscopy (IR), thermogravimetric analysis (TG), differential scanning calorimetry (DSC) and nuclear magnetic resonance (NMR). The association constants (K), calculated from the modified Benesi–Hidebrand equation, of eugenol with α-, β-, γ- and DMβ-CD is 4.95 × 10⁴, 3.96 × 10⁵, 1.47 × 10⁵ and 9.33 × 10⁴ mol⁻¹ dm³, respectively.     

Transformation of steroidal cyclohexadienyl anion without fragmentation: Unexpected synthesis of methylenesteroid

In contrast with androsta-1,4-diene-3α/β, 17β-diol, its 3-O-methyl ether is transformed upon C(3)-deprotonation into the corresponding 3-methylene steroid with migration of theO-methyl group on the steroid skeleton (by the scheme of Wittig rearrangement) rather than eliminating the 19-methyl group. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1393–1395, July, 1999.     

Mercaptan addition to 1-<Emphasis Type="Italic">O</Emphasis>-allyl-2,3,4,6-tetra-<Emphasis Type="Italic">O</Emphasis>-acetyl-<Emphasis Type="Italic">β</Emphasis>-D-galactopyranose

Addition of ethyl-, propyl-, and n-butylmercaptans to 1-O-allyl-2,3,4,6-tetra-O-acetyl-β-D-galactopyranose in the presence of benzoyl peroxide catalyst was studied for the first time. The products were 1-O-(3-ethylthiopropyl)-2,3,4,6-tetra-O-acetyl-β-D-galactopyranose, 1-O-(3-propylthiopropyl)-2,3,4,6-tetra-O-acetyl-β-D-galactopyranose, and 1-O-(3-butylthiopropyl)-2,3,4,6-tetra-O-acetyl-β-D-galactopyranose. Deacetylation of 1-O-(3-ethylthiopropyl)-2,3,4,6-tetra-O-acetyl-β-D-galactopyranose produced 1-O-(3-ethylthiopropyl)-β-D-galactopyranose. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 209–211, May–June, 2007.     

Triterpene glycosides from <Emphasis Type="Italic">Astragalus</Emphasis> and their genins. LXXX. Cyclomacroside D,a new bisdesmoside

The structure of the new cycloartane glycoside cyclomacroside D, which was isolated from Astragalus macropus Bunge (Leguminosae) and is 24R-cycloartan-1α,3β,7β,24,25-pentaol 3-O-α-L-rhamnopyranoside–24-O-β-D-xylopyranoside, was proved. Presented at the 7th International Symposium on the Chemistry of Natural Compounds (SCNC, Tashkent, Uzbekistan, October 16–18, 2007). Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 48–50, January–February, 2009.     

Determination and Pharmacokinetic Study of Calycosin-7-O-β-d-glucoside in Rat Plasma After Intravenous Administration of Aidi Lyophilizer

Aidi injection is a clinical medicine used in China for the treatment of cancer. Calycosin-7-O-β-d-glucoside is the main effective components of the formulas. In this study, a high performance liquid chromatographic (LC) method was developed to quantify calycosin-7-O-β-d-glucoside in rat plasma using a liquid–liquid extraction and ultraviolet (UV) absorbance detection. LC analysis was performed on a Diamonsil C₁₈ column (200 × 4.6 mm i.d., 5 μm particle size) with isocratic mobile phase consisting of acetonitrile–0.05% phosphoric acid (19.5:80.5, v/v) of a flow rate of 1.0 mL min⁻¹. The linear range was 0.11–17.6 μg mL⁻¹ and the low quantification limit was 0.11 μg mL⁻¹ (S/N = 10). The intra- and inter-day relative standard deviations (RSD) in the measurement of quality control (QC) samples 0.11, 0.22, 1.32 and 8.80 μg mL⁻¹ ranged from 4.1 to 6.3 and 4.3 to 6.2%, respectively. The accuracy was from −6.7 to 4.3% in terms of relative error (RE). Calycosin-7-O-β-d-glucoside was stable in storage at −20 °C for 2 weeks and stable after three freeze–thaw cycles in rat plasma. This method was validated for specificity, accuracy, precision and was successfully applied to pharmacokinetic study of calycosin-7-O-β-d-glucoside in rat plasma after intravenous administration of Aidi lyophilizer.     

Phenolic compounds from Filipendula ulmaria

A chromatographically inseparable crystalline mixture of the previously undescribed quercetin-4′-O-β-galactopyranoside and the known quercetin-3-O-β-glucopyranoside (isoquercitrin) in a 7:5 ratio was isolated from the extract of the aerial part of Filipendula ulmaria (L.) Maxim. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 122–124, March–April, 2006.     

Reactions of functionalized alkyl halides withN-(β-hydroxyalkyl)-N′-hydroxydiazeneN-oxide salts

Some characteristic features of reactions ofN-(β-hydroxyalkyl)-N′-hydroxydiazeneN-oxide salts with various α- and β-functionalized alkyl halides were established. Some α-and β-functionalizedN-(β-hydroxyalkyl)-N′-alkoxydiazeneN-oxides and e ethylenebis[N-(β-hydroxyalkyl)-N′-oxydiazeneN-oxides] were synthesized for the first time. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 123–129, January, 1999.     

Antioxidant flavonoids from <Emphasis Type="Italic">Tamus communis</Emphasis> ssp. <Emphasis Type="Italic">cretica</Emphasis>

A new flavonoid, kaempferol-3,4′-di-O-α-L-rhamnopyranoside (1), and three known flavonoids (2–4) were isolated from the aerial parts of T. communis L. The structure of the new compound was elucidated on the basis of spectroscopic data. Compounds 1 and 2 showed significant antioxidant activity (IC₅₀ 187.151 ± 0.821 μM, and 92.079±0.513 μM, respectively), whereas compounds 3 and 4 showed moderate activity in DPPH free radical scavenging assays. Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 295–297, May–June, 2009.     

New genistein monogalactoside from the aerial part of <Emphasis Type="Italic">Trifolium pratense</Emphasis>

Formononetin, prunetin, genistein, genistin, and a new genistein glycoside genistein-7-O-β-D-galactopyranoside were isolated from the aerial part of Trifolium pratense L. The structures of the isolated compounds were established based on chemical transformations and UV, ¹H, and ¹³C NMR spectra. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 141–143, March–April, 2008.