Acylated kaempferol diglycoside from Allium senescens

Full text of DOI:10.1007/s10600-009-9179-3

Chemistry of Natural Compounds, Vol. 44, No. 6, 2008
ACYLATED KAEMPFEROL DIGLYCOSIDE
FROM
Allium senescens
I. Yu. Selyutina,1 L. M. Tankhaeva,2
and D. N. Olennikov2*
UDC 547.972:582.572.225
L. s. str. (Liliaceae) is a medicinal plant used in Tibetan medicine for treating diseases of the
Allium senescens
hematopoietic system [1]. The chemical composition of this species has been insufficiently studied. It is known to contain
ascorbic acid [2], the alkaloid alliin [3], and two spirostanol glycosides gracillin and rhamnosidodioscin [4]. The goal of our
work was to investigate flavonoids from the aerial part of
.
A. senescens
found flavonoids. Hydrolysis by HCl (2 M, 2 h, 100°C)
Preliminary investigations of the aerial part of
A. senescens
of the total alcohol extract produced quercetin and kaempferol (HPTLC, solvent system 1; HPLC, conditions A).
Flavonoids were isolated by extracting raw material (aerial part of collected near Ulan-Ude, Buryatiya,
A. senescens
2006; 1 kg) with ethanol (70%, 1:10). The alcohol extract was concentrated to an aqueous residue that was extracted
successively with CHCl , ethylacetate, and -butanol.
n
3
The butanol fraction (19 g) was chromatographed over a column of polyamide (Woelm for CC) using H O→5-95%
2
ethanol (HPTLC monitoring, solvent system 1). Fractions obtained by elution with ethanol (20%) (176 mg) were
rechromatographed over silica gel (Chemapol, Silicagel L 100/400) using benzene:methanol (100:0→0:100) and then were
separated by preparative HPLC (conditions B) to afford 35 mg of 1, the purity of which was confirmed by HPLC (conditions
13
A). Based on spectral data (UV, PMR, and C NMR) and chemical transformations, 1 was identified as kaempferol-3- -β-
O
neohesperidoside-7-O-[2-O-(trans-feruloyl)]-β-D-glucopyranoside.
Fer
O
OH
O
HO
HO
O
O
O
O
CH OH
2
O
CH OH
2
OH
OH
OH
CH
OH
O
3
O
OH
1
OH
Kaempferol-3-O-β-neohesperidoside-7-O-[2-O-(trans-feruloyl)]-β-D-glucopyranoside. UV (MeOH, λ , nm):
max
253, 268 sh., 300, 320 sh., 355; +NaOH: 263, 269, 296, 370 sh., 395; +AlCl : 264, 295, 300, 322, 354, 391: +AlCl + HCl:
3
3
267, 294, 299, 316, 354, 390; +AcONa: 269 sh., 299, 315, 360. Spectral ratios (HPLC, conditions A, λ , nm/λ , nm): 0.58
1
2
(280/360), 0.65 (300/360), 0.78 (320/360), 0.91 (340/360). Hydrolysis by HCl (2 M, 2 h) produced kaempferol and ferulic acid
(HPTLC, solvent system 1) in addition to glucose and rhamnose in a 2:1 ratio (HPTLC/densitometry, solvent system 2). Table
13
1 lists the PMR spectrum (500 MHz, DMSO-d ) and C NMR spectrum (125.7 MHz, DMSO-d ).
6
6
1) Central Siberian Botanical Garden, Siberian Branch, Russian Academy of Sciences, 630090, Novosibirsk-90,
ul. Zolotodolinskaya, 101, fax: (83832) 30 19 86, e-mail:inessa@csbg.nsc.ru; 2) Institute ofGeneral and Experimental Biology,
Siberian Branch, Russian Academy of Sciences, 670047, Ulan-Ude, ul. Sakh′yanovoi, 6, fax: (83012) 43 30 34, e-mail:
oldaniil@rambler.ru. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 621-622, November-December, 2008.
Original article submitted June 25, 2008.
0009-3130/08/4406-0769 ©2008 Springer Science+Business Media, Inc.
769

TABLE 1. PMR and 13C NMR Spectra of 1
C atom
δH (ppm, J/Hz)
δC (ppm)
C atom
δH (ppm, J/Hz)
δC (ppm)
2
3
4
5
6
7
8
-
-
-
-
159.01 s
135.05 s
178.90 s
162.95 s
101.03 d
163.84 s
95.65 d
Rha
1
2
3
4
5
6
5.18 br.s
3.80 s
4.00 s
3.34 s
4.10 s
104.57 d
72.38 d
71.29 d
75.00 d
69.95 d
17.97 q
6.40 (d, J = 2.5)
-
6.80 (d, J = 2.5)
1.00 (d, J = 6.5)
9
10
1′
2′
3′
4′
5′
6′
-
-
-
158.08 s
106.20 s
123.32 s
132.00 d
116.32 d
166.87 s
16.32 d
7-O-Glc
1
2
3
4
5
6
Fer
5.40 (d, J = 8.0)
5.15 m
3.78 (dd, J = 10.0, 10.0)
3.54 (dd, J = 10.0, 10.0)
3.69 (dd, J = 10.0, 7.0)
2.72 (AB, J = 12.0, 2.0)
98.35 d
74.68 d
72.38 d
71.30 d
78.31 d
62.50 d
8.08 (d, J = 9.0)
6.90 (d, J = 9.0)
-
6.90 (d, J = 9.0)
8.08 (d, J = 9.0)
132.00 d
3-O-Glc
1
2
3
4
5
6
7
8
-
7.81 (d, J = 3.0)
7.80 (d, J = 8.0)
-
125.22 s
131.72 d
157.61 s
161.92 s
116.89 d
131.90 d
148.64 d
115.91 d
168.81 s
57.12 q
1
2
3
4
5
6
5.63 (d, J = 7.0)
3.69 (dd, J = 10.0, 7.0)
3.56 (dd, J = 10.0, 7.0)
3.30 (dd, J = 10.0, 7.0)
3.22 (d, J = 6.0)
100.72 d
80.54 d
78.22 d
72.14 d
77.89 d
62.53 t
7.80 (d, J = 8.0)
6.78 (dd, J = 8.0, 3.0)
7.70 (d, J = 17.5)
6.51 (d, J = 17.5)
-
3.60 (AB, J = 12.0, 6.0)
9
CH3O
3.84 s
HPTLCwasperformedon Sorbfil PTSKh-AF-Vplates. Solventsystemsweretoluene:ethylacetate:HCOOH(1, 20:11:3)
and -PrOH:CHCl :H O (2, 7:4:1). Chromatograms were developed twice to heights of 4 and 8 cm. Flavonoids in
i
3
2
chromatograms were detected by AlCl (5%); phenolic acids, by NH vapor and UV; carbohydrates, by anilinium phthalate.
3
3
HPLC conditions: A, Milikhrom A-02 liquid chromatograph, Nucleosil C18 column (2 × 75 mm, 5 μm particle size),
mobile phase TFA (0.1%) in CH CN, flow rate 150 μL/min, UV detector (λ = 220, 254, 360 nm); B, Waters 600E liquid
3
chromatograph, Lichrospher RP-18 column (4.6 × 200 mm, 5 μm particle size), mobile phase CH CN gradient in water
3
10%→50%, UV detector (λ = 310 nm).
The total content of flavonoids in the aerial part of
was 0.77% of the mass of air-dried raw material
A. senescens
(differential spectrophotometry[5]). According toHPLC (conditions A), 1 was the main component of the phenolic compounds
(0.11-0.19% of the air-dried mass of raw material).
Kaempferol-3- -β-neohesperidoside-7- -[2- -(
-feruloyl)]-β-D-glucopyranoside (1) was observed previouslyin
O
O
O trans
the aerial part of
[6] and
[7] and was isolated for the first time from
.
A. senescens
A. ursinum
A. neapolitanum
REFERENCES
1.
2.
3.
4.
5.
6.
7.
T. A. Aseeva and Ts. A. Naidakova,
[in Russian], Ulan-Ude (1983).
Food Plants in Tibetan Medicine
I. Yu. Selyutina,
, 2, 79 (2007).
Sib. Bot. Vestn.
K. Samikov, R. Shakirov, T. P. Antsupova, and S. Yu. Yunusov,
Khim. Prir. Soedin.
T. Inoue, Y. Mitaki, Y. Sashida, A. Nishino, Y. Samoti, and H. Nishino,
, 383 (1986).
, 40, 521 (1995).
Phytochemistry
, No. 2, Moscow (1990).
USSR State Pharmacopeia
A. Carotenuto, V. de Feo, E. Fattorusso, V. Lanzotti, S. Magno, and C. Cicala,
A. Carotenuto, E. Fattorusso, V. Lanzotti, S. Magno, V. de Feo, and C. Cicala,
, 41, 531 (1996).
, 44, 949 (1997).
Phytochemistry
Phytochemistry
770