New Flavone Glycosides from Astragalus tanae Endemic to Georgia

Article abstract of DOI:10.1007/s10600-020-02946-y

The new flavone glycosides tanoside I and II in addition to three known flavonoids and daucosterol were isolated from the Georgian endemic species Astragalus tanae Sosn. Their structures were elucidated as chrysoeriol-7-O-β-D-glucopyranosyl-4′ -O-α-L-rham

Full text of DOI:10.1007/s10600-020-02946-y

DOI 10.1007/s10600-020-02946-y
Chemistry of Natural Compounds, Vol. 56, No. 1, January, 2020
NEW FLAVONE GLYCOSIDES FROM Astragalus tanae
ENDEMIC TO GEORGIA
1
*
1
2
N. Kavtaradze, M. Alaniya, M. Masullo,
2
2
A. Cerulli, and S. Piacente
The new flavone glycosides tanoside I and II in addition to three known flavonoids and daucosterol were
isolated from the Georgian endemic species Astragalus tanae Sosn. Their structures were elucidated as
chrysoeriol-7-O-β-D-glucopyranosyl-4′-O-α-L-rhamnopyranoside,
chrysoeriol-4′-O-α-L-
rhamnopyranoside, kaempferol-3-O-β-D-glucopyranosyl(2→1)-O-α-L-rhamnopyranoside (kaempferol-3-
O-β-D-neohesperidoside), tamarixin, apigenin, and β-sitosterol-3-O-β-D-glucopyranoside (daucosterol).
Keywords: Astragalus tanae, flavonoids, glucosides, chrysoeriol, tanoside I, tanoside II, tamarixin, kaempferol-3-
O-β-D-neohesperidoside, daucosterol.
Plants of the genus Astragalus provide raw material for biologically active additives [1–3] and valuable excipients
used in the pharmaceutical industry and other sectors [4] and the manufacturing of medicines [5, 6].
Astragalus tanae Sosn. is one of 16 endemic species of the 72 species inhabiting Georgia [7]. Flavonoid kaempferol
derivatives [8] and triterpenes [9] were previously isolated and characterized from A. tanae. Later, new flavone glycosides
(
1 and 2), three known flavonoids (3–5), and a sterol glycoside (6) were isolated and identified. The present work describes them.
OCH
3
OR
R
1
O
O
O
OH
1
, 2
1
: R = Rhap; R = Glcp
1
2
: R = Rhap; R = H
1
Compounds 1–6 were isolated by fractionation of total extracted substances from aerial parts over Sephadex LH-20
followed by separation of the obtained fractions by HPLC and separation over silica gel of total slightly polar substances.
Compound 1 formed pale-yellow crystals of molecular formula C H O that was established using ESI-MS
2
8
32 15
–1
–
(
m/z 607.5356, [M – H] ). The IR spectrum showed vibrations for OH (3400 cm ) and carbonyl (1653) and characteristic
absorption bands for aromatic systems (1606, 1554, 1495). A Bryant cyanidin test was positive [10], confirming that the
compound was a flavonoid glycoside. The UV spectrum showed absorption maxima at 260 and 345 nm, which was typical of
flavones. The PMR spectrum (Table 1) exhibited the H-3 resonance at 6.80 ppm. A resonance for the corresponding C atom
1
3
appeared at δ 103.9 in the C NMR spectrum. Addition of ionizing and complexing reagents established that the substituents
in the aglycon were located on C-7, C-3′, and C-4′; C-3 lacked a hydroxyl; and the molecule was ortho-substituted. Acid
hydrolysis formed the sugars D-glucose and L-rhamnose.
1
) I. Kutateladze Institute of Pharmacochemistry, Tbilisi State Medical University, 36 P. Sarajishvili St., Tbilisi,
0
159, Georgia, e-mail: kavtaradzenana@yahoo.com; 2) Dipartimento di Farmacia, Universita degli Studi di Salerno, Via
Giovanni Paolo II, 84084 Salerno, Italy. Translated from Khimiya Prirodnykh Soedinenii, No. 1, January–February, 2020,
pp. 65–68. Original article submitted June 12, 2019.
7
0
0009-3130/20/5601-0070 ©2020 Springer Science+Business Media, LLC

TABLE 1. PMR and 13C NMR Spectra of 1 and 2 (CD OD, δ, ppm, J/Hz)
3
1
2
C atom
δH
δC
HMBC (Í→Ñ)
δH
δC
HMBC (Í→Ñ)
2
3
4
5
6
7
8
9
–
164.4
103.9
182.5
161.9
99.2
164.3
95.0
157.9
104.7
122.8
110.6
149.1
151.3
116.1
120.8
56.3
–
–
164.5
104.2
182.1
161.7
99.3
163.9
95.1
156.9
104.5
122.7
110.5
149.4
150.8
116.2
120.5
56.4
–
6.80 (s)
2, 4, 10
6.45 (s)
2, 4, 10
–
–
–
–
–
–
–
–
6.55 (d, J = 2.0)
5, 7, 8, 10
6.20 (d, J = 2.0)
5, 7, 8, 10
–
–
–
–
6.92 (d, J = 2.0)
7, 9, 10
6.71 (d, J = 2.0)
6, 7, 9, 10
–
–
–
–
–
–
–
–
–
–
–
–
10
1
2
3
4
5
6
′
′
′
′
′
′
7.68 (d, J = 2.1)
1′, 3′, 4′
7.60 (d, J = 2.1)
1′, 3′, 4′
–
–
–
–
–
–
–
–
7.34 (d, J = 8.3)
7.62 (dd, J = 8.3, 2.1)
3.97 (s)
1′, 3′, 4′, 6′
1′, 2′, 5′
3′
7.32 (d, J = 8.3)
7.55 (dd, J = 2.1, 8.3)
3.98 (s)
1′ 3′, 4′, 6′
1′, 2′, 5′, 4′
3′
3
′-OCH
3
D-Glcp
1
2
3
4
5
6
′′
′′
′′
′′
′′
′′
5.12 (d, J = 7.6)
3.32 (d, J = 11.4)
3.55 (d, J = 11.4)
3.20–3.80 (m)
100.6
75.1
76.6
71.3
77.1
63.2
7
1′′, 3′′
2′′
3′′, 5′′
4′′, 6′′
4′′, 5′′
3.20–3.86 (m)
3.72 (dd, J = 12.0, 4.2)
3
.58 (dd, J = 12.0, 4.5)
L-Rhap
1′′′
2
′′′
3′′′
4′′′
5′′′
5.55 (d, J = 4)
99.6
70.2
70.3
71.7
67.9
18.1
4′
1′′′, 3′′′
2′′′
3′′′
4′′′, 6′′′
5.52 (d, J = 4)
4.51 (dd, J = 1.7, 3.2)
3.87 (dd, J = 3.2, 9.3)
3.24–3.83 (m)
98.8
72.1
69.8
73.4
67.7
18.0
4′, 2′′′
1′′′, 3′′′
2′′′
3′′′, 5′′′
4′′′, 6′′′
4′′′, 5′′′
4.62 (dd, J = 1.7, 3.2)
3.94 (dd, J = 3.2, 9.3)
3.20–3.80 (m)
3.20–3.86 (m)
3.24–3.89 (m)
1.22 (d, J = 6)
6
′′′ (CH
3
)
0.99 (d, J = 6)
5′′′
The PMR spectrum showed six resonances for aromatic protons at 6.5–7.7 ppm and resonances for anomeric protons
at 5.55 and 5.12 ppm. The SSCC (J = 2.0 Hz) of doublets at δ 6.55 (H-6) and δ 6.92 (H-8) were indicative of meta-coupling
of aromatic protons. Doublets at δ 7.68 (H-2′), 7.34 (H-5′), and 7.62 (H-6′) suggested that the protons in the flavonoid side
aromatic ring were asymmetric.
A singlet at 3.97 ppm and the corresponding resonance at 56.3 ppm in the 13C NMR spectrum were consistent with
a methoxyl in the molecule (Table 1). A correlation between resonances at δ 149.1 and 3.97 indicated that the methoxyl was
1
3
bonded to C-3′. The C NMR spectrum contained chemical shifts for 28 C atoms. UV spectra of the aglycon obtained by acid
hydrolysis confirmed that C-3′ was substituted by a methoxyl. Methyl protons of L-rhamnose appeared at 0.99 ppm and
correlated with a resonance at 18.1 ppm in the 13C NMR spectrum. Based on these results, the aglycon of 1 was
3
′-methoxyapigenin or chrysoeriol [11–13].
The site of attachment of the sugar to the aglycon was established using a heteronuclear correlation spectrum (HMBC)
in which correlations were observed between the D-glucose (δ 5.12) and L-rhamnose anomeric protons (δ 5.55) and C-7
(
δ 164.3) and C-4′ (δ 151.3), respectively.
Considering these results, 1 was chrysoeriol-7-O-β-D-glucopyranosyl-4′-O-α-L-rhamnopyranoside. A flavone
glycoside with this structure has not been reported so 1 was new and called tanoside I (1).
Compound 2 was also pale-yellow crystals with molecular formula C H O that was established by ESI-MS
2
2
22 10
–1
–
–1
(
m/z 445.3967 [M – H] ). The IR spectrum showed vibrations for OH (3460 cm ), carbonyl (1654 cm ), and aromatic
systems (1606, 1415, 1252 cm ). A Bryant cyanidin test was positive [10]. The UV spectrum showed absorption maxima at
–
1
2
70 and 340 nm that were typical of flavones. Addition of ionizing and complexing reagents indicated that substituents in the
7
1

aglycon were located on C-7, C-3′, and C-4′; C-3 lacked an OH; and the molecule was ortho-substituted. Proton H-3 (Table 1)
appeared at 6.45 ppm in the PMR spectrum, which also showed six resonances for aromatic protons at 6.20–7.62 ppm and
1
3
a resonance for an anomeric proton at 5.52 ppm. The methoxyl gave a singlet at 3.98 ppm and the corresponding C resonance
1
3
at δ 56.4. The C NMR spectrum had chemical shifts for 22 C atoms (Table 1). A correlation between resonances at δ 149.4
and 3.98 ppm proved that the methoxyl was bonded to C-3′. Methyl protons of L-rhamnose were found at 1.22 ppm and
1
3
correlated with a C resonance at δ 18.0. Acid hydrolysis gave L-rhamnose and the aglycon, which was identical to that of 1.
Based on the experimental results, the aglycon of 2 was chrysoeriol.
The location of the sugar in 2 was established by a correlation between the L-rhamnose anomeric proton (δ 5.52) and
the C-4′ resonance (δ 150.8) in the HMBC spectrum.
According to the results, 2 was chrysoeriol-4′-O-α-L-rhamnopyranoside. A flavonoid with this structure has not
been reported so 2 was a new compound and was called tanoside II.
Compounds 3–5 were identified as the known flavonoids apigenin (3) [5, 11], tamarixin (4) [14], and kaempferol-3-
O-β-D-glucopyranosyl(2→1)-α-L-rhamnopyranoside (5) [15]. Compound 6 was characterized as β-sitosterol-3-O-β-D-
glucopyranoside or daucosterol [16].
EXPERIMENTAL
General Comments. UV and IR spectra were taken on Jasco V-730 and Jasco FT/IR-4600 V-730 instruments.
NMR spectra were recorded in CD OD (99.95%, Sigma-Aldrich) on a Bruker DRX 600 spectrometer (Bruker BioSpin GmbH,
3
Rheinstetten, Germany) equipped with a Bruker 5-mm TCI CryoProbe at 300 K. Mass spectra were taken using an Agilent
6
240 ESI-MS. HPLC was performed on a Waters 590 apparatus equipped with a Waters R401 refractive-index detector and
a Waters Bondapak™ C18 chromatography column (8 × 300 mm). Column chromatography used Kieselgel 60 (0.06–0.2 mm,
Carl Roth GmbH) and Sephadex LH-20 (Pharmacia); TLC, silica gel 60 F254 plates (Merck); paper chromatography (PC),
FN-11 (Whatman). The solvent systems for TLC and PC were n-BuOH–AcOH–H O (60:15:25, 1); CHCl –MeOH (10:1, 2);
2
3
and C H N–C H –n-BuOH–H O (3:1:5:3, 3). TLC plates were detected by spraying Ce(SO ) solution in dilute H SO
5
5
6
6
2
4 2
2
4
followed by heating at 110°C for 2–3 min. Sugars in paper chromatograms were detected using anilinium phthalate reagent.
Plant Material. A. tanae Sosn. (Leguminosae) was collected in the environs of Tbilisi (Digmistskali gorge, Didgori)
at the end of June 2013 during flowering. Specimens were determined at the Direction of Pharmacobotany, I. Kutateladze
Institute of Pharmacochemistry (Tbilisi, Georgia), herbarium No. 13 076.
Extraction and Isolation. Air-dried milled flowers (0.7 kg) were extracted with EtOH (80%). The obtained extract
was evaporated to a watery residue. A viscous resinous precipitate was filtered off. The residue on the filter did not contain
flavonoids and triterpenoids according to TLC. The filtrate was purified by CHCl . White needle-like crystals precipitated at
3
the interface between the layers and turned out to be a mixture of two compounds [9]. The crystalline precipitate was separated.
The remaining aqueous layer was extracted sequentially with CHCl (4 × 200 mL) and EtOAc (5 × 200 mL).
3
The obtained CHCl extract was evaporated. The solid (2 g) was separated over a silica gel column (1.5 × 40 cm)
3
with elution by CHCl and CHCl –MeOH mixtures with increasing concentration of the latter. Fraction 26 yielded yellow
3
3
crystals (compound 3, 12 mg); fractions 30 and 31, white crystals (6, 10 mg).
The dry solid (3 g) obtained by evaporating the aqueous layer was dissolved in MeOH (15 mL). The insoluble part
was separated by centrifugation. The liquid was transferred to a Sephadex LH-20 column (100 × 5 cm) and eluted by MeOH
to produce 97 fractions (10 mL each). Fractions that had identical compositions by TLC using system 1 were combined.
Fraction 35 afforded 5 (11 mg); combined 37–49, 1 (9 mg).
Separation of the EtOAc fraction by isocratic HPLC (40% MeOH, flow rate 2.5 mL/min) produced 2 (8 mg) and 4 (6 mg).
Chrysoeriol-7-O-β-D-glucopyranosyl-4′-O-α-L-rhamnopyranoside or tanoside I (1), yellow crystals,
–
1
mp 256–259°Ñ. IR spectrum (KBr, ν, cm ): 3400 (OH), 1653, 1606, 1554, 1495, 1354. UV spectrum (ÌåÎÍ, λmax, nm):
60, 345; +NaOMe – 268, 350; +AlCl – 271, 396; + AlCl /HCl – 270, 390; + NaOAc – 263, 345. Mass spectrum,
2
3
3
–
–
–
m/z: 607.5356 [M – H] (calcd for C H O , 608.5386); 299 [M – H – Glc – Rha] ; 284 [M – H – Glc – Rha – CH ] ;
2
8
32 15
3
–
–
445 [M – H – Glc] ; 461 [M – H – Rha] .
Acid Hydrolysis of 1. A MeOH solution of 1 (3 mg) was treated with H SO solution (5%), hydrolyzed on a water
2
4
bath at 80°C for 2 h, cooled, diluted with H O, and extracted with EtOAc. The extract was washed with H O, dried over
2
2
anhydrous Na SO , and evaporated to dryness. The solid was dissolved in MeOH, after which the aglycon crystallized,
2
4
7
2

mp 325–330°Ñ. UV spectrum (ÌåÎÍ, λmax, nm): 265, 345; +NaOMe – 267, 405; +AlCl – 274, 396; + AlCl /HCl – 275,
3
3
–
3
94; + NaOAc – 274, 355. The aqueous fraction was neutralized by AV-17 anion-exchanger (OH -form). Sugars were
identified by comparing paper chromatograms with authentic D-glucose and L-rhamnose using system 3.
Chrysoeriol-4′-O-α-L-rhamnopyranoside or tanoside II (2), yellow crystals, mp 272–275°Ñ. IR spectrum
–
1
(
+
KBr, ν, cm ): 3460 (OH), 1654, 1606, 1415, 1252. UV spectrum (ÌåÎÍ, λ , nm): 266, 346; +NaOMe – 265, 345;
max
–
AlCl – 270, 380; + AlCl /HCl – 280, 360; + NaOAc – 282, 346. Mass spectrum, m/z: 445.3967 [M – H] (calcd for
C H O , 446.3978), 299.2671 [M – H – Rha] ; 284.2581 [M – H – Rha – CH ] . Table 1 lists the PMR and C NMR
3
3
–
–
13
22
22 10
3
spectra.
Acid hydrolysis of 2 (3 mg) was performed analogously to that for 1 to produce the aglycon, mp 327–330°Ñ.
UV spectrum (ÌåÎÍ, λmax, nm): 260, 343; +NaOMe – 265, 400; +AlCl – 267, 396; + AlCl + HCl – 273, 394;
3
3
+
NaOAc – 263, 345. The sugar component was identified as L-rhamnose.
–
Apigenin (3), pale-yellow crystals, mp 340–342°Ñ, sublimes at 230°C. Mass spectrum, m/z: 269.0533 [M – H]
1
(
5
calcd for C H O , 270.0528). Í NMR spectrum (δ, ppm, J/Hz): 7.55 (2H, d, J = 8.9, Í-2′, 6′), 7.41 (2Í, d, J = 8.9, Í-3′,
′), 7.18 (1H, d, J = 2.0, Í-8), 7.10 (1Í, s, H-3), 7.01 (1H, d, J = 2.0, Í-6). C NMR spectrum (δ, ppm): 165.2 (Ñ-2), 104.3
1
5 10 5
1
3
(
1
Ñ-3), 183.1 (Ñ-4), 162.1 (Ñ-5), 100.2 (Ñ-6), 164.9 (Ñ-7), 95.6 (Ñ-8), 159.7 (Ñ-9), 105.1 (Ñ-10), 122.7 (Ñ-1′), 129.8 (Ñ-2′, 6′),
17.4 (Ñ-3′, 5′), 161.8 (Ñ-4′).
Tamarixin or tamarixetin-3-O-β-D-glucopyranoside (4), pale-yellow crystals, mp 315°Ñ (dec.). IR spectrum (KBr,
–
1
ν, cm ): 3400 (OH), 1652, 1600, 1561, 1506, 1290, 1207, 1165. UV spectrum (ÌåÎÍ, λ , nm): 255, 288, 375; + AlCl :
2
C H O , 478.406); 315.230 [M – H – Glc] ; 300.042 [M – H – Glc – CH ] . Í NMR spectrum (δ, ppm, J/Hz): 7.96 (1H, d,
max
3
–
70, 300, 390; + AlCl /HCl: 270, 300, 375; + NaOMe: 270, 330, 410. Mass spectrum, m/z: 477.401 [M – H] (calcd for
3
–
– 1
22
22 12
3
J = 2.0, Í-2′), 7.63 (1H, dd, J = 2.0, 8.4, Í-6′), 6.92 (1Í, d, J = 8.4, Í-5′), 6.44 (1H, d, J = 2.0, Í-8), 6.23 (1H, d, J = 2.0, Í-6), 5.48
1Í, d, J = 7.2, Í-1′′), 3.30–3.75 (m, D-glucose protons), 3.96 (3H, s, 4′-OCH3). 13C NMR spectrum (δ, ppm): 160.2 (Ñ-2),
36.7 (Ñ-3), 173.9 (Ñ-4), 164.1 (Ñ-5), 100.1 (Ñ-6), 167.7 (Ñ-7), 94.4 (Ñ-8), 159.8 (Ñ-9), 104.9 (Ñ-10), 125.2 (Ñ-1′), 114.9
(
1
(
(
Ñ-2′), 152.4 (Ñ-3′), 150.3 (Ñ-4′), 115.1 (Ñ-5′), 129.8 (Ñ-6′), 105.4 (Ñ-1′′), 75.1 (Ñ-2′′), 77.8 (Ñ-3′′), 71.4 (Ñ-4′′), 78.7
Ñ-5′′), 63.4 (Ñ-6′′).
Kaempferol-3-O-β-D-glucopyranosyl(2→1)-O-α-L-rhamnopyranoside or kaempferol-3-O-β-D-
–
1
neohesperidoside (5), yellow compound, mp 195–199°Ñ. IR spectrum (KBr, ν, cm ): 3400 (OH), 1662, 1615, 1514, 1494.
UV spectrum (ÌåÎÍ, λmax, nm): 266, 295, 350; +NaOMe – 276, 320, 405; +AlCl – 275, 315, 390; + AlCl /HCl – 275,
3
3
–
3
[
10, 386; + NaOAc – 272, 316, 390. Mass spectrum, m/z: 593.513 [M – H] (calcd for C H O , 594.5121); 447.192
M – H – Rha] ; 285.219 [M – H – Rha – Glc] . Í NMR spectrum (δ, ppm, J/Hz): 8.10 (1H, d, J = 2.1, Í-2′, 6′), 6.92 (1H, dd,
27 30 15
–
– 1
J = 2.1, 8.3, Í-3′, 5′), 6.42 (1H, d, J = 2.0, Í-8), 6.22 (1H, d, J = 2.0, Í-6), 5.76 (1Í, d, J = 7.2, Glc Í-1), 5.22 (1Í, s,
1
3
Rha Í-1), 3.40–4.45 (m, sugar protons), 1.29 (3H, d, J = 6, CH -Rha). C NMR spectrum (δ, ppm): 155.4 (Ñ-2), 133.6 (Ñ-3),
3
1
78.1 (Ñ-4), 161.5 (Ñ-5), 98.6 (Ñ-6), 164.3 (Ñ-7), 94.0 (Ñ-8), 156.7 (Ñ-9), 104.3 (Ñ-10), 120.5 (Ñ-1′), 131.2 (Ñ-2′), 115.2
(
Ñ-3′), 160.2 (Ñ-4′), 115.2 (Ñ-5′), 131.2 (Ñ-6′), 99.0 (Ñ-1′′), 77.3 (Ñ-2′′), 76.7 (Ñ-3′′), 70.4 (Ñ-4′′), 77.0 (Ñ-5′′), 62.7 (Ñ-6′′),
1
00.4 (Ñ-1′′′), 71.0 (Ñ-2′′′), 71.7 (Ñ-3′′′), 72.0 (Ñ-4′′′), 66.7 (Ñ-5′′′), 17.8 (ÑH -Rha).
3
β-Sitosterol-3-O-β-D-glucopyranoside or daucosterol (6), white crystals, mp 289–292°C. Mass spectrum, m/z 576.86,
–1
1
C H O . IR spectrum (KBr, ν, cm ): 3425 (OH), 2960 (CH ), 1460, 1075, 1020 (ÑÍ-ÑÍ). Í NMR spectrum (δ, ppm,
35
60
6
3
J/Hz): 0.74 (3Í, s, CH -18), 0.84 (3H, d, J = 6.8, CÍ -27), 0.87 (3H, d, J = 5.5, CÍ -26), 0.88 (3H, t, J = 7.4, CÍ -29), 0.95 (3Í,
3
3
3
3
d, J = 5.1, CÍ -21), 0.93 (1Í, m, Í-24), 0.96 (1Í, m, Í-9), 1.02 (1H, m, Í -11), 1.03 (1H, m, Í-14), 1.05 (3H, s, CÍ -19), 1.09
3
a
3
(
(
(
1H, m, Í -1), 1.12 (1H, m, Í -15), 1.14 (1H, m, Í-17), 1.19 (1H, m, Í -12), 1.22 (2Í, m, H-23), 1.28 (2H, m, Í-28), 1.33
a a a
1H, m, Í -16), 1.32 (1H, m, Í -22), 1.40 (1H, m, Í-20), 1.45 (2H, m, Í -11), 1.48 (1H, m, Í-8), 1.55 (1H, m, Í -7), 1.55
1H, m, Í -22), 1.61 (1H, m, Í -15), 1.63 (1H, m, Í -2), 1.69 (1H, m, Í-25), 1.88 (1H, m, Í -16), 1.89 (1H, m, Í -1), 1.93 (1H,
a
a
b
a
b
b
a
b
b
m, Í -2), 1.99 (1H, m, Í -7), 2.05 (1H, m, Í -12), 2.27 (1H, br.t, J = 10.0, Í -4), 2.43 (1H, m, Í -4), 3.16 (1H, dd, J = 7.8,
b
b
b
a
b
9
1
.0, Í-2′), 3.27 (1H, m, Í-5′), 3.28 (1H, m, Í-4′), 3.36 (1H, dd, J = 9.0, 9.0, Í-3′), 3.59 (1H, m, Í-3), 3.66 (1H, dd, J = 4.7,
2.0, Í -6′), 3.90 (1H, dd, J = 1.7, 12.0, Í -6′), 4.39 (1H, dd, J = 7.8, Í-1′), 5.38 (1H, d, J = 5.0, Í-6). C NMR spectrum (δ,
1
3
a
b
ppm): 38.2 (Ñ-1), 30.4 (Ñ-2), 79.7 (Ñ-3), 39.4 (Ñ-4), 141.8 (Ñ-5), 122.5 (Ñ-6), 32.7 (Ñ-7), 33.0 (Ñ-8), 51.4 (Ñ-9), 37.6 (Ñ-10),
1.8 (Ñ-11), 40.8 (Ñ-12), 43.4 (Ñ-13), 57.8 (Ñ-14), 25.3 (Ñ-15), 29.0 (Ñ-16), 57.1 (Ñ-17), 12.0 (Ñ-18), 19.7 (Ñ-19), 37.1
Ñ-20), 19.1 (Ñ-21), 32.8 (Ñ-22), 27.0 (Ñ-23), 47.1 (Ñ-24), 30.0 (Ñ-25), 19.6 (Ñ-26), 19.6 (Ñ-27), 23.9 (Ñ-28), 12.0 (Ñ-29),
02.1 (Ñ-1′), 74.8 (Ñ-2′), 77.9 (Ñ-3′), 71.4 (Ñ-4′), 77.7 (Ñ-5′), 62.7 (Ñ-6′).
2
(
1
7
3

REFERENCES
1
.
D. Bensky, A. Gamble, and T. Kaptchuk, Chinese Herbal Medicine: Materia Medica, Rev. Ed., Eastland Press, Seattle,
993, 556 pp.
L Braun, Herbs and Natural Supplements. An Evidence-based Guide, 4 Ed., Vol. 2, Elsevier, Marrickville, NSW,
Australia, 2015, 1384 pp.
1
th
2.
3
.
K. Chatfield, Astragalus: Ancient Herb for Modern Times, CreateSpace Independent Publishing Platform, 2014, 140 pp.
A. Hamedia, G. Youse, S. Farjadiane, M. S. B. Bourf, and E. Parhizkar, Iran. J. Pharm. Res., 16, 1520 (2017).
M. D. Alaniya, E. D. Kemertelidze, and N. F. Komissarenko, Flavonoids from Several Astragalus Species in the Flora
of Georgia [in Russian], Metsniereba, Tbilisi, 2002, 152 pp.
4
.
5.
6
.
E. P. Kemertelidze, M. D. Alaniya, K. G. Shalashvili, T. G. Sagareishvili, and N. Sh. Kavtaradze, Original Drugs from
Flavonoid-bearing Plants of Georgia [in Russian], Izd. Natsional′noi Akademii Gruzii, Tbilisi, 2016, 121 pp.
Flora of Georgia [in Russian], Vol. VII, Metsniereba, Tbilisi, 1981, 516 pp.
7
.
8.
M. D. Alaniya and N. F. Chkadua, Chem. Nat. Compd., 36, 537 (2000).
9.
M. D. Alaniya, N. Sh. Kavtaradze, A. V. Skhirtladze, and J. N. Aneli, Chem. Nat. Compd., 53, 682 (2017).
10.
E. F. Bryant, J. Am. Pharm. Assoc. Sci. Ed., 39, 480 (1950).
11.
L. A. Lemos da Silva, L. G. Faqueti, F. H. Reginatto, A. D. C. Santos, A. Barison, and M. W. Biavatti,
Rev. Bras. Farmacogn., 25 (4), 375 (2015).
12.
13.
14.
15.
16.
A. Plazonic, F. Bucar, Z. Males, A. Mornar, B. Nigovic, and N. Kujundzic, Molecules, 14, 2466 (2009).
P. Bashyal, P. Parajuli, R. P. Pandey, and J. K. Sohng, Catalysts, 9 (2), 112 (2019).
B. P. da Silva, R. R. Bernardo, and J. A. P. Parente, Phytochemistry, 53, 87 (2000).
K. Nakano, K. Murakami, T. Nohara, T. Tomimatsu, and T. Kawasaki, Chem. Pharm. Bull., 29 (5), 1445 (1981).
M. D. Alaniya, M. G. Sutiashvili, N. Sh. Kavtaradze, and A. V. Skhirtladze, Chem. Nat. Compd., 53, 1202 (2017).
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