Flavonoids from Cephalaria grossheimii

Full text of DOI:10.1007/s10600-009-9328-8

Chemistry of Natural Compounds, Vol. 45, No. 3, 2009
FLAVONOIDS FROM Cephalaria grossheimii
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1
2*
I. S. Movsumov, E. A. Garaev, and M. I. Isaev
UDC 547.944/945
We have continued research on chemical components from representatives of the family Dipsacaceae Lindl. (teasel)
[
1, 2], one species of which, Cephalaria grossheimii Bobr., is endemic to Azerbaidzhan [3]. According to Cherepanov [4], this
species is synonymous with C. kotschyi Boiss et Hoh. However, this contradicts the literature on the phytochemistry of these
plants. Thus, roots of C. kotschyi contained the alkaloids gentianine, gentianadine, and gentianaine [5] whereas alkaloids were
not observed in those of C. grossheimii.
Flowers of C. kotschyi contained the flavonoids kaempferol, hyperoside, quercimeritrin, cinaroside, cephaside, and
cephacoside [2]. The flavonoid composition of C. grossheimii has not been studied.
Therefore, we studied the flavonoid composition of C. grossheimii flowers. Flowers of this plant contained oleanolic
acid in addition to apigenin, hyperoside, quercimeritrin, cinaroside, and palustroside. It can be seen that the flavonoid composition
of flowers differed significantly for the two compared plants. The recent literature is consistent with this [6, 7].
Dry flowers of C. grossheimii (2 kg) that were collected near Rozgov, Lerik Region, Republic of Azerbaidzhan,
during full flowering (beginning of July 2007) were extracted with ethanol (96%, 1:8) for 1 d. The extract was decanted. The
extraction was repeated two more times using a fresh portion of ethanol (1:6) each time. The extracts were combined and
evaporated in a rotary evaporator (fraction 1). The processed raw material was extracted a fourth time with ethanol (80%, 1:8)
for 1 d. The extract was filtered and evaporated to a watery residue (fraction 2).
Fraction 1 was treated with water (300 mL), shaken, and extracted successively with CHCl , EtOAc:hexane, and
3
EtOAc.
Purification of the CHCl extract over Al O and recrystallization afforded oleanolic acid, C H O , mp 305-306°C
3
2
3
30 18 3
(
EtOH), [α]20 +79 ± 2° (c 1.2, MeOH). The crystals were white; soluble in alcohols, CHCl , and Py; and insoluble in H O.
D
3 2
The EtOAc:hexane extract was evaporated. Recrystallization from aqueous EtOH gave apigenin, C H O ,
1
5 10 5
mp 342-343°C. The crystals were light-yellow, soluble in alcohols, and insoluble in H O.
2
The EtOAc extract was dried over Na SO and evaporated to dryness. The solid was dissolved in MeOH (50 mL)
2
4
and left at room temperature for 2 d. The resulting crystals were filtered off and recrystallized from MeOH to afford hyperoside,
C H O , mp 230-232°C. UV spectrum (λ , MeOH, nm): 361, 305 sh, 277; +AlCl : 434, 342 sh, 275. Light-yellow
2
1
20 12
max
3
crystalline powder, soluble in alcohols and DMF, insoluble in CHCl . Acid hydrolysis produced quercetin (64%) and
3
D-galactose.
The mother liquor was evaporated to dryness. Recrystallization of the solid from acetone afforded quercimeritrin,
2
0
C H O , mp 250-252°C, [α] −58 ± 2° (c 0.3, Py:MeOH). UV spectrum (λmax, MeOH, nm): 370, 256; +CH COONa:
2
1
20 12
D
3
3
50, 256. Acid hydrolysis produced quercetin (65%) and D-glucose.
The acetone solution was evaporated to dryness. Recrystallization of the solid from aqueous EtOH afforded cinaroside,
C H O , mp 230-232°C. UV spectrum (λ , EtOH, nm): 352, 266 sh, 256; +CH COONa: 352, 268 sh, 258. Acid
2
1
20 11
max
3
hydrolysis produced luteolin (66%) and D-glucose.
A precipitate that formed in fraction 2 after 1 d was filtered off. The filtrate was evaporated to a small volume and
extracted with n-BuOH. The extract was evaporated. Recrystallization of the solid from aqueous EtOH afforded palustroside,
2
0
C H O , mp 172-173°C, [α] −50 ± 2° (c 0.3, DMF), soluble in DMF and aqueous alcohols, slightly soluble in EtOH,
2
7
30 15
D
insoluble in EtOAc [8].
1
) Azerbaidzhan Medical University, Baku, e-mail: eldargar@mail.ru; 2) S. Yu. Yunusov Institute of the Chemistry
of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax: (99871) 120 64 75,
e-mail: m_isaev@rambler.ru. Translated from Khimiya Prirodnykh Soedinenii, No. 3, p. 359, May-June 2009. Original
article submitted December 29, 2008.
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0009-3130/09/4503-0422 ©2009 Springer Science+Business Media, Inc.

The isolated compounds were identified by comparison with authentic samples and using PMR and 13C NMR spectra
obtained on a Bruker AM-300 spectrometer.
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.
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[
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A. M. Aliev, I. S. Movsumov, and E. Kh. Batirov, Khim. Prir. Soedin., 667 (1975).
O. Emiagaoglu and R. Ansin, Turk. J. Bot., 27, 1 (2003).
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