Zur Kenntnis des Loganins Mitteilung

Merz, K. W.; Lehmann, H.

doi:10.1002/ardp.19572901107

Cited by 11 publications

(2 citation statements)

References 17 publications

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“…Characterization of loganic acid (2) was less difficult. Acetylation and/or methylation provided compounds which had physical properties consistent with those reported for loganin derivatives (Merz and Lehmann, 1957;Birch and Grimshaw, 1961;Sheth et ai., 1961). Noteworthy is the typical iridoid uv chromophore at 230 nm (log E 4.2).…”

Section: Resultssupporting

confidence: 71%

Monoterpene biosynthesis. I. Occurrence and mevalonoid origin of gentiopicroside and loganic acid in Swertia caroliniensis

Coscia¹,

Guarnaccia²,

Botta³

1969

Biochemistry

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Gentiopicroside (l), a secoiridoid monoterpene glucoside, and loganic acid (2), a new naturally occurring iridoid monoterpene glucoside, have been isolated from the same higher plant, Swertia caroliniensis. These congeners have been characterized by chemical and spectral means. Doubleresonance nuclear magnetic resonance studies corroborated a recently revised structure 1 for gentiopicroside, isomeric to the previously designated one l a . Loganic acid has been identified by methylation to loganin (3), and acetylation to pentaacetate derivatives. Tracer experiments with acetate-2-14C, mevalonate-2-14C (6), and me~alonate-2-~H have established the mevalonoid origin of the aglucone moieties of the glucosides. Conversion of mevalonate-labeled gentiopicroside into genti-G entiopicroside (1) and loganic acid (2) belong to a class of highly oxygenated monoterpene glucosides referred to as secoiridoids and iridoids, respectively. (For a review of the iridoids (cyclopentanoid monoterpenes), see Bobbitt and Sege-

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Section: Resultssupporting

confidence: 71%

Monoterpene biosynthesis. I. Occurrence and mevalonoid origin of gentiopicroside and loganic acid in Swertia caroliniensis

Coscia¹,

Guarnaccia²,

Botta³

1969

Biochemistry

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“…The Mannich reaction on phenols is a classic organic reaction. The essential feature of the reaction is the replacement of the active hydrogen atoms in phenols, especially active hydrogen atoms in positions ortho and para to phenolic hydroxyl groups, by aminomethyl or substituted aminomethyl groups (10)(11)(12)(13)(14)(15).…”

Section: Introductionmentioning

confidence: 99%

Coupling P-31 NMR with the Mannich reaction for the quantitative analysis of lignin

Jiang¹,

Argyropoulos²

1998

Rev. Can. Chim.

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The reactivity of lignin model compounds under Mannich conditions with piperidine and formaldehyde was studied. The piperidinomethyl group was confirmed to be introduced quantitatively at sterically unhindered positions ortho to a phenolic hydroxyl when the substrate was allowed to react under ambient conditions. The sequential application of the Mannich reaction followed by quantitative 31 P NMR on a variety of lignin samples allowed the amounts of various aromatic groups bearing free phenolic hydroxyls to be determined. More specifically, the technique allowed the quantification of para-hydroxyl phenols, catechols, guaiacols, and phenols bearing C 5 or C 6 substituents. The quantitative reliability of the technique was also examined with a series of dissolved kraft lignins, isolated at various degrees of delignification. The data were found to favourably compare to those obtained by permanganate oxidation.Résumé : On a étudié la réactivité de composés modèles de la lignine dans la réaction de Mannich avec de la pipéridine et du formaldéhyde. Il a été confirmé que, lorsque le substrat réagit dans des conditions ambiantes, le groupe pipéridinométhyle s'introduit quantitativement dans les positions stériquement non empêchées en ortho de l'hydroxyle phénolique. L'application séquentielle de la réaction de Mannich sur divers échantillons de lignine, suivie d'une étude quantitative RMN du 31 P, permet de déterminer les quantités de divers groupes aromatiques portant des hydroxyles phénoliques. D'une façon plus spécifique, la technique permet de quantifier les para-hydroxyphénols, les catéchols, les guaïacols et les phénols portant des substituants en C 5 et en C 6 . On a aussi évalué la fiabilité quantitative de la technique avec une série de lignines kraft dissoutes, isolées à divers degrés de délignification. On a trouvé que les données se comparent favorablement à celles obtenues par oxydation avec le permanganate.Mots clés : lignine, composés modèles de la lignine, réaction de Mannich, résonance magnétique nucléaire (RMN), phénols, phosphore, pipéridine, analyse quantitative. [Traduit par la rédaction]Can.

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Iridoide, IV. Totalsynthese von Hydroxyloganin und Hydroxyloganinsäure

Tietze

1974

Chem. Ber.

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Umsetzung des Ketons 7a mit Magnesiummethylcarbonat, anschlieDende Reduktion und Acetylierung ergaben die Acetoxycarbonsaure 9b, die mit (-)-und (+)-x-Methylbenzylamin in die Enantiomeren gztrennt wurde. Reduktion des ( --)-Antipoden 9c mit Diboran und nachfolgende Epimerisierung an C-6 fiihrten zum Acetal12a. Nach Hydrolyse zum Anomerengemisch der Halbacetale 12 b/c und Glycosidierung mit 2,3.4,6-Tetraacetyl-B-~-glucose erhielt man Hydroxyloganinhexaacetat (17a). Iridoids, IV 1) Total Synthesis of Hydroxyloganin and HydroxylogPnic AcidReaction of the ketone 7 a with methyl magnesium carbonate followed by reduction and acetylation yielded the acetoxyacid 9b. Resolution with ( -)-and ( .t)-a-methylbenzylamine gave 9c, which was reduced with diborane and epimerized at C-6 to give the acetall2a. After hydrolysis to the anomeric mixture of the h-miacetals 12b and c and glycosidation with 2,3,4,6-tetraacetyl-B-~-glucose hydroxyloganin hexaacetate (17a) was obtained.Das naturlich vorkommende Monoterpenglycosid Secologanin (4) ist eine Schlusselverbindung in der' Biogenese der Indolalkaloide vom Typ Corynanthe 2), Aspidosperma 2) und Iboga 2), der Cinchona-3), Ipecacuanha-4) und einfacher Monoterpenalkaloides) sowie zahlreicher Monoterpenglycoside6). Durch Futterungsversuche konnte gezeigt werden, daI3 Loganin (1 a) ein biogenetischer Precursor des Secologanins (4) ist7). Die Biosynthese des Loganins (la) ist weitgehend aufgeklartg). Ebenfalls untersucht ist die Kondensation von Secologanin (4) mit Tryptamin unter Bildung von Vincosid (3), der ersten stickstoffhaltigen Vorstufe der Indolalkaloide9).

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Zur Kenntnis des Loganins Mitteilung

Cited by 11 publications

References 17 publications

Monoterpene biosynthesis. I. Occurrence and mevalonoid origin of gentiopicroside and loganic acid in Swertia caroliniensis

Monoterpene biosynthesis. I. Occurrence and mevalonoid origin of gentiopicroside and loganic acid in Swertia caroliniensis

Coupling P-31 NMR with the Mannich reaction for the quantitative analysis of lignin

Iridoide, IV. Totalsynthese von Hydroxyloganin und Hydroxyloganinsäure

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