Contribution à la phytochimie du genre Gentiana. XXII. Identification de nouveaux O-glucosides de la mangiférine dans Gentiana asclepiadeaL.

Phytochemistry of genus Gentiana. XXII. Identification of new O-glucosides of mangiferin in Gentiana asclepiadea L. Two new O-glucosides of mangiferin (mangiferin-7-O-β-D -glucoside ( 1 ) and mangiferin-6-O-β-D -glucoside ( 2 )) have been isolated from the leaves of Gentiana asclepiadea L . This is the first full structure elucidation of naturally occurring O-glucosides of C-glucosylxanthones. The known C-glucosylflavone, saponarin ( 5 ) was also identified.     

Contribution à la phytochimie du genre Gentiana XXI; Les cinnamoyl-C-glucosylflavones et leurs O-glucosides dans Gentiana punctataL.

Phytochemistry of genus Gentiana XXI: The cinnamoyl-C-glucosylflavones and their O-glucosides in Gentiana punctata L . Three new ( 1 – 3 ) and three previously identified ( 4 – 6 ) cinnamoyl-C-glucosyl-flavones have been isolated from the leaves of Gentiana punctata L . The structures of the new compounds were established as: trans-cafeoyl-2″-iso-orientin-4′-O-β-D -glucoside ( 1 ), trans-feruloyl-2″-isovitexin-4′-O-β-D -glucoside ( 2 ) and trans-feruloyl-2″-isovitexin ( 3 ). Isoscoparine ( 8 ) and O-β-D -glucosyl-2″-iso-orientin ( 7 ) were also isolated and identified.     

Contribution à la phytochimie du genre Gentiana IX. Etude de composés flavoniques et xanthoniques dans les feuilles de gentiana CampestrisL. 1ère communication

Two new xanthone-O-glycoside, the 1,3,5-trihydroxy-xanthone-8-O-β-D -glucopyranoside ( 3 ), the 1,5-dihydroxy-3-methoxyxanthone-8-O-β-D -glucopyranoside ( 4 ), have been isolated from the leaves of Gentiana campestris L . by means of column chromatography on polyamid. Two known xanthones ( 1 , 2 ) which are respectively the aglycones of 3 and 4 and a flavone: iso-orientine ( 5 ) have also been isolated and identified.     

Phytochemistry of genus Gentiana, XX. Identification of new di-O-glucosides of C-glucosylflavones in Gentiana asclepiadea l (author's transl)

Phytochemistry of genus Gentiana, XX. Identification of new di-O-glucosides of C-glucosylflavones in Gentiana asclepiadea L. Two new O-glucosides of C-glucoside flavonic compounds [isoorientin-2″,4′-di-O-β-D -glucoside ( 1 ) and isovitexin-2″-4′-O-β-D -glucoside ( 2 )] have been isolated from leaves of Gentiana asclepiadea L . This is the first case of di-O-glucosides of C-glucoside flavones occurring in nature.     

Contribution à la phytochimie du genre Gentiana. XXV. Etude des composés flavoniques et xanthoniques dans les feuilles de Gentiana X marcailhouana RY. Nouveaux cinnamoyl-C-glucosides flavoniques

Phytochemistry of genus Gentiana XXV: Study of the flavonic and xanthonic compounds in leaves of Gentiana X marcailhouana RY . New cinnamoyl-C-glucosyl-flavones Nine flavonic compounds: isoorientin ( 1 ), isovitexin ( 2 ), isoorientin-4′-O-β-D -glucoside ( 3 ), isovitexin-4′-O-β-D -glucoside ( 4 ), luteolin-7-O-β-D -glucoside ( 5 ), trans-cafeoyl-2′′-isoorientin ( 6 ), trans-feruloyl-2′′-isoorientin ( 7 ), trans-p-coumaroyl-2′′-isoorientin ( 8 ), p-O-β-D -glucosyl-trans-cafeoyl-2′′-isoorientin ( 9 ) and three xanthones: gentioside ( 10 ), isogentisine ( 11 ), mangiferin ( 12 ), have been identified from leaves of Gentiana X marcailhouana RY . Compounds 8 and 9 were described for the first time. The cyclitol L -(+)-bornesitol ( 13 ) has been also isolated.     

Contribution à la phytochimie du genre Gentiana. VII. Etude des composés flavoniques et xanthoniques dans les feuilles de Gentiana vernaL. (1ère communication)

A new xanthone-O-glycoside, the 1,7-dihydroxy-3-methoxyxanthone-8-O-β-D-glucopyranoside ( 7 ), has been isolated from the leaves of Gentiana verna L. by means of column chromatography on polyamid. Six known xanthones: 1-hydroxy-3,7,8-trimethoxyxanthone-1-O-primerveroside ( 2 ); 1,7,8-trihydroxy-3-methoxyxanthone ( 3 ); 7-hydroxy-3,8-dimethoxyxanthone-1-O-primeveroside ( 4 ); 7,8-dihydroxy-3-methoxyxanthone-1-O-primeveroside ( 5 ); mangiferin 6 and the flavone C-glycoside isoorientin 8 have also been isolated and identified.     

Contribution à la phytochimie du genre Gentiana. XIV: Identification de nouveaux dérivés de l'isoorientine extraits des feuilles de Gentiana burseri LAPEYR (2e communication)

Phytochemistry of genus Gentiana XIV: Identification of new derivatives of iso-orientin in the leaves of Gentiana burseri LAPEYR . 2nd Communication. Two new derivatives of iso-orientin have been isolated and identified. The structures of the new compounds were established as: trans-feruloyl-2″-iso-orientin ( 1 ) and trans-feruloyl-2″-iso-orientin-4′-O-β-D -glucoside ( 2 ).     

Contribution à la phytochimie du genre Gentiana,XIII. Etude des composés flavoniques et xanthoniques dans les feuilles de Gentiana campestris L. 2ème communication

Phytochemistry of genus Gentiana XIII. Study of flavocic and xantonic compounds in the leaves of Gentiana campestris L. 2nd communication. By means of column chromatography on polyamide, we have isolated from the leaves of Gentiana campestris L. a new xanthone-O-glucoside, the 3,4-dimethoxy-5, 8-dihydroxy-xanthone-1-O-β-D-glucopyranoside ( 2 ) and its aglucone, the 3,4-dimethoxy-1,5,8-trihydroxy-xanthone ( 1 ). The C-glucosides mangiferin ( 3 ) and swertisin ( 4 ) have also been isolated and identified.     

Contribution à la phytochimie du genre Gentiana. X. Etude des composés flavoniques et xanthoniques dans les feuilles de Gentiana vernaL.

One new ( 1 ) and one previously identified ( 2 ) flavone-C-glycosides were isolated from leaves of Gentiana verna L . by means of column chromatography. The columns used were polyamid and cellulose. The structure of the new compound was established as iso-orientin-2″-O-glucoside by means of UV. and NMR. spectrosocpy. The known compound was shown to be isoorientin-4′-O-glucoside.     

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 ).     

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.     

Isolierung und Strukturaufklärung von Neapolitanose (O-β-D-Glucopyranosyl-(1→2)-O-[β-D-glucopyranosyl-(1→6)]-(D-glucose), einem neuen Trisaccharid aus den Stempeln von Gartenkrokussen (Crocus neapolitanus var.)

Isolation and Structure Elucidation of Neapolitanose (O-β-D -Glucopyranosyl-(1→2)-O-[β-D -glucopyranosyl-(1→6)]-D -glucose), New Trisaccharide from the Stigmas of Garden Crocusses (Crocus neapolitanus var.) From the stigmas of Crocus neapolitanus var. ‘Blue Bird’ two new crocetin glycosyl esters were isolated. They contained a hitherto unknown trisaccharide. For the structure elucidation a homonuclear 2D-¹H-NMR-shift-correlation experiment was carried out with the peracetate of the isolated trisaccharide. This experiment revealed that the carbohydrate is O-β-D -glucopyranosyl-(1→2)-O-[β-D -glucopyranosyl-(1→6))]-D -glucose, for which we suggest the name ‘neapolitanose’. The two new C₂₀-carotenoids from Crocus neapolitanus are crocetin (β-gentiobiosyl) (β-neapolitanosyl) ester ( 4 ) and crocetin di(β-neapolitanosyl) ester ( 5 ).     

Contribution à la phytochimie du genre Gentiana III. Etude des composés flavoniques et xanthoniques dans les feuilles de Gentiana lutea L. (2me communication)

The xanthone isogentisin and two flavonic heterosides (isocrientin-4′-O-glucoside and isovitexin-4′-O-glucoside) have been isolated from leaves of Gentiana lutea L. by means of column chromatography on polyamide. The determination of the structures and the NMR. spectra of the acetylated derivatives are reported.     

Contribution à la phytochimie du genre Gentiana. XXVI.. Identification d'une nouvelle di-O-glucosyl cinnamoyl-C-glucosylflavone extraite des feuilles de Gentiana X marcailhouana RY.

Phytochemistry of Genus Gentiana. XXVI. Identification of a New Di-O-glucosyl Cinnamoyl-C-glucosylflavone in the Leaves of Gentiana X marcailhouana RY . A new di-O-glucosyl cinnamoyl-C-glucosylflavone has been identified as 4′-O-β-D -glucosyl-2″-O-[2-O-β-D -glucosyl-2,4,5-trihydroxy-(E)-cinnamoyl]isoorientin ( 1 ).     

Contribution à la phytochimie de genre Gentiana. XXIV.. Nouveaux C-glycosides flavoniques dans les feuilles de Gentiana asclepiadeaL.

Phytochemistry of genus Gentiana, XXIV. New C-glycosylflavones from the leaves of Gentiana asclepiadea L. p-Hydroxybenzoyl-2″-isoorientin-4′-O-β-D-glucoside ( 1 ) was isolated from the leaves of Gentiana asclepiadea L. by means of column chromatography. This is the first occurrence in nature of a p-hydroxybenzoate of isoorientin. p-Hydroxybenzoyl-2″-isoorientin ( 2 ) was also shown to be present in the same plant.     

Contribution à la phytochimie du genre Gentiana. V. Identification d'un nouveau O-glucoside de C-glucoside flavonique dans les feuilles de Gentiana nivalis L

A new flavonic heteroside, isoorientin-3′-O-glucoside, has been isolated from leaves of Gentiana nivalis L . by means of column chromatography on polyamide. The determination of the structure is described.     

Ilwensisaponins A,B, C,and D: Triterpene Saponins from Scrophularia ilwensis

From the aerial parts of Scrophularia ilwensis, four new triterpene saponins, ilwensisaponins A–D ( 1 – 4 ) were isolated. The structures of the compounds were elucidated using chemical and spectral data as 13β, 28-epoxy-3-β-{{[β-D -glucopyranosyl-(1→2)]-[α-L -rhamnopyranosyl-(1→4)-β-D -glucopyranosyl-(1→3)]-β-D -fucopyranosyl}-oxy} olean-11-en-23-ol ( 1 ), 3-β-{{[β-D -glucopyranosyl-(1→2)]-[α-L -rhamnopyranosyl-(1→4)-β-D -glucopyranosyl-(1→3)]-β-D -fucopyranosyl}oxy}olena-11, 13(18)-diene-23, 28-diol ( 2 ), 3-β-{{[β-D -glucopyranosyl-(1→2)]-[α-L -rhamnopyranosyl-(1→4)-β-D glucopyranosyl-(1→3)]-β-D fucopyranosyl}oxy}-11α-methoxyolean- 12-ene-23, 28-diol (3) , and 3-β-{{[β-D -glucopyransoyl-(1→2)]-[α-L -rhamnopyranosyl-(1→4)-β-D -glucopyranosyl-(1→3)]-β-D -fucopyranosyl}oxy}olean-12-ene-11α,23,28-triol (4) .     

Contribution à la phytochimie du genre Gentiana,XVIII. Structure du gentiabavarutinoside,un nouveau glycoside xanthonique acylé isolé de Gentiana bavaricaL

Phytochemistry of genus Gentiana, XVIII: Structure of gentiabavarutinoside, a new acylated xanthone glycoside from Gentiana bavarica L. In a previous work [1], we isolated from Gentiana bavarica L . an acylated xanthone glycoside (1,8-dihydroxy-3-methoxy-xanthone-7-O-acetylrutinoside 1 or gentiabavarutinoside) without locating the acetyl group. By ¹³C-NMR. spectroscopy, the attach position of the acetyl is now shown to be at 4 of the rhamnose moiety. In addition, a new compound ( 2 ), the desacetyl derivative of 1 , has also been isolated and identified.     

Struktur der Pachybiose und Asclepobiose. Desoxyzucker, 44. Mitteilung

Pachybiose (1) is shown to be 4-O-(3-O-methyl-6-deoxy-β-D -allopyranosyl)-D -oleandrose and asclepobiose (14) 4-O-(3-O-methyl-6-deoxy-β-D -allopyranosyl)-D -cymarose.     

Contribution à la phytochimie du genre Gentiana,VI. Etude des xanthones dans les feuilles de Gentiana bavarica L.

Ten tetraoxygenated xanthones (1-hydroxy-3, 7, 8-trimethoxyxanthone I; 1, 7-dihydroxy-3, 8-dimethoxyxanthone II; 1, 7, 8-trihydroxy-3-methoxyxanthone III; 1, 3, 7, 8-tetrahydroxyxanthone IV; 3, 7, 8-trimethoxyxanthone-1-O-primeveroside V; 7-hydroxy-3, 8-dimethoxyxanthone-1-O-primeveroside VI; 1, 8-dihydroxy-3-methoxyxanthone-7-O-acetylrutinoside VII; 7, 8-dihydroxy-3-methoxyxanthone-1-O-primeveroside VIII; 3, 7, 8-trihydroxyxanthone-1-O-primeveroside IX; 3, 7, 8-trihydroxyxanthone-1-O-glucoside X) have been isolated from leaves of Gentiana bavarica L . by means of column chromatography on polyamid. Among these xanthones, VI, VII, VIII and IX were not encountered before in nature.