547.973Continuing an investigation of the polyphenols of some species of sumac (Rhus coriaria, Rh. typhina, and Rh. glabra) [1, 2], we have now studied the chemical compositions of the fruits of these plants.The total polyphenols were isolated from them by a procedure developed previously. It was established by PC in system 1 (butan-l-ol-acetic acid-water (40:12:28)) that the polyphenols of the fruits included not only flavonols, phenolic acids, and hydrolyzable tannins but also anthocyans.Each total polyphenol preparation was dissolved in system 1 and subjected to chromatographic separation on a colunm of cellulose, using the same system as eluent. The anthocyans appeared in the form of yellow bands. These zones were cut out, eluted with methanol, and rechromatographed on columns of cellulose. Eluents containing individual compounds were combined, concentrated to small volume, and treated with a fivefold volume of petroleum ether, and the resulting precipitates were filtered off and dried.Compound (1). Dark violet powder with mp 216-218~ UV spectrum (0.01% HCI in MeOH, Xma x, nm) 525, with 5% A1C13 in EtOH -568; Rf 0.36 in system 2 (butan-l-ol-acetic acid-water (4:1:5), upper phase), 0.22 in system 3 (water-acetic acid-hydrochloric acid (82:15:3)); identified as cyanidin 3-fl-D-glucoside (chrysanthemin). Compound (2). Dark violet powder with nap 180-183~ UV spectrum (0.01% HCI in MeOH, )~max, urn) 535, with 5% A1C13 in EtOH -570; Rf 0.16 and 0.26 in systems 2 and 3, respectively; identified as delphinidin 3-fl-D-glucoside (myrtillin).Compound (3). Dark violet crystals with mp> 300"C (decomp.), Rf 0.21 (system 4: acetic acid-hydroehioric acid-water (5:1:6) and 0.35 (system 5:2 N hydrochloric acid in n-butanol), UV spectrum (0.01% HCI in MeOH, )'max, nm) 545, identified as delphinidin. It was also found that the fruits of all the sumac species investigated contained considerable amounts (5-7%) of organic acids.In Rhus glabra we detected the following acids: malic with Rf0.31 (system 6: isoamyl alcohol-5 M formic acid (1:1), descending PC); Rf O. 18 (system 7: ethanol-NH4OH-water (16:1:3), descending PC); citric with Rf 0.22 (system 6), 0.04 (system 7); succinic with Ry0.60 (system 2); fumaric with Rf0.80 (system 6); maleic with Rf0.54 (system 6) and 0.23 (system 7); and tartaric with Rf0;15 (systems 6 and 7); in Rhus corariaria: malic, citric, fumaric, and tartaric; and in Rhus typh/na: malic, succinic, fumaric, and ascorbic with Rf0.37 (system 2, descending PC) and 0.35 (system 8: water-saturated phenol + 1% acetic acid; descending PC).The malic acid formed a considerable-part (up to 25%) of the total amount of acids in all the sumac species investigated. REFERENCES 1..

UDC 547.972A study has been made of the phenolic compounds of Geranium sanguineum. One tannin of the hydrolyzable series has been isolated from the epigeal part, and for this the structure of 1,3-bis-O-digalloyl-2-O-galloyl-4, 6-(hexahydroxydiphenoyl) [13], and other types of activity [14][15][16][17][18][19][20][21][22][23]. All this accounts for the great interest in the study of the structure of this class of natural compounds.We have reported previously that flavanols, phenolic acids, and hydrolyzable tannins have been isolated from the epigeal part of Geranium sanguineum -blood-red geranium -and have been characterized; two of them -bis0aexahydroxy-diphenoyl)trigalloylglucose and 1,2,3-tri-O-gaUoyl-4,6-(hexahydroxydiphenoyl)-/~-D-glucose -proved to be new compounds, not previously described in the literature [24, 25].We have continued the study of the polyphenols of this plant. Using the procedure described in [24], the polyphenolic complex of the epigeal part of the plant was subjected to fractionation on a column of rawhide powder. The total polyphenols isolated from an aqueous acetone fraction were chromatographed on a column of silica gel using eluent systems 3 and 4. In the case of system 4, fractions were obtained containing a substance with Rf 0.43, contaminated with a substance having Ry 0.40 (system 1). After rechromatography on a column of silica gel, a substance was isolated that consisted of a f'mely disperse powder, light yellow with a greenish tinge, having mp 261~ UV spectrum of the substance (MeOH, kmax, nm): 226, 276 (log e 4.80, 4.34).The products of the complete acid hydrolysis of the substance obtained were gallic acid, glucose, and eUagic acid, in a ratio of 5:1:1, respectively. The gallic acid was determined colorimetrically [26], the ellagic acid gravimetrically, and the glucose by the semimicromethod of determining sugars [27]. Together with other compounds, 2-O-galloylglucose was detected among the products of mild acid hydrolysis. The rate of hydrolytic splitting out of the hexahydroxydiphenie acid showed that it esterified the hydroxy groups of the fourth and sixth atoms of glucose.In the IR spectrum of the substance we observed an absorption band in the 3500-3100 cm -1 region, showing the presence of free and bound hydroxy groups in the molecule. In the PMR spectrum (acetone-d6) there were overlapping signals of the protons of galloyl and hexahydroxydiphenoyl groups in the 7.20-6.65 ppm region. The signal of one of the glucose protons appeared at 6.60 ppm (1H) and those of the other six protons in the 5.60-4.21 ppm region. On the basis of the only slight change in the chemical shifts of the glucose protons and the considerable displacement of the signals of the aromatic protons of the acetylated substance into the weak-field region, it could be concluded that all the hydroxy groups of the glucose were substituted and only the phenolic hydroxyls were acetylated.A comparison of the results of chemical transformations and of spectral investigations of this compound with literature i...

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Continuing a search for promising tannide-bearing plants [1][2][3] with the aim of using them to produce drugs and highquahty tanning agents, we have investigated the polyphenols of the fruits of several varieties of Punica granatum (Kazaki, Shirindona, Aehchikdona, Kai, Kizil) growing on the territory of Uzbekistan, By a method developed earlier [1], from the peel of pomegranates of the Kazaki variety we isolated ethyl acetate and butanol fractions of the total polyphenols (2.9% and 6.8%, respectively, of the weight of the raw material). Their tannlde contents, determined by the VEM method [4], were 74 and 89 %, respectively.By means of two-dimensional PC in the solvent systems butan-1 -oi -acetic acid-water (40:12:28) and 2 % acetic acid it was established that the ethyl acetate extract contained 11 polyphenols, and the butanol extract seven. The ethyl acetate fraction was first separated on a column of rawhide powder into fractions soluble in water, in acetone, and in aqueous acetone. It was established by qualitative reactions (mixture of 1% aqueous solutions of FeCI 3 and K3Fe(CN) 6, 5% aqueous solution of Na2CO3) that the water-soluble fraction contained mainly flavonols, and the other fractions phenolic acids and hydrolyzable tanning.agents and compounds related to them. The water-soluble fraction was rechromatographed on polyamide using as eluents mixtures of chloroform and methanol in various ratios, The fractions soluble in acetone and in aqueous acetone were ehromatographed on column of silica gel using as eluents diethyl ether and ethyl acetate in various ratios.As a result, we isolated several compounds, which were identified from their physicochemical properties as pelargonldin 3-O-glucoside, quereetin, quereimeritrin, gallic and ellagie acids, punicalin,-and ptmicalagin [5] and corylagin [6]. The main compound of the polyplienol complex was a substance with the composition C41H28027.xH20 in the form of yellow crystals, which were identified as granatin B.The qualitative and quantitative compositions of the products of complete acid hydrolysis (ellagic and gallic acids, glucose) were identical with those of geranin [7][8][9][10][11]. However, in the PMR and 13C NMR spectra of the compound under investigation there were slight differences in the chemical shifts of the signals from the latter. The results of a study of the spectral characteristics of the methyl and acetyl derivatives of the compound isolated, and also of its derivative with ophenylenediamine, permitted the conclusion that it was identical with granatin B, isolated previously from Japanese varieties of Punica granatum [12].A comparison with the aid of high-pressure liquid chromatography (HPLC, Milikhrom-lA, Separon C18 column) of the qualitative composition and the polyphenols content of the peel of a Kazami pomegranate with the polyphenols of the pomegranate varieties mentioned above showed the identity of their qualitative compositions and only slight differences in the quantitative levels of individual components.It was also establi...

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