Flavonoid glycosides ofSalix rubra

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  • TMS) showed that 8:4 ratio of the sugar protons that is typical for rutinose in the regions = 4.5 and 5.5 ppm (8 H) and 6 = 3.4-4.4 ppm (4 H). At 4.72 ppm (J = 1.0 Hz) there was the

    signal of the C-I proton of an acetylated rhamnose residue [3] on the basis of which it was concluded that substance (I) was isosakuranetic 7-rutinoside, which has been described under the name didymin [4].

    This is the first time that this substance has been isolated from satsuma blossoms.

    The investigation of the flavonoids of the blossoms is continuing.

    i 2. 3. 4.

    LITERATURE CITED

    H. G. Krishnamurty and T. R. Seshadri, Curt. Sci. (India), 34, No. 24, 681 (1965). V. A. Bandyukova and V. D Ponomarev, Khim. Prir. Soedin., 418 (1970). H. Rosler, T. J. Mabry, M. F. Cranmer, and J. Kagan, J. Org. Chem., 30, 4346 (1965). H. Wagner, L. Hbrhammer, and G. Aurnhammer, Tetrahedron Lett., No. 19, 1837 (1967).

    FLAVONOID GLYCOSIDES OF Saliz rubra

    I. I. Vinokurov UDC 547.918.581.19

    The ether-soluble fraction of a total preparation of polyphenols from the bark of SaZi~ r~bra was chromatographed on a column with a polyamide sorbent by a method described previous- ly [i]. Fractions of eluate corresponding to the zones on the column fluorescing in UV light were collected.

    In the first fractions pyrocatechol, p-coumaric, and naringenin 5-glucoside were detected by paper chromatography The last two fractions, eluted from the column with a 30% solution of acetone and with pure acetone, yielded two individual glycosides of flavonoid nature

    The first of them formed yellow prisms with mp 170-171C and [~]~o _19.6 (etha~o!). UV

    tary analysis corresponded to that calculated for C~,H=zO,o. From these properties, the fla- vonoid proved to be identical with chalcononaringenin 6'-glucoslde, which is present in the bark of S. p~pumea and S. a~t~folia [3]

    The second compound formed bright orange needles with mp 181-182C and i~]~ +151.5 (c 0 5 ethanol) UV s ectra (nm~ l C2HsOH 319 372. %C2HsOH+AcNa qe&. ~CzHsOH+A[CIs &9~ l~sO,+ZrOCl= 425. PGlucose. narin~in, and'p-co~c acid were+idei~++ied as the products of the acid hydrolysis of the glycoside. On alkaline hydrolysis, it formed the chalcononarin- genin 6'-glucoside described above and p-coumaric acid. Its elementary analysis corresponded to that calculated for CsoH=80,=

    Thus, on the basis of chemical properties and the results of spectral investigations with ionizing and complex-forming reagents it may be concluded that this compound is an ester of chalcononaringenin 6'-glucoside and p-coumaric acid The presence of an ester grouping in it was confirmed by the corresponding absorption band in the IR spectrum: 1690 cm-* (VC=n of an Ar--CH=CH--COO--R group), 1290 and ii00 om-1, and others. These bands were absent from the IR spectrum of the deacylated glycoside. On the basis of the absence of an absorption band of 1050 cm-* (VC=O of a glucose CH~OH group) from the IR spectrum of the compounds under inves- tigation and its appearance after the splitting out of the p-coumaric acid, we assumed that the acid residue in it substitutes the hydroxyl at C6 of the glucose. Consequently, the acylated chalcone from the bark of Salix rubra is 2',4,4',6'-tetrahydroxychalcone 6'-O-(p- coumaroylglucopyranoside). This compound proved to be identical with the chalcone that we have isolated previously [i] from the bark of S. aeutifolia.

    i.

    LITERATURE CITED

    I. I. Vinokurov and A. I. Skrigan, Izv. Akad. Nauk BSSR, Set. Khim. Nauk, No. 5, 112 (1969)

    Virsk State Pedagogic Institute Translated from Khimiya Prirodnykh Soedinenni, No. 3, p. 406, May-June, 1979. Original article submitted January 16, 1979.

    0009-3130/79/1503-0355507.50 1979 Plenum Publishing Corporation 355

  • 2. C. Charaux and J. Rabate, Compt. Rend., 192, 1478 (1931); 196, 816 (1933). 3. A. I, Skrigan and I. I. Vinokurov, Izv. Akad. Nauk BSSR, Ser. Khim., No. 3, 72 (1969).

    PHENOLIC COMPOUNDS OF THE EPIGEAL PART OF VALERIAN.

    II. COMPOSITION OF THE PHENOLIC COMPOUNDS OF Valez~.~na ~rens~8

    N. S. Fursa UDC547.972

    According to two-dimensional chromatography on paper F No. 7, the epigeal part of V~l- er~na ~rens i8 P. Smirn. (Amur valerian), collected in the flowering phase in the Maritime Territory in 1974 contains not less than ten flavonoid glycosides and ten phenolic carboxylic acids. The purified aqueous extract obtained by extracting the air-dry raw material with 80% ethanol was investigated in the manner described previously [i]. As a result, ten compounds (l-X) were isolated in the individual state. For substances (I) and (II) the color reactions and absorption in the UV region of hydroxycinnamic acids were characteristic. Substance (I) was identified as caffeic acid, (II) as chlorgenic acid, and (III) as p-hydroxyhenzoic acid.

    Substances (IV-VII) were flavone aglycones and (VIII) and (IX) were flavonol aglycones, and these were identified from their physicochemical constants and chromatographic behavior in comparison with markers as the following known compounds: apigenin (IV), luteolin (V), diosmetin (VI), acacetin (VII), kaempferol (VIII), and quercetin (IX). In a comparison with samples of Valeriana offie~nal~s L. growing in the territory of the Ukrainian SSR [I], it was found that the sample of the Valeri~na csnurensi8 studied contained acacetin glycosides in predominating amount.

    Substance (X) had the composition C~,H2o01o, mp 227-229C (from isopropanol), Rf 0.14 (15% acetic acid), 0.62 (isobutanol--acetic acid-water (4:1:2)). Its quantitative acid hy- drolysis formed equimolar amounts of D-glucose and apigenin. The results of qualitative re- actions, spectral investigations in the UV region with the use of diagnostic reagents (E,%cm = 421), and enzymolysis with the 8-hydrolase from the fungus Asp~rgilZu8 ol~jzae enabled the substance under investigation to be characterized as apigenin 7-O-8-D-glucosi4e.

    This is the first time that information has been given on the qualitative composition of the phenolic compounds of Valer~ana ~numensis. In addition to these compounds, valepotriates were detected in the epigeal and hypogeal parts of the plant.

    i.

    LITERATURE CITED

    A. S. Rybal'chenko, N. S. Fursa, and V. I. Litvinenko, Khim. Prir. Soedin., 106 (1976).

    Zaporozhe Medical Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 3, p. 407, May-June, 1979. Original article submitted January 22, 1979.

    356 0009-3130/79/1503-0356507.50 1979 Plenum Publishing Corporation