Flavonoids from physospermum acteaefolium

Full text of DOI:10.1007/s10600-012-0281-6

Chemistry of Natural Compounds, Vol. 48, No. 3, July, 2012 [Russian original No. 3, May–June, 2012]
FLAVONOIDS FROM Physospermum acteaefolium
1
1
Reguia Bencheraiet, Ahmed Kabouche,
UDC 547.972
1*
2
Zahia Kabouche, Rachid Touzani,
3
and Maurice Jay
The genus Physospermum (Apiaceae) comprises some 16 species. Cytotoxic triterpene saponins have recently been
isolated from the roots of Physospermum verticillatum, the single reported species [1]. Two Physospermum species, P. acteaefolium
Presl. and P. cornubiense, which is used to flavor sweet foods, grow in Algeria [2].
The aerial parts of Physospermum acteaefolium Presl. were collected on May 2008 in the region of the Babors
Mountains [2]. A voucher specimen was deposited in the Herbarium of the Laboratory of Therapeutic Substances (LOST) at
Mentouri University (LOST.Pa.05.06).
Air-dried and powdered aerial parts (800 g) of Physospermum acteaefolium were extracted with 70% MeOH. The
residue was dissolved in boiling water and extracted with ethyl acetate and n-BuOH, successively. The butanolic extract 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) and TLC on polyamid DC6, eluted
2
with H O–MeOH–metylethylketone–acetylacetone (13:3:3:1), followed by column flash chromatography over Sephadex LH-20
2
1
13
in MeOH, led to seven compounds 1–7, which were identified using UV, H NMR, C NMR, and MS analysis [3, 4].
Acid Hydrolysis. The pure compounds were treated with 2 M HCl at 100ꢁC 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 impregnated
with 0.2 M NaH PO , solvent Me CO–H O (9:1), revealed with aniline malonate.
2
4
2
2
Compound 1. C H O , yellow powder (acetone), mp 278–279ꢁC. UV (MeOH, ꢂ , nm): 266, 322 sh, 366.
15 10
6
max
Characterized as kaempferol [3, 4].
Compound 2. C H O , yellow needles (acetone), mp >300ꢁC. UV (MeOH, ꢂ , nm): 375, 265. Characterized as
15 10
7
max
quercetin [3, 4].
Compound 3. C H O , mp 232–233ꢁC. UV (MeOH, ꢂ , nm): 370, 258. Characterized as kaempferol
21 20 10
max
7-O-rhamnoside [3–5].
Compound 4. C H O , yellow crystals, mp 184–185ꢁC. UV (MeOH, ꢂ , nm): 350, 256. Characterized as
21 20 11
max
quercetin 7-O-rhamnoside [3, 4, 6].
Compound 5. C H O , yellow amorphous powder, mp > 300ꢁC. UV (MeOH, ꢂ , nm): 263, 343; + NaOAc:
27 30 14
max
263, 393; + NaOAc/H BO : 265, 345; +AlCl : 277, 295 (sh), 345; + AlCl /HCl: 270, 290 (sh), 340, 393; + NaOMe: 271, 399
3
3
3
3
+ 1
(increase in intensity). Positive FAB-MS m/z 579 [M + 1] . H NMR (400 MHz, DMSO-d , ꢃ, ppm, J/Hz): 6.47 (d, J = 2.1,
6
H-6), 6.84 (d, J = 2.1, H-8), 7.83 (d, J = 9.1, H-2ꢀ, H-6ꢀ), 6.97 (d, J = 9.1, H-3ꢀ, H-5ꢀ), 5.56 (d, J = 2.1, H-1ꢀꢀ Rha-1), 5.31 (d,
J = 2.1, H-1ꢀꢀꢀ Rha-2), 3.05–3.92 (sugar protons), 1.16 (d, J = 6.3, CH -Rha-1), 0.83 (d, J = 6.4, CH -Rha-2). Acid hydrolysis
3
3
of 5 gave kaempferol and L-rhamnose. Compound 6 was identified as kaempferol 3,7-dirhamnoside [5].
1) Universite Mentouri, Constantine, Laboratoire dꢀObtention de Substances Therapeutiques (L.O.S.T), Campus
Chaabat Ersas, 25000 Constantine, Algeria, fax: 212 31818859, e-mail: zkabouche@yahoo.com; 2) Universite Mohamed
Premier, LCAE-URAC 18; COSTE; Faculte des Sciences, Oujda & Faculte Pluridisciplinaire Nador, Morocco; 3) Laboratoire
de Biologie Moleculaire et Phytochimie, Universite Claude Bernard, Lyon, France. Published in Khimiya Prirodnykh Soedinenii,
No. 3, May–June, 2012, pp. 432–433. Original article submitted February 11, 2011.
480
0009-3130/12/4803-0480 02012 Springer Science+Business Media, Inc.

Compound 6. C H O , yellow amorphous powder, mp 197–199ꢁC. UV (MeOH, ꢂ , nm): 268, 348; + NaOH:
27 30 17
max
1
276, 402; + AlCl : 273, 328, 425; + AlCl /HCl: 275, 295, 353, 387; + NaOAc: 269, 350, 407. H NMR (400 MHz, DMSO-d ,
3
3
6
ꢃ, ppm, J/Hz): 7.51 (1H, dd, J = 8.5, 2.0, H-6ꢀ), 7.47 (1H, d, J = 2.0, H-2ꢀ), 6.83 (1H, d, J = 8.5, H-5ꢀ), 6.84 (1H, s, H-8), 6.62
(3H, s, H-6), 4.84 (1H, d, J = 8.2, H-1ꢀꢀ), 4.66 (1H, d, J = 7.8, H-1ꢀꢀꢀ), 3.05–3.90 (sugar protons). Acid hydrolysis of 6 gave
quercetin and D-glucose. Compound 6 was identified as quercetin 3,7-diglucoside [7].
Compound 7. C O H , yellow needles, mp 226–228ꢁC. UV (MeOH, ꢂ , nm): 245 sh, 266, 318 sh, 352; + AlC1 :
33 20 40
max
3
256 sh, 275, 302, 356, 400; + AlCl /HC1): 275, 300 sh, 350, 400; + NaOMe: 245, 270, 300 sh, 350 sh, 390; + NaOAc: 267,
3
+
+ 1
320 sh, 360, 405 sh; + NaOAc/H BO : 266, 320 sh, 353. Positive FAB-MS: m/z 779 [M + Na] , 757 [M + H] . H NMR
3
3
(400 MHz, DMSO-d , ꢃ, ppm, J/Hz): 6.42 (1H, d, J = 1.8, H-6), 6.75 (1H, d, J = 1.8, H-8), 8.15 (2H, d, J = 8.9, H-2ꢀ, H-6ꢀ),
6
6.85 (2H, d, J = 8.9, H-3ꢀ, H-5ꢀ), 5.70 (1H, d, J = 7.5, H-1ꢀꢀ Gal), 5.20 (1H, d, J = 6.8, H-1ꢀꢀꢀ Rha), 5.15 (1H, d, J = 7.8, H-1ꢀꢀꢀꢀ
Glc), 3.10–3.90 (sugar protons), 0.82 (d, J = 6.5, CH -Rha).
3
13
C NMR (100 MHz, DMSO-d , ꢃ, ppm): 156.4 (C-2), 134.4 (C-3), 178.1 (C-4), 161.4 (C-5), 100.0 (C-6), 161.8
6
(C-7), 95.1 (C-8), 156.4 (C-9), 105.1 (C-10), 120.9 (C-1ꢀ), 131.3 (C-2ꢀ, C-6ꢀ), 115.8 (C-3ꢀ, C-5ꢀ), 161.7 (C-4ꢀ), 99.1 (C-1ꢀꢀ Gal),
77.1 (C-2ꢀꢀ Gal), 76.7 (C-3ꢀꢀ Gal), 68.4 (C-4ꢀꢀ Gal), 78.1 (C-5ꢀꢀ Gal), 60.5 (C-6ꢀꢀ Gal), 101.4 (C-1ꢀꢀꢀ Rha), 71.8 (C-2ꢀꢀꢀ Rha),
71.7 (C-3ꢀꢀꢀ Rha), 72.7 (C-4ꢀꢀꢀ Rha), 69.9 (C-5ꢀꢀꢀ Rha), 18.2 (CH Rha), 100.1 (C-1ꢀꢀꢀꢀ Glc), 73.8 (C-2ꢀꢀꢀꢀ Glc), 78.9
3
(C-3ꢀꢀꢀꢀ Glc), 71.1 (C-4ꢀꢀꢀꢀ Glc), 77.5 (C-5ꢀꢀꢀꢀ Glc), 61.2 (C-6ꢀꢀꢀꢀ Glc) [8]. Acid hydrolysis of 7 gave kaempferol, D-galactose,
L-rhamnose, and D-glucose. Compound 7 was identified as kaempferol-3-O-ꢄ-D-glucosyl(1ꢅ2)-ꢄ-D-galactoside 7-O- -L-
rhamnoside [8].
Compounds 1–7 are reported for the first time from the genus Physospermum. Compound 7 is reported for the second
time from a natural source.
ACKNOWLEDGMENT
The authors thank the ANDRS and MESRS (DG/RSDT), Algeria for financial support.
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