Lagotoside: A New Phenylpropanoid Glycoside from Lagotis stolonifera

From the aerial parts of Lagotis stolonifera (Scrophulariaccae), a new phenylpropanoid glycoside, lagotoside ( 8 ), and the three known glycosides ehrenoside ( 5 ), verbascoside (= acteoside; 6 ), and plantamajoside ( 7 ) were isolated, together with the four known iridoid glucosides aucubin ( 1 ), catalpol( 2 ), globularin ( 4 ), and lythantosalin ( 3 ). The structure of the new compound 8 was elucidated on the basis of chemical and spectral data as 2-(3-hy-droxy-4-methoxyphenyl)ethyl O-[α-L -arabinopyranosyl-(1 → 2)]-O-[α-L -rhamnopyranosyl-(1 → 3)]-4-O-feruloyl-β-D -glucopyranoside.     

Secondary metabolites from the aerial parts of <Emphasis Type="Italic">Verbascum dudleyanum</Emphasis> and their biological activities

From the overground parts of Verbascum dudleyanum, six iridoid glycosides, aucubin, ajugol, catalpol, 6-O-α-L-rhamnopyranosylcatalpol, saccatoside, and 6-O-(3″-O-trans-p-coumaroyl)-α-L-rhamnopyranosylcatalpol, and two saponins, ilwensisaponin A and C, as well as a flavonoid, luteolin-7-O-β-glucopyranoside, together with an acetophenone glucoside, picein, were isolated. The structures of isolated compounds were elucidated by spectroscopic methods. These compounds showed biological acitivites. __________ Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 232–234, May–June, 2008.     

Allobetonicoside and 6-O-Acetylmioporoside: Two new iridoid glycosides from Betonica officinalis L.

A new allose-containing iridoid diglycoside, allobetonicoside ( 1 ), and a new acyl iridoid glucoside, 6-O-acetylmioporoside ( 2 ) have been isolated from the aerial parts of Betonica officinalis L. in addition to two known iridoid glucosides, acetylharpagide ( 3 ) and reptoside ( 4 ). Their structures have been determined by spectroscopic methods as well as by means of chemical evidence.     

Iridoids ofVerbascum georgicum

From the epigeal part ofVerbascum georgicum Benth., in addition to aucubin, as the main component of the total iridoids a new iridoid has been isolated — 6-α-L-(4′-p-methoxy-trans-cinnamoyl)rhamnopyranosylcatalpol, the structure of which has been shown by UV, PMR, and mass spectroscopy and a comparison of the¹³C NMR spectrum with that of 6-α-L-rhamnopyranosylcatalpol (I). The presence of catalpol and (II) in the plant has been shown by PC and TLC.     

Two new sucrose esters from the rhizome of Sparganium stoloniferum Buch.-Ham.

Two new sucrose esters, β-D-(1-O-acetyl-3,6-O-trans-diferuloyl)fructofuranosyl-α-D-2′-O-acetylglucopyranoside (1) and β-D-(1-O-acetyl-3-O-cis-feruloyl-6-O-trans-feruloyl)fructofuranosyl-α-D-2′,4′,6′-O-triacetylglucopyranoside (2), together with four known sucrose esters (3–6) have been isolated from the rhizome of Sparganium stoloniferum Buch.-Ham. Their structures were elucidated by physical and chemical evidence and spectral analysis.     

Iridoid and Phenylethyl Glycosides from Globularia sintenisii

A new iridoid glycoside, sintenoside ( 1 ) and two new phenylethyl glycosides, globusintenoside (=2‐(3,4‐dihydroxyphenyl)ethyl‐O‐6‐O‐feruloyl‐β‐D ‐glucopyranosyl‐(1→4)‐α‐L ‐rhamnopyranosyl‐(1→3)‐4‐O‐caffeoyl‐β‐D ‐glucopyranoside; 2 ) and 3′′′‐O‐methylcrenatoside (=1,2‐O‐[2‐(3,4‐dihydroxyphenyl)ethan‐1,2‐diyl]‐3‐O‐α‐L ‐4‐O‐feruloyl‐rhamnopyranosyl‐β‐D ‐glucopyranose; 3 ) were isolated from the underground parts of Globularia sintenisii, along with three known iridoid glycosides, lytanthosalin, globularin, catalpol, and six known phenylethyl glycosides, verbascoside, isoverbascoside, leucoscepthoside A, plantainoside C, martynoside, and isocrenatoside. The structure elucidation of the isolated compounds was performed by spectroscopic methods (MS and 1D and 2D NMR).     

Iridoid glycosides ofVerbascum laxum

The epigeal part ofVerbascum laxum Filar, ét Jav. has yielded in addition to the known sinuatol, a new iridoid glycoside — 6-0-(3-0-p-coumaroyl--L-rhamnopyranosyl)aucubin (I), [] _D ²⁰ –174.2±0.7° (c 1.4; MeOH). From the roots of the plant, as the main components giving an iridoid reaction, have been isolated harpagoside and the new iridoid glycoside 6-0-(2,3-di-0-acyl[acetyl,p-methoxy-trans-cinnamoyl]--L-rhamnopyranosyl)aucubin (V) [] _D ¹⁸ –130±2° (c 0.5; MeOH). The structures of the substances isolated were established with the aid of UV, IR, NMR, and mass spectra.A. L. Mndzhoyan Institute of Fine Organic Chemistry, Academy of Sciences of the Armenian SSR, Erevan. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 90–96, January–February, 1987.     

Die Herzglykoside des Pfeilgiftes von Lophopetalum toxicum LOHER. 13. Mitteilung über Celastraceen-Inhaltsstoffe

The Heart Glycosides of the Arrow Poison of Lophopetalum toxicum LOHER From the cytotoxic and positive inotropic acting bark extract of the Philippinan Lophopetalum toxicum eight heart glycosides have been isolated and their structures have been elucidated mainly by field-desorption-MS- and ¹- and ¹³C-NMR spectroscopy. Besides the known k-Strophanthidin ( 1 ), Antiarigenin ( 6 ) and β-Antiarin (Antiarigenin-3-β-O-α-L -rhamnoside, 10 ) the following mono- and diglycosides could be identified: strophanthidin-3-β-O-α-6-desoxy-D -allopyranoside (strophalloside, 2 ), strophanthidin-3-β-O-β-6-desoxy-D -glucopyranoside (= Strophanthidin chinovoside, 3 ), strophanthidin-3-β-O[-4Oβ-D -allopyranosyl-β-6-desoxy-D -allopyranoside] ( 4 ), strophanthidin-3-β-O-[3-O-β-D -glucopyranosyl-β-6-desoxy-D -talopyranoside] ( 5 ), antiarigenin-3-β-O-[3-O-β-D -gulopyranosyl-β-6-desoxy-D -talopyranoside] ( 7 ), antiarigenin-3-β-O-[4O-β-D -allopyranosyl-β-6-desoxy-D -allopyranoside] ( 8 ), and antiarigenin-3-β-O-β-6-desoxy-D -allopyranoside (antiallosid) ( 9 ). The structure of strophanthidinchinovoside ( 3 ) could be confirmed by synthesis.     

Verproside,a New Iridoid Glucoside from Veronica officinalis L. (Scrophulariaceae)

A new iridoid glucoside, verproside (2) , has been isolated from Veronica officinalis L. and its structure has been established to be 6-O-protocatechuoylcatalpol.     

Zwei weitere Iridoid-glycoside und ein Monoterpen-glycosid aus Sambucus ebulus L. (Caprifloiaceae). 3. Mitteilung über die Inhaltsstoffe der Zwergholunderwurzel

New Iridoid Glycosides and a Monoterpene Glycoside from Sambucus ebulus L. (Caprifloiaceae) From the roots of Sambucus ebulus L., two novel valeriana-type ester iridoid glycosides, 6′-O-apiosylebuloside ( 1 ) and 7,7-O-dihydroebuloside ( 3 ), along with the open-chain monoterpene glycoside 5 were isolated. Their structure elucidation is based mainly on one- and two-dimensional NMR methods. ¹H,¹H-COSY experiments permitted complete assignment of signals arising from the disaccharide unit in 1 . Biogenetically, 3 seems to represent the equivalent of loganin in the valeriana-type series of iridoid glycosides.     

Phytochemical constituents and chemosystematic significance of Chrozophora tinctoria (L.) Raf

Twelve compounds were isolated from Chrozophora tinctoria (L.) Raf. They were identified as kaempferol, kaempferol 3-O-β-glucopyranoside, kaempferol 3-O-(6″-α-rhamnopyranosyl)-β-glucopyranoside, quercetin, quercetin 3-O-β-glucopyranoside, quercetin 3-O-(6″-α-rhamnopyranosyl)-β-glucopyranoside, apigenin, apigenin 7-O-β-glucopyranoside, acacetin, gallic acid, methyl gallate and β-sitosterol-3-O-β-glucopyranoside. Their structures were elucidated by chemical and spectral methods. Furthermore, chemosystematics of the isolated compounds is briefly discussed. It was indicated that C. tinctoria is the only species of Chrozophora that has the capability to synthesis kaempferol aglycone and their glycosides, and the finding is supported by its distinct morphological and anatomical aspects.     

Iridoid and Aryl Glucosides from Globularia nudicaulis and Globularia nana

The iridoid and aryl glycosidic constituents of Globularia nudicaulis L. and G. nana LAM . are reported. The structure determination of lytanthosalin (10-O-(E)-cinnamoylaucubin), a new acylated iridoid glucoside, isolated from the latter species, is described.     

A new iridoid diglucoside from Harpagophytum procumbens

A new iridoid diglucoside has been isolated from an aqueous extract of Harpagophytum procumbens secondary roots, together with six known compounds. Its structure has been assigned as 6′-O-glucopyranosyl-8-O-trans-coumaroylharpagide by spectroscopic means.     

New Triterpene Saponins from Herniaria glabra

Three new saponins 1–3 were isolated from Herniaria glabra by means of prep. HPLC and TLC. The structures were established mainly by a combination of 2D-NMR techniques (COSY, TOCSY, ROESY, HMQC, and HMBC) as O-α-L -rhamnopyranosyl-(1→4)-O-β-D -glucopyranosyl-(1-→6)-O-[β-D -glucopyranosyl-(1→2)]-β-D -glucopyranosyl medicagen-28-ate (herniaria saponin 4; 1 ), O-β-D -glucopyranosyl-(1→3)-O-α-L -rhamnopyranosyl-(1→2)-O-[β-(3R)-D -apiofuranosyl-(1→3)]-β-D -4-O-acetylfucopyranosyl 3-O-(β-D -glucuronopyranosyl)-16α-hydroxymedicagen-28-ate (herniaria saponin 5; 2 ), and O-α-L -rhamnopyranosyl-(1→4)-O-β-D -glucopyranosyl-(1→6)-O-[β-D -6-O-acetylglucopyra nosyl-(1→2)]-β-D -glucopyranosyl medicagen-28-ate (herniaria saponin 6; 3 ).     

A new furostanol saponin from Dendrobium chrysanthum Lindl. with cytotoxic activity

A new furostanol saponin, (25R)-26-O-(α-d-glucopyranosyl)-(1→2)-α-l-rhamnopyranosyl-furost-5-ene-3β, 22α, 26-triol-3-O-α-d-glucopyranoside (1), together with four known compounds 2–5 were isolated from the ethanolic extract of the stems of Dendrobium chrysanthum Lindl. The structures of these new compounds were identified by extensive spectroscopic analysis including 1D and 2D NMR and HR-ESI-MS, as well as chemical methods. Compounds 1–3 were isolated from D. chrysanthum for the first time. Furthermore, the inhibitory effects of the compounds on tumor cells were evaluated, and compounds 1–2 exhibited significant cytotoxic activities potentially against SPC-A1, MCF-7 and HeLa human cancer cell lines. Compounds 3–5 showed inhibitory activity against the SPC-A1 and MCF-7.     

A novel dimeric flavonol glycoside from Cynanchum acutum subsp. sibiricum

A novel dimeric flavonol glycoside, Cynanflavoside A (1), together with six analogues, kaempferol-3-O-α-L-rhamnopyranosyl-(1→2)-β-D-glucopyranoside (2), quercetin-3-O-α-L-rhamnopyranosyl-(1→2)-β-D-glucopyranoside (3), kaempferol-3-O-α-L-rhamnopyranosyl-(1→2)-β-D-xylopyranoside (4), quercetin-3-O-α-L-rhamnopyranosyl-(1→2)-β-D-xylopyranoside (5), kaempferol-3-O-β-D-glucopyranosyl-7-O-α-L-rhamnopyranoside (6), and quercetin-3-O-galactoside (7) were isolated from the n-butyl alcohol extract of Cynanchum acutum subsp. sibiricum. Their structures were determined spectroscopically and compared with previously reported spectral data. All compounds were evaluated for their anti-complementary activity in vitro, and only compound 5 exhibited anti-complement effects with CH₅₀ value of 0.33 mM.     

Iridoids ofVerbascum georgicum

From the epigeal part ofVerbascum georgicum Benth., in addition to aucubin, as the main component of the total iridoids a new iridoid has been isolated — 6--L-(4-p-methoxy-trans-cinnamoyl)rhamnopyranosylcatalpol, the structure of which has been shown by UV, PMR, and mass spectroscopy and a comparison of the¹³C NMR spectrum with that of 6--L-rhamnopyranosylcatalpol (I). The presence of catalpol and (II) in the plant has been shown by PC and TLC.A. L. Mndzhoyan Institute of Precision Organic Chemistry, Academy of Sciences of the Armenian SSR, Erevan. Central Research Institute of Chemistry, Academy of Sciences of the Hungarian People's Republic, Budapest. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 446–451, July–August, 1982.     

27-Ald-triterpenoid saponins from Adina rubella

Four new triterpenoid saponins were isolated from the roots of Adina rubella Hance. They were characterized as adinaic acid 3β-O-[α-L-rhamnopyranosyl(l→2)-β-D-glucopyranosyl(l→2)-β-D-glucurono-pyranoside-6-O-methyl ester]-28-O-β-D)-glucopyranoside, adinaic acid 3β-O-[α-L-rham-nopyranosyl(l→2)-β-D-glucopyranosyl(l→2)-β-D-glucuronopyranoside-6-O-butyl ester]-28-O-β-D-glu-copyranoside, adinaic acid 3β-O-[β-D-glucopyranosyl(l→2)-β-D-glucopyranosyl]-(28→1)-β-D-gluco-pyranosyl(l→6)-β-D-glucopyranosyl ester, 27-hydroxyursolic acid 3β-O-[α-L-rhamnopyranosyl (l→2)-β-O-glucopyranosyl(l→2)-β-D)-glucuronopyranoside-6-O-methyl ester]-28-O-β-D)-glucopyranoside. Their structures were elucidated by spectral methods, especially with the aid of 2D NMR techniques. Their complete assignments of the 1H and 13C NMR signals were carried out.     

Über Pterinchemie. 85. Mitteilung. Polyacetylierte 5,6,7,8-Tetrahydro-D- und -L-neopterine. Ein besonderer Fall von N(5)-Alkylierung des 5,6,7,8-Tetrahydroneopterin-Gerüstes

Polyacetylated 5,6,7,8-Tetrahydro-D - and L -neopterins. A Special Case of N(5)-Alkylation of 5,6,7,8-Tetrahydroneopterins Improved conditions are reported for the preparation of the earlier described (6R)- and (6S)-1′-O,2′-O,3′-O,2-N,5-pentaacetyl-5,6,7,8-tetrahydro-L -neopterins, one of which could be obtained as pure crystals. Its structure, determined by X-ray-diffraction analysis, corresponds to the (6R)-enantiomer. The method has also been used to make the corresponding D -diastereoisomers. Further acetylation of (6RS)-1′-O,2′-O,3′-O,2-N-tetraacetyl-5,6,7,8-tetrahydro-D -neopterin under drastic conditions yields a mixture of several polyacetylated D -neopterin derivatives and a polyacetylated ethyl-tetrahydro-D -neopterin which was isolated in crystalline form and established by X-ray-diffraction analysis to be (6R)-1′-O,2′-O,3′-O,4-O,2-N,2-N,8-heptaacetyl-5-ethyl-5,6,7,8-tetrahydro-D -neopterin.     

A new triterpenoid glycoside from the leaves and stems of Duranta repens

A new triterpenoid glycoside (1) was isolated from the methanol extract of the leaves and stems of Duranta repens L. (Verbenaceae) along with 14 known compounds consisting of eight triterpenoids, four iridoids, one phenylethanoid glycoside and one flavonoid. The chemical structure of 1 was determined to be bayogenin 3-O-[β-D-glucopyranoside]-28-O-[α-L-rhamnopyranosyl-(1→5)-O-β-D-apiofuranosyl-(1→4)-O-α-L-rhamnopyranosyl-(1→2)-O-α-L-arabinopyranosyl] ester, based on spectroscopic data. In addition, the inhibitory effects of the isolates on lipoxygenase activity were examined. Among them, acteoside and apigenin resulted in 94 ± 3.6% and 82 ± 4.7% inhibition, respectively, at 0.5 mM.