Flavonoids from Gleditsia triacanthos

Full text of DOI:10.1007/s10600-016-1870-6

DOI 10.1007/s10600-016-1870-6
Chemistry of Natural Compounds, Vol. 52, No. 6, November, 2016
FLAVONOIDS FROM Gleditsia triacanthos
1
2*
M. A. Duchenko, O. V. Demeshko,
2
and V. N. Kovalev
The genus Gleditsia L. (Fabaceae) numbers from 8 to 12 species according to different sources [1]. Young leaves and
fruits from G. triacanthos are medicinal raw materials. The pharmacological activity of the leaves is due to the alkaloid
triacanthin, which exhibits spasmolytic activity, reduces arterial pressure, and expands coronary vessels. The spasmolytic
activity is highest for smooth intestinal muscle and bronchi. Anthraglycosides in the plant pericarp have laxative activity
[2, 3]. The contents of biologically active compounds in leaves depend on the collection time (from June to September), e.g.,
flavonoids 2.75–2.23%; hydroxycinnamic acids, 1.80–1.77%; and phenolic compounds, 4.91–3.36%. The quality of the raw
material is unaffected by insignificant oscillations of biologically active compounds from June to September and allows leaves
to be collected as they are falling [4].
The goal of the present work was to study the flavonoid composition of G. triacanthos leaves collected in June in
Kharkov Oblast.
Plant leaves (1.5 kg) were exhaustively extracted with EtOH (70%) by combining maceration (24 h) and subsequent
thermal extraction at 85–90°C. The aqueous EtOH extracts were combined, evaporated in vacuo to a thick residue (~700 mL),
and left in a refrigerator at 4–5°C for 1 d. The resinous residue was separated by filtration and rinsed with hot H O. The
2
rinsings were combined with the filtrate and evaporated to the initial volume. The purified aqueous solution was worked up
sequentially with CHCl , EtOAc, and n-BuOH.
3
The solvents were distilled to afford CHCl (86.0 g), EtOAc (38.1 g), n-BuOH (46.4 g), and aqueous (81.2 g) fractions.
3
Compounds in the EtOAc and n-BuOH fractions were separated using absorption chromatography over a polyamide
column with elution by H O and aqueous EtOH with gradually increasing EtOH concentrations. This isolated flavonoids
2
1–12 from the EtOAc fraction and 13–16 from the n-BuOH fraction.
Comparisons of the results with the literature and authentic samples identified 1 as quercetin; 2, isorhamnetin; 3,
myricetin; 6, rutin; 11, apigenin; 12, sapigenin-7-O-ꢀ-D-glucoside; 13, luteolin; 14, vitexin; 15, saponaretin; 16, orientin; and
17, homoorientin [4–8].
Myricetin-3-O-ꢀ-D-rutinoside (4). C H Î , mp 190–192ꢁÑ (70% MeOH). UV (ꢂ , nm): 256, 308, 363. IR
27 30 17
max
–1
spectrum (KBr, ꢃ , cm ): 2960 (OH), 1672 (C=O), 1615, 1570, 1500 (C=C), 1080–1010, 885 (ꢀ-glycoside bond). Acid
max
hydrolysis of 4 produced myricetin in addition to D-glucose and L-rhamnose.
Myricetin-3-O-ꢀ-D-glucoside (5). C H Î , mp 275–277ꢁÑ (MeOH). UV (ꢂ , nm): 256, 304, 360. IR spectrum
21 20 13
max
–1
(KBr, ꢃ , cm ): 2940 (OH), 1670 (C=Ñ), 1620, 1560, 1542 (C=C), 1070–1000, 885 (ꢀ-glycoside bond). Acid hydrolysis
max
of 5 produced myricetin and D-glucose.
Quercetin-3-O-ꢀ-D-gentiobioside (7). C H O , mp 180–182ꢁÑ (70% MeOH). UV (ꢂ , nm): 258, 267, 367.
27 30 17
max
–1
IR spectrum (KBr, ꢃ , cm ): 3350 (OH), 1662 (C=O), 1600–1445 (C=C), 1100–1010, 890 (ꢀ-glycoside bond). Enzymatic
max
hydrolysis by rhamnodiastase produced quercetin and gentiobiose. Isoquercitrin and D-glucose resulted from stepwise acid
hydrolysis by H SO (2%).
2
4
Isoquercitrin (8). C H O , mp 248–250°C. Acid hydrolysis of 8 produced quercetin and D-glucose.
21 20 12
Isorhamnetin-3-O-ꢀ-D-gentiobioside (9). C H O , mp 198–201ꢁÑ (70% MeOH). UV (ꢂ , nm): 257, 268,
28 32 17
max
–1
357. IR spectrum (KBr, ꢃ , cm ): 3285 (OH), 1670 (C=O), 1625–1514 (C=C), 2920, 2852 (OCH ), 1100–1010, 890
max
3
(ꢀ-glycoside bond). Stepwise acid hydrolysis produced isorhamnetin-3-O-glucoside and D-glucose. Enzymatic hydrolysis by
rhamnodiastase produced isorhamnetin and gentiobiose.
1) Vinnitsa State Pirogov Memorial Medical University, Ukraine; 2) National Pharmaceutical University, 4
Valentinovskaya St., Kharkov, 61146, Ukraine, e-mail: olgademeshko@gmail.com. Translated from Khimiya Prirodnykh
Soedinenii, No. 6, November–December, 2016, pp. 941–942. Original article submitted March 11, 2016.
©
0009-3130/16/5206-1093 2016 Springer Science+Business Media New York
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Isorhamnetin-3-O-ꢀ-D-glucoside (10). C H O , mp 250–252°C (MeOH). Acid hydrolysis of 10 produced
22 22 12
isorhamnetin and D-glucose [4, 5].
Compounds 2–5 and 7–10 were isolated for the first time from G. triacanthos leaves. Myricetin and apigenin glycosides
prevailed according to quantitative HPLC.
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