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.     

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.     

Identification de xanthones et de nouveaux arabinosides de C-glucosides flavoniques dans Swertia perennisL.

Identification of xanthones and new arabinosides of flavone C-glucosides from Swertia perennis L. – Seven tetraoxygenated xanthones [1,3,7,8-tetrahydroxy-xanthone ( 1 ); 1,8-dihydroxy-3,7-dimethoxy-xanthone ( 2 ); 1,7-dihydroxy-3,8-dimethoxy-xanthone ( 3 ); 1-hydroxy-3,7,8-trimethoxy-xanthone ( 4 ); 3,7,8-trihydroxy-xanthone-xanthone-1-0-β-glucoside ( 5 ); 3,7,8-trimethoxy-xanthone-1-0-primeveroside ( 6 ); 8-hydroxy-3,7-dimethoxy-xanthone-1-0-primeveroside ( 7 )] have been isolated chromatographically, using polyamide columns, from roots of Swertia perennis L . From leaves and stems of the same plant, six xanthones [1,5,8-trihydroxy-3-methoxy-xanthone ( 8 ); 1,5-dihydroxy-3-methoxy-xanthone-8-0-β-glucoside ( 9 ); mangiferin ( 10 ); 1 ; 4 ; 5 ] and four flavone C-glycosides [iso-orientin ( 11 ); isovitexin ( 12 ); iso-orientin-6″-arabinoside ( 13 ); isovitexin-6″-arabinoside ( 14 )] have also been isolated. Among these compounds, 7 , 13 and 14 were not encountered before in nature. In the last two compounds, the position of arabinose on the C-glucoside moiety of the flavone was established by ¹³C-NMR. spectroscopy.     

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.     

Contribution à la phytochimie du genre Gentiana,XIX. Identification de nouveaux C-glucosides flavoniques dans Gentiana pyrenaicaL

Phytochemistry of genus Gentiana, XIX: Identification of new C-glycosylflavones in Gentiana pyrenaica L . Five flavone C-glucosides [6-C-β-D -glucopyranosyl-tricine ( 1 ) or isopyrenine; 7-O-β-D -glucopyranosyl-6-C-β-D -glucopyranosyltricine ( 2 ) or isopyrenine-7-O-glucoside; isoscoparine-7-O-glucoside ( 3 ); 7-O-β-D -glucopyranosyl-6-C-β-D -glucopyranosylacacetine ( 4 ) and isovitexine-7-O-glucoside ( 5 ) or saponarine] as well as the flavonol glucoside isoquercitrine ( 9 ) have been isolated chromatographically, using polyamide and cellulose columns, from the aerial parts of Gentiana pyrenaica L . 1 and 2 are new compounds and the first glycoflavones trisubstituted on cycle B. Compound 4 is also encountered for the first time in nature.     

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.     

Phenanthrenes from Juncus effusus with anxiolytic and sedative activities

Eight phenanthrenes, 7-carboxy-2-hydroxy-1-methyl-5-vinyl-phenanthrene (1); 2,7-dihydroxy-1-methyl-5-aldehyde-9,10-dihydrophenanthrene (2); dehydroeffusol (3); dehydrojuncusol (4); 7-carboxy-2-hydroxy-1-methyl-5-vinyl-9,10-dihydrophenanthrene (5); 8-carboxy-2-hydroxy-1-methyl-5-vinyl-9,10-dihydrophenanthrene (6); effusol (7) and juncusol (8), were isolated from the aerial part of Juncus effusus. Compounds 1 and 2 were identified as new constituents. Compounds 7 and 8 showed anxiolytic and sedative activities.     

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. 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.     

Diterpenoide Chinomethane,vinyloge Chinone und ein Phyllocladan-Derivat aus Plectranthus purpuratus HARV. (Labiatae)

Diterpenoids from Leaf Glands of Plectranthus purpuratus: p-Quinomethanes, Extended Quinones, p-Acylcatechols and a Novel Phyllocladanon Derivative From the complex mixture of terpenoids from the title plant, the following novel diterpenoids have been isolated: 11-hydroxy-19-(3-methyl-2-butenoyloxy)- and 11-hydroxy-19-(3-methylbutanoyloxy)-5,7,9 (11), 13-abietatetraen-12-one ( 1a / 1b ), 11-hydroxy-19-(3-methyl-2-butenoyloxy)- and 11-hydroxy-19-(3-methylbutanoyl-oxy)-7,9(11), 13-abietatrien-6,12-dione ( 2a / 2b ), 6α, 11-dihydroxy-19-(3-methyl-2-butenoyloxy)- and 6α, 11 -dihydroxy-19-(3-methylbutanoyloxy)-7,9 (11), 13-abieta-trien-12-one ( 3a / 3b ), 11,12-dihydroxy-19-(3-methyl-2-butenoyloxy)- and 11,12-di-hydroxy-19-(3-methylbutanoyloxy)-8,11,13-abietatrien-7-one ( 4a / 4b ), and (16R)-17,19-diacetoxy-16-hydroxy-13β-kauran-3-one (=(16R)-17,19-diacetoxy-16-hydro-xyphyllocladan-3-one; 10 ). Compounds 2 and 3 are derivates of taxodione and taxodone, respectively, 4 is a derivative of cryptojaponol. The structure of 10 is Wised on a single-crystal- X -ray analysis and CD . data.     

Diterpenoide Drüsenfarbstoffe aus Labiaten: 3β-Acetoxyfuerstion,Nilgherron A und Nilgherron B,neue Chinomethane aus Plectranthus nilgherricus BENTH.; absolute Konfiguration von Fuerstion

Leaf-gland Pigments: 3β-Acetoxyfuerstione, Nilgherron A and Nilgherron B, New Quinomethanes from Plectranthus nilgherricus BENTH . (Labiatae); Absolute Configuration of Fuerstione We have isolated from leaf-glands of the above mentioned plant the following deeply coloured quino-methane derivatives: (1) traces of the already known fuerstione ( 1a ); 11,15-dihydroxy-5,7,9 (11), 13-abietatetraen-12-one; (2) the new 3β-acetoxy-fuerstione ( 1b ); (3) nilgherron A ( 5a , I or II), a new dimeric diterpenoid quinomethane, C₄₀H₅₂O₇, formed in the plant obviously by cycloaddition of the o-quinone 8 (9aS, 11R)-11 -hydroxy-2-(1-hydroxy-1-methylethyl-9,9-dimethyl-3,4,7,8,9,9a,10,11- octahydro-5H-dibenzo [a, d]cycloheptene-3,4-dione) with fuerstione; (4) nilgherron B ( 5b , I or II), C₄₂H₅₄O₉, likewise a new compound, formed by the same type of cycloaddition (heterodiene synthesis) of 8 with 3β-acetoxyfuerstione. On the basis of ¹H-NMR. shift arguments structure I is slightly preferred to II for 5a and 5b . Model experiments have shown the easy formation of the dihydrodioxin ring by reaction of an o-benzoquinone with p-quinomethanes. The absolute configuration of fuerstione and 3β-acetoxyfuerstione has been determined by chiroptical methods.     

Isolation and Structure of Pseurotin A,a Microbial Metabolite of Pseudeurotium ovalis STOLK with an Unusual Heterospirocyclic System

The structure and absolute configuration of pseurotin A, a new metabolite, isolated from culture filtrates of Pseudeurotium ovalis STOLK (Ascomycetes) has been shown to be (1′S, 2′S, 5S, 8S, 9R, 3′Z)-8-benzoyl-2 (1′,2-dihydroxy-3′-hexenyl)-9-hydroxy-8-methoxy-3-methyl-1-oxa-7-azaspiro [4,4]non-2-ene-4,6-dione ( 1 ).     

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.     

Isolation of four new flavonoids from Melicope triphylla

Four new flavonoids, 3,5-dihydroxy-7,8-dimethoxy-3',4'-methylenedioxyflavone (1), 3,5-dihydroxy-7-methoxy-3',4'-methylenedioxyflavone (2), 3,5-dihydroxy-7-isopentenyloxy-8-methoxy-3',4'-methylenedioxyflavone (3) and 5-hydroxy-3-isopentenyloxy-7-methoxy-3',4'-methylenedioxyflavone (4), were isolated from the leaves of Melicope triphylla. In addition, two known flavonoids were detected including 5-hydroxy-3,7-dimethoxy-3',4'-methylenedioxyflavone (5) and 5-hydroxy-7-isopentenyloxy-3,8-dimethoxy-3',4'-methylenedioxyflavone (6). The structures of the new compounds were established by spectroscopic methods.     

The mutagenic constituents of Rubia tinctorum.

Twenty compounds were isolated from the roots of Rubia tinctorum which are used as a commercial source of madder color. Among these compounds, mollugin (1), 1-hydroxy-2-methylanthraquinone (2), 2-ethoxymethylanthraquinone(11), rubiadin (13), 1,3-dihydroxyanthraqunone (14), 7-hydroxy-2-methylanthraquinone (16), lucidin (17), 1-methoxymethylanthraquinone (18) and lucidin-3-O-primeveroside (19) showed mutagenicity with Salmonella typhimurium TA 100 and/or TA 98. Since the mutagenic compounds isolated are anthraquinone derivatives with the exception of compound 1, structure-mutagenicity relationships of the anthraquinones were also studied. The results suggested that the greatest activity is exhibited by 1,3-dihydroxyanthraquinones possessing methyl or hydroxylmethyl group on carbon 2.     

Studies on the chemical constituents of Eucalyptus robusta Sm.: Isolation and identification of robustaol B and other constituents

Nine known compounds, 5-hydroxy-4′,7-dimethoxy-6,8-dimethylflavone, 4′,5-dihydroxy-7-methoxy-6,8-dimethylflavone, 3β-hydroxy-urs-11-ene-28-oic-13(28)-lactone, 3β-acetoxy-urs-11-ene-28-oic-13(28)-lactone, uvaol, β-sitosterol, 7β-O-glucoside of 5,7-dihydroxy-2-methylchromone, 1-triacontanol and 1-triacontanoic acid, and a new acylphloroglucinol named robustaol B 6 were isolated from the leaves of Eucalyptus robusta Sm. 6 was shown to be 4,6-dihydroxy-2-methoxy isobutyrophenone by spectral analyses and was confirmed by synthesis. 6 showed inhibition against Staphylococcus aureus 209P and Bacillus subtilis 6633 in vitro.     

13C NMR spectroscopy of isomerism in series of arylazo derivatives of sulfonaphthols and aminosulfonaphthols

¹³C NMR has been used in a study of the isomers formed in azo coupling of 1,8-dihydroxy-3,6-naphthalenedisulfonic acid (chromotropic acid), 1-hydroxy-8-amino-3,6-naphthalenedisulfonic acid (H acid), 1-hydroxy-6-amino-3-naphthalenesulfonic acid (J acid), and 1-hydroxy-7-amino-3-naphthalenesulfonic acid (gamma acid); and indicators have been established through which individual isomers in mixtures can be recognized spectroscopically.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2721–2728, December, 1989.     

Enzyme inhibitory constituents from Duranta repens

Isoprenylated flavonoids 5,7-dihydroxy-3'-(2-hydroxy-3-methyl-3-butenyl)-3,6,4'-trimethoxyflavone (1), 3,7-dihydroxy-3'-(2-hydroxy-3-methyl-3-butenyl)-5,6,4'-trimethoxyflavone (2) and an isoprenylated acetophenone derivative (3) have been isolated from Duranta repens along with known compounds, 5-hydroxy-3,6,7,4'-tetramethoxyflavone (4), rosenonolactone (5), 6,7-dimethoxycoumarin (6), 5alpha,8alpha-epidioxyergosta-6,22-dien-3beta-ol (7) and 5alpha,8alpha-epidioxyergosta-6,9(11),22-trien-3beta-ol (8), isolated for the first time from this species. Their structures and the relative configuration were determined by spectroscopic methods (1H- and 13C-NMR, IR, UV and MS) and two-dimensional (2D)-NMR experiments. The compounds 1-5 showed inhibitory activity against prolyl endopeptidase while 4 and 5 were also active against thrombin.     

Microbial transformation of cannabinoids. Part 3: Major metabolites of (3R, 4R)-Δ1-tetrahydrocannabinol

The metabolic transformations of the psychotropic cannabinoid (3R, 4R)-Δ¹-tetrahydrocannabinol (5) (=Δ¹-THC) by cultures of Fusarium Nivale, Gibberella fujikuroi (both Ascomycetes) and Thamnidium elegans (Phycomycetes) were investigated. A number of metaboilites, 1–4 and 6–9 were isolated from the incubations, partly purified and their structures elucidated by combined gas chromatography/mass spectrometry. Four of these metabolites, 1″-hydroxy-Δ¹-THC (4) 2″-hydroxy-β¹-THC (1) 6Δ-hydroxy-ζ¹-THC (8) and 2″,6Δ-dihydroxy-Δ¹-THC (9) so far have not been reported as microbial transformation products of 5 .     

Synthesis of 5,7-Dihydroxy-6-methoxy-2-(2-hydroxy-4-methoxyphenyl)-4H-1-benzopyran-4-one and Reassignment of Structure of Tamaridone1

The proposed structure of a new flavone, tamaridone, isolated from Tamarix dioica Roxb is untenable on the basis of comparison with its synthetic sample. Its structure has been now revised to 5,7-dihydroxy-8-methoxy-2-(3-hydroxy-4-methoxyphenyl)-4H-1-benzopyran-4-one by careful spectral studies.