THE CHEMISTRY OF <scp>D</scp>-APIOSE: PART II. THE CONFIGURATION OF <scp>D</scp>-APIOSE IN APIIN

Hulyalkar, R. K.; Jones, J. K. N.; Perry, Malcolm B.

doi:10.1139/v65-279

Cited by 38 publications

(8 citation statements)

References 8 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…[ P P~I Literaturwerte van Decurosid IV, aufgenommen in (D,)DMSO; es werden nur die S, des Zucker-Restes aufgefuhrt [7]: die Losungsmittel-Verschiehung betragt hei Vergleich der Apiose-Reste -3 ppm ( 7-0 -@-D-Glucopyranosyl)apigenin [9] hergeleitet werden'). Aus der in der Grossenordnung dem [MI, des Methyl-glycosids von P-D-Apiose ([MI, = -405" [9]) ahnlichen Differenz zwischen Di-und Monoglycosid der beiden Substanzpaare wurde fur den Apiosyl-Rest in 1 P-D-Konfiguration abgeleitet.…”

Section: 6unclassified

See 1 more Smart Citation

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

Gross

Sticher

Anklin

1987

Helvetica Chimica Acta

View full text Add to dashboard Cite

New Iridoid Glycosides and a Monoterpene Glycoside from Sumbucus ebulus L. (Caprifoliaceae)From the roots of Sumbucus 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. 'H,'H-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. HELVETICA CHIMICA ACTA ~-Vol. 70 (1987) uber die Hauptkomponente, Ebulosid, berichteten wir bereits [2] wie auch uber Isoswerosid, ein neuartiges, zum Secoiridoid-glycosid Swerosid konstitutionsisomeres Glycosid [3]. Im gleichen Extrakt, aus dem Ebulosid isoliert worden war, konnten in geringeren Mengen zwei weitere bisher unbekannte, rnit Ebulosid strukturell verwandte Iridoid-glycoside aufgefunden werden: das Diglycosid 6'-O-Apiosylebulosid (l), welches das erste Apiose enthaltende Iridoid-glycosid ist, und 7,7-0 -Dihydroebulosid (3), das mogliche biogenetische Aquivalent von Loganin in der Reihe der Valerianaceen-Iridoide. Verbindung 5 ist ein ebenfalls bisher nicht beschriebenes offenkettiges Monoterpen-glycosid. Das Kopplungsmuster der zur Disaccharid-Einheit gehorenden H-Atome konnte aus dem Vergleich der 2D-'H,'H-NMR-COSY-Experimente an Ebulosid und 1 (Fig. 2) sowie aus denjenigen von 2 (Fig. 3) ermittelt werden. Danach enthielt die gesuchte Pentofuranose 3 getrennte Spinkopplungssysteme, ein A X -sowie zwei AB-Systeme, die untereinander weitreichende Kopplungen aufwiesen. Daraus wurde auf das Vorliegen eines verzweigtkettigen Zuckers vom Typ der Apiose geschlossen; die vermutete, schwer acetylierhare OH-Gruppe war somit erklart. Das bei tiefem Feld liegende AB-System in den Spektren von 1 und 2 wurde einer CH,OH-Gruppe (25 = CH,(S"')), das hei hohem Feld erscheinende der CH,-Gruppe im Furanose-Ring (24 = CH2(4)) zugeordnet. Aus dem COSY-Experiment an 2 ging hervor, ddSS H-C(1"') ( = Z1) und H--C(2) ( = 22) weitreichende Kopplungen (4J, W-Stellung) rnit je einem Proton der am Ring gegenuberliegenden CH,-Gruppe (24 = CH2(4")) zeigten; dies war ein Hinweis auf die trans-Stellung von H-C(1"') und H-C(2"'). Die Verknupfung uber CH2(6') ( = G6) der Glucose folgte aus der Lage bei hoherem Feld (3,5 ppm) dieser Protonen beim Peracetat 2 verglichen mit Tetraacetylehulosid. Einleitung. -Die Wurzeln des Zwergholunders (Surnbucus ebulusL Ergebnisse und'3C-NMR-Spektrurn uon 1 (vgl. Tab 2CH,-C(3") 0,88 20-'H,'H-NMR-COSY-Experimente imBereich der Zuckerprotonen con a) 3,8 3,63)4[ P P~I Die 'H-NMR-Spektren von 5 und 6 standen in Einklang mit dem obengenannten Strukturvorschlag: Zur Zuordnung der in einem komplexen m zwischen 1,2 und 1,7 ppm absorbierenden Signale von CH2(5), CH(6) und CH,(7) von 5 genugte die Entkopplung von CH2(4); eines der Protonen der zum AB-Teil eines ABX-Spinsystems vereinfachten CH2(5)-Grup...

show abstract

Section: 6unclassified

“…Aus der in der Grossenordnung dem [MI, des Methyl-glycosids von P-D-Apiose ([MI, = -405" [9]) ahnlichen Differenz zwischen Di-und Monoglycosid der beiden Substanzpaare wurde fur den Apiosyl-Rest in 1 P-D-Konfiguration abgeleitet. (7) und H-C(9) ableiten: 3 zeigt fur H-C (9) und H-C (7) …”

Section: 6unclassified

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

Gross

Sticher

Anklin

1987

Helvetica Chimica Acta

View full text Add to dashboard Cite

show abstract

“…14) Because 4 and 5 showed negative and positive optical rotations, respectively, 4 and 5 should be the (3S,6S)-and (3S,6R)-forms. Therefore 4, 5, 6, and 7 were characterized as (3S,6S)-6,7-dihydroxy-6,7-dihydrolinalool, (3S,6R)-6,7-dihydroxy-6,7-dihydrolinalool, (3S,6S)-6,7-dihydroxy-6,7-dihydrolinalool 3-O-b-D-glucopyranoside, and 6,7,18) apiose was confirmed to be the D-form. Therefore 9 was characterized as (1R,4S,6S)-…”

mentioning

confidence: 99%

Water-Soluble Constituents of Coriander.

2003

View full text Add to dashboard Cite

From the water-soluble portion of the methanol extract of coriander (fruit of Coriandrum sativum L.), which has been used as a spice and medicine since antiquity, 33 compounds, including two new monoterpenoids, four new monoterpenoid glycosides, two new monoterpenoid glucoside sulfates and two new aromatic compound glycosides were obtained. Their structures, were clarified by spectral investigation.

show abstract

“…50, No. 4 9) suggested that 6 was a b-D-apiofuranoside of 5. Thus, 6 was characterized as (1S,2S,4R)-p-menth-8- ϩ ion peak at m/z 153 in the positive FAB-MS. Enzymatic hydrolysis of 7 gave 6a and D-glucose, and thus, 7 was suggested to be a monoglucoside of 6a.…”

mentioning

confidence: 99%

Water-Soluble Constituents of Dill

2002

View full text Add to dashboard Cite

Dill [Anethum graveolens L.; Umbelliferae] has been cultivated in Europe since antiquity and used as a popular aromatic herb and spice. Its fruit has also been used for medicinal purposes in the relief of digestive problems and to stimulate milk for nursing mothers.1) Dill water was believed to have a soothing effect on the digestive system and was given to babies to relieve hiccups and colic. The fruit contains essential oil (3-4%) rich in d-carvone (main; 50-60%), and trans-and cis -dihydrocarvone, trans-and cis-carveol, limonene, d-dihydrocarveol, l-dihydrocarveol, a-and g-ter-pinene, a-phellandrene, b-terpineol, terpinene-4-ol p-cymene, thymol, carvacrol et al. were reported as other constituents. 2)However, only dillanoside has been published as a constituent of the water-soluble portion of this fruit.3) In continuation of our studies on the water-soluble constituents of spices, 4) and to show the relationship between the essential oil and the water-soluble constituent, we undertook a detailed investigation of this fruit. In this paper, we discuss the isolation and structure elucidation of monoterpenoids, monoterpenoid glycosides, aromatic compound glycosides, alkyl glycosides, glucides and nucleosides.The commercial dill was extracted with 70% methanol, and the methanolic extract was suspended in water and successively extracted with ether and ethyl acetate. The aqueous layer was chromatographed on Amberlite XAD-II to give water and methanol eluate fractions. These fractions were chromatographed on Sephadex LH-20, and subjected to a combination of silica gel, Lobar RP-8 column chromatography and HPLC to separate monoterpenoid ketodiols (1 to 2), monoterpenoid glycosides (3 to 10) and aromatic compound glycosides (11 to 17) from the methanol eluate fraction, and three alkyl glycosides (18 to 20), eleven glucides (21 to 31) and two nucleosides (32, 33) from the water eluate fraction. Among them, 2-4, 6-8, 10, 11 and 18 are new compounds. All new glucosides described in this paper were b-Dglucopyranosides as shown by their 1 H-and 13 C-NMR data (Tables 1, 2 ϩ ion peak at m/z 167 in the positive FAB-MS. The glycoside 3 was hydrolyzed with hesperidinase and, from the hydrolyzed mixtures, 1 and D-glucose were obtained. Consequently, 3 was a monoglucoside of 1. The position of the b-glucosyl unit was proved to be C-9 by the down-field glycosylation shift of the C-9 (by 8.1 ppm) signal and up-field glycosylation shift of the C-8 (by 0.7 ppm) signal, and from the observed nuclear Overhauser effect (NOE) interaction between the glucosyl H-1/H 2 -9 in the nuclear Overhauser and exchange spectroscopy (NOESY) spectrum of 3. So, 3 was characterized as (4S,8S)-8,9-dihydroxy-8,9-dihydrocarvone 9-O-b-D-glucopyranoside.Monoterpenoid ketodiol 2 (C 10 H 18 O 3 , an amorphous powder, [a] D 21 Ϫ23°) showed an [MϩH] ϩ ion peak at m/z 187 and was suggested to have one tert-methyl, one sec-methyl, one hydroxymethyl, three methylenes, two methine, one oxygenated quaternary carbon and one carbonyl group by the 1 H-and 13 C-NMR ...

show abstract

THE CHEMISTRY OF D-APIOSE: PART II. THE CONFIGURATION OF D-APIOSE IN APIIN

Cited by 38 publications

References 8 publications

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

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

Water-Soluble Constituents of Coriander.

Water-Soluble Constituents of Dill

Contact Info

Product

Resources

About