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_OBTAINING CELLULOSE FROM THE MEDICINALPLANT MILK THISTLE
10. Jahan S. M., RahmanH, Rani S. P., Rahman M. Department of Chemistry, Eden Girls College, Dhaka. Ethylenediamine in alkaline cooking of jute stick for producing dissolving pulp Bangladesh. Res.,-No. 2. 2015.- P. 7-14.
11. Israel A. U., Obot I. B., Umoren S. A., Mkpenie Vand Asuquo J. E. Production of Cellulosic Polymers from Agricultural Wastes E-Journal of Chemistry,- Vol. 5.- No. 1. 2008.- P. 81-85.
https://doi.org/10.29013/AJT-22-3.4-82-86
Kaypnazarov Turdibay Nzamatdinovich, Junior Researcher S. Yu. Yunusov Institute, of the Chemistry of plant Substances AS Uzbekistan Uteniyazov Karimbay Kuanishbaevich, Candidate of Chemical Sciences, Department "Organic and inorganic chemistry" Karakalpak State University, Mirzaeva Makhira Risbaevna, Candidate of Chemical Sciences, associate professor of chemistry and chemical technology of Faculty of Natural Science, Tourism and agricultural technologies of Osh State University Abdullayev Nasir Dzhalilovich, S. Yu. Yunusov Institute of the Chemistry of Plant Substances Candidate of Chemical Sciences, Academy of Sciences of Uzbekistan
Ramazonov Nurmurod Sheralievich, S. Yu. Yunusov Institute of the Chemistry of Plant Substances Doctor of Sciences, (in chemistry), Professor, Head of the laboratory Chemistry of glycosides, Academy of Sciences of Uzbekistan
TRITERPENE GLYCOSIDES TRAGACANTHA STIPULOSA AND THEIR GENINS. STRUCTURE OF CYCLOSTIPULOSIDE D
Abstract. Three renowned compounds cycloartane series are highlighted from aboveground organs Tragacantha stipulosa Boriss- cyclosiversiosides E and F, cyclonifolioside B and a new glycoside -cyclostipuloside D that has structure 3-0-^-0 - glucopyranoside, 6-O-^-D - xylopyranoside -20R, 24S - epoxycycloartan -3^,6a, 16^, 25 - tetraola. Structure of glycosides is determined based on NMR spectra 1H and 13C interpreted with 2M NMR - spectroscopy 1H -1H COSY, ROESY, TOCSY, HSQC, HMBC.
Keywords: Cycloartans, cyclosiversiosides E and F, cyclonifolioside B, cyclostipuloside D.
Keeping research of cycloartan triterpe-noids of Tragacantha stipulosa Boriss plant (сем. Leguminosae) [1; 2], renowned compounds of cyclosiversiosides Е (1) и F (2) [3], cyclounifolioside B (3) [4] and new cycloartan glycoside cyclostipuloside D (4) had been extracted.
In IR spectrum compunds 4 has absorption band at 3035 sm-1, cased CH2 the cyclopropane ring group.
In the PMR spectrum (table) of cyclostipuloside D (4) as in specter of cyclostypuloside C [1] in strong field areas at 0.21 and 0.60 ppm we can see
that single - proton doublets spitted according to AB system (2J=3.5 Hz) belonging to the protons of the methylene group of the cyclopropane ring.
Acid hydrolysis of compound 4 shows presence of glucose and xylose and cyclosiversigenin (5) In its composition as aglikon [3].
Except that as a result of hydrolysis we had connection 6 identical in its physico-chemical constants and spectral data with sievers and genin [5].
In NMR spectra 1H of siversigenina (6) there is single - proton signal at 5.25 ppm., applicable to olefin proton. There are not cyclopropane ring signals in NMR spectra 1H.
It is known that under the influence of acids 9,19-cyclopropane ring is disclosed with the formation of a double bond 9(11) [6].
In NMR spectra 1H compunds 4 at 4.85 (2H, d. 3J=7.5 Hz) and 4.92 (2H, d. 3J=7.5 Hz) we can see signals of two anomeric protons. Anomeric carbon atoms of two monosaccharide residues (3-D- glu-copyranoses and (3-D - xylopyranoses resonates at 107.37 and 105.44 ppm. accordingly (table).
Signals of anomeric protons of monosaccharide residues in the PMR spectrum are revealed as doublets with SSCC3J=7.5 Hz, signifying ^-configuration
OH
of glycoside bonds, C-1 conformation, and the pyra-nose form of both monosaccharide residues.
Based on results of comparative analysis of the values of chemical shifts of carbon atom signals in the 13C NMR spectra of cyclostypuloside D (4) and cyclosiversigenin (5) found that the effect of glyco-sylation was subjected to hydroxyl groups at C-3 and C-6. Accordingly, it can be assumed that sugar residues are attached to genin via hydroxyl at C-3 and C-6.
Localization of carbohydrate residues was found by analyzing the spectra of COSY, TOCSY, HSQC and HMBC. The location of (3-D-glucopyranose at C-3 aglycone is confirmed by the presence in the ROESY spectrum of correlation peaks of H-1 glu-copyranose with H-3 and H-29 aglycone and in the spectrum of HMBC - correlation peak of H-1 glu-copyranose and C-3 aglycone.
Based on the above data, it can be concluded that glucopyranose is attached to the hydroxyl group at C-3 and, consequently, xylopyranose is attached to the hydroxyl at C-6 of the aglycone.
Thus compound 4 us glycoside of cyclosiversigenin and has the structure of 3-O-^-D- glucopyran-oside, 6-O-^-D- xylopyranoside -20R, 24S - epoxy-cycloartan - 3^, 6a, 16^, 25 - tetraola.
OH
RiO T
' OR2
1. R1=R2=Xylp;
2. R1=Xylp, R2=Glcp;
3. R1=Glcp(-2-Glcp), R2=H;
4. R1=Glcp, R2=Xylp;
5. R.,=R2=H.
HO Y 6
' OH
Table 1.- Chemical shifts of signals in the NMR spectrum 1H and 13C of cyclosiversiosides E (1), F (2), cyclonifolioside B (3), cyclostipuloside D (4), cyclosiversigenine (5) and siversigenine (6) (C5D5N, O-TMC, 8, ppm.)
No Compound
1[3] 2[3] 3 [4] 4 5[3] 6
^ ^ ^ ^ ^ ^ ^
1 2 3 4 5 6 7 8
1 34.86 34.66 32.38 1.61; 1.26 31.97 35.16 33.24
2 26.68 29.03 30.62 2.37; 1.97 29.93 33.01 28.43
3 88.27 88.27 88.93 3.55 88.29 78.53 74.65
4 42.55 42.67 42.76 — 42.39 42.69 42.04
5 52.07 52.56 53.97 1.90 52.30 52.20 56.65
6 78.53 79.20 67.80 3.82 78.92 68.57 71.20
7 34.86 34.92 38.51 2.30; 1.87 34.38 39.08 39.94
8 44.11 46.24 46.81 1.96 45.49 47.50 47.58
9 21.15 21.13 21.02 — 20.83 21.19 142.13
10 28.38 28.89 29.42 — 28.63 30.11 45.18
11 26.24 26.49 26.28 1.83; 1.26 25.93 26.51 115.01
12 33.43 33.41 33.47 1.65; 1.57 33.15 33.65 36.97
13 45.15 45.08 45.10 — 44.82 45.28 45.18
14 46.13 46.24 46.19 — 46.00 46.41 42.04
15 45.18 45.75 46.66 2.36; 1.85 46.00 46.99 46.71
16 73.40 73.41 73.47 5.01 73.14 73.69 73.16
17 58.08 58.23 58.40 2.55 57.98 58.64 56.65
18 20.44 21.13 21.44 1.42 20.83 21.87 19.01
19 30.05 30.23 30.21 0.60; 0.21 28.77 31.70 23.64
20 87.27 87.27 87.28 — 87.00 87.48 86.98
21 27.10 28.60 28.59 1.30 28.63 27.38 27.86
22 31.89 32.24 34.96 3.12; 1.65 34.67 31.21 30.83
23 26.44 26.20 26.47 2.33; 2.06 26.20 26.69 26.83
24 81.60 81.69 81.75 3.90 81.44 81.93 81.43
25 71.23 71.29 71.28 — 71.00 71.48 72.48
26 28.13 28.21 28.21 1.58 27.92 28.44 29.10
27 28.57 28.60 27.15 1.30 26.81 28.81 29.75
28 28.38 27.10 20.16 0.96 19.60 29.67 32.04
29 16.64 16.65 28.87 2.02 28.34 16.38 17.90
30 20.44 19.87 16.59 1.37 16.37 20.47 19.81
Table 2.
1 2 3 4 5 6
3-O-ß-] D-Xylp 3-0-ß-D-Glcp(1*2) Glcp 3-O-ß-D-Glcp
1 107.59 107.56 106.12 4.85 107.37
2 75.57 75.61 77.05 4.08 75.34
3 78.53 78.15 78.15 4.17 78.24
4 71.05 71.28 71.88 4.22 71.65
1 2 3 4 5 6
5 67.04 67.07 78.08 3.93 77.84
6 62.95 4.48;4.32 62.88
6-O-ß-D-Xylp 6-O-ß-D-Glcp ■>2) ß-D-Glcp(1>3) Agl 6-O-ß-D-Xylp
1 105.70 105.46 105.05 4.92 105.44
2 75.37 75.61 83.61 4.05 75.34
3 77.77 79.31 78.42 4.22 79.03
4 71.25 71.29 71.67 4.27 71.00
5 66.95 78.55 77.95 4.36;3.72 66.78
6 63.10 62.89
EXPERIMENT
For general remarks and selection methods see [1].
Separation of the butanol fraction. When the column is eluted by the chloroform-methanol-water system (70:23:3) 27 mg of cyclosiversioside E had been isolated (1) (output 0,001%, here and further is given in terms of air-dry raw materials), 23 mg of cyclosiversioside F (2) (output 0,00092%), 17 mg of cyclonifolioside B (3) (output 0,00068%). With further elution by the same system we had1.45 g of cyclostipuloside D (4) (output 0.058%).
Cyclosiversioside E (1). C40H66013, melt. temp. 257-258° C (from methanol).
PMR spectrum (C5D5N, M.g.): 0.15 and 0.60 (by 1H, d., 3J=4.3 Hz, 2H-19), 1.11, 1.31 (2 x CH3), 1.32, 1.40, 1.59, 1.94 (c., by 3H, tertiary methyl groups), 3.45 (1H, d.d., J=11.7 and 4.5 Hz, H-3), 3.80 (1H, d.d.d., 3J=8.4; 8.4 and 5.0 Hz, H-6), 2.52 (1H, d., 3J=7.8 Hz, H-17), 3.15 (2H, q, 3J=11.0 Hz, H-22), 3.90 (1H, d.d., 3J=9.2 h 5.2 Hz, H-24), 4.82 and 4.86 (by 1H, d., 3J=7.3 and 7.6 Hz accordingly H-1' h H-1") [3].
Acid hydrolysis. 20 mg of cyclosiversioside E (1) 15 ml 0.5% methanol solution of sulfuric acid had been hydrolyzed at 70 ° C within 4 hours. Upon its cooling we fed 25 ml of water to reaction mix and methanol had been distilled. The precipitate had been filtered, flushed with water and, after drying, chromatographed on a column with silica gel. Eluting system chloroform-
methanol-water (70 : 23 : 3) we had 7 mg of cyclosiversigenin (5), С30Н50О5, melt. temp. 240-242 °C (from methanol).
For NMR spectra 13С refer to table.
Cyclosiversioside F (2). Provided 23 mg (0,00092%) of С41Н68О14, melt. temp. 260-261 oC (from methanol).
PMR Spectrum: 0.21 and 0.60 (by 1Н, d., 3J=4.2 and 4.1 Hz, 2Н-19), 0.94, 1.30, 1.31, 1.39, 1.42, 1.60, 2.06 (s., by 3Н, tertiary methyl groups), 2.53 (1Н, d. 3J=7.8 Hz, Н-17), 3.54 (1Н, d.d., 3J=11.7 and 4.6 Hz, Н-3), 3.81 (1Н, d.d.d., 3J=8.4, 8.4 and 4.2 Hz, Н-6), 3.15 (2Н, q, J=11.5 Hz, Н-22), 3.90 (1Н, d.d., 3J=9.1 and 6.5 Hz, Н-24), 5.05 (1Н, q, 3J=7.4 Hz, Н-16), 4.86 and 4.92 (by 1Н, d., 3J=7.4 and 7.7 Hz accordingly Н-1' и Н-1'') [3].
Acid hydrolysis. 13 mg cyclosiversioside F (2) had been hydrolyzed according to above method and had 5 mg of cyclosiversigenin (5). In hydrolysate, paper chromatography comparison with authentic samples we revealed xylose and glucose.
For NMR spectra 13С refer to table.
Cycloinofolioside В (3). Provided 17 mg (0,00068%) of С42Н70О15, melt. temp. 210-215 oC (from methanol).
IR spectrum (KBr, v, sm-1): 2935 (cyclopropane group).
PMR spectrum (С5Б5Н S, ppm., J/ Hz): 1.51;1.11(Н-1), 2.43;1.94(Н-2), 3.58;(Н-3), 1.66(Н-5), 3.73 (Н-6), 1.82;1.64(Н-7), .95(Н-8), 1.90;1.21(Н-11), 1.68;1.60(Н-12), 2.13;1.77(Н-15)
