Chemistry of Natural Compounds, Vol. 48, No. 3, July, 2012 [Russian original No. 3, May–June, 2012]
COMPONENTS OF Matricaria pubescens FROM ALGERIAN
SEPTENTRIONAL SAHARA
1
1
2
O. Gherboudj, N. Benkiki, E. Seguin,
UDC 547.972
3
1*
F. Tillequin, and Z. Kabouche
The air-dried aerial parts (1200 g) of Matricaria pubescens (Desf.) Schultz, collected during flowering (April 2008)
at Ghardaia (Algerian Septentrional Sahara), were macerated at room temperature in a methanol solution (70%). The extract
was concentred under low pressure, diluted and filtered to remove chlorophyll, then successively extracted with petroleum
ether, dichloromethane, ethyl acetate, and n-butanol.
The butanolic extract (10 g) was column chromatographed on polyamid SC6, eluted with toluene–methanol with
increasing polarity. Whatman 3MM paper chromatography using 15%AcOH and BAW (n-BuOH–AcOH–H O, 4:1:5; upper phase)
2
and TLC on polyamid DC6, eluted with H O–MeOH–methylethylketone–acetylacetone (13:3:3:1) followed by column flash
2
chromatography over Sephadex LH-20 in MeOH, led to four pure flavonoids (1–6).
The dichloromethane extract (8 g) was column chromatographed on silica gel (35–70 ꢁm), eluted with petroleum
ether–ethyl acetate with increasing polarity and then with methanol.
The major fraction was chromatographed on a silica gel column (20–45 mm), eluted with cyclohexane–ethyl acetate
with increasing polarity. Further, TLC using silica gel plates, eluted with cyclohexane–ethyl acetate, led to compounds 7–9.
1
13
All compounds were identified by H NMR, C NMR, EI-MS, and UV analytical methods and acid hydrolysis.
Acid Hydrolysis. Compounds 4–6 were treated with 2M HCl at 100ꢂC for 1 h. The hydrolysates were extracted with
EtOAc, and the aglycones were identified by their UV spectra in methanol and by comparison of their R with authentic
f
samples. Sugars were identified in the aqueous residue by comparison with authentic samples on silica gel TLC plates
impregnated with 0.2 M NaH PO , solvent Me CO–H O (9:1), and revealed with aniline malonate.
2
4
2
2
Compound 1, C H O , mp 345ꢂC, identified as apigenin [1].
1
5 10 5
Compound 2, C H O , mp 330ꢂC, identified as luteolin [2].
1
5 10 6
Compound 3, C H O , yellow needles (acetone), mp >300ꢂC, identified as quercetin [3].
1
5 10 7
Compound 4, C H O , mp 220–222ꢂC, identified as apigenin 7-O-glucoside [4].
2
1 20 10
Compound 5, C H O , mp 239–242ꢂC, identified as luteolin 7-O-glucoside [5].
2
1 20 11
Compound 6, mp 218–212ꢂC, identified as quercetin 3-O-glucoside [6].
Compound 7, C H O , mp 115–117ꢂC (diethyl ether). UV spectrum (MeOH, ꢃmax, nm, log ꢄ): 203.4 (1.332), 204
1
0 8 3
–
1
(
1.903), 214 (1.191), 322 (1.162). IR (KBr, ꢅmax, cm ): 1707 (CO), 2840 (OCH ), 1613 (aromatic ring). PMR (500 MHz,
3
CDCl , ꢆ, ppm, J/Hz): 7.65 (1H, d, J = 10, H-4), 7.35 (1H, d, J = 10, H-5), 6.85 (1H, d, J = 2, H-6), 6.75 (1H, dd, J = 8 and 2,
3
13
H-8), 6.25 (1H, d, J = 10, H-3), 3.85 (3H, s, OCH3). C NMR (500 MHz, CDCl , ꢆ, ppm): 161.1 (C-2), 113.1 (C-3), 143.4 (C-4),
3
1
28.7 (C-5), 112.6 (C-6), 162.8 (C-7), 100.9 (C-8), 155.9 (C-9), 11.5 (C-10), 55.7 (OCH ). Mass spectrum (DiC, NH ),
3 3
+
m/z 177 [M – H] . Characterized as herniarin [7].
1
) Laboratoire dꢀObtention de Substances Therapeutiques (L.O.S.T), Faculte des Sciences, Universite Mentouri-
Constantine, Campus Chaabat Ersas, 25000, Constantine, Algerie, fax: 213 31 81 88 59, e-mail: zkabouche@yahoo.com;
) Equipe Pharmacomodulation dꢀAntitumoraux dꢀOrigine Naturelle et Synthetique, Laboratoire de Pharmacognosie, Faculte
2
de Pharmacie, 22, Boulevard Gambetta, F-76183 Rouen Cedex 1, France; 3) Laboratoire de Pharmacognosie de lꢀUniversite
Rene Descartes, U.M.R./C.N.R.S. N 8638, Faculte des Sciences Pharmaceutiques et Biologiques, 4 Avenue de lꢀObservatoire,
F-75006 Paris, France. Published in Khimiya Prirodnykh Soedinenii, No. 3, May–June, 2012, pp. 423–424. Original article
submitted July 14, 2010.
0
470
0009-3130/12/4803-0470 2012 Springer Science+Business Media, Inc.
Gherboudj
