Flavonoids of Haplophyllum foliosum and H. pedicellatum

Full text of DOI:10.1023/A:1012546830140

Chemistry of Natural Compounds, Vol. 37, No. 3, 2001
FLAVONOIDS OF Haplophyllum foliosum AND H. pedicellatum
M. P. Yuldashev
UDC 547.972
In continuation of the study of flavonoids from plants of the Haplophyllum A. Juss. genus, we studied the aerial part
of H. foliosum Vved. [1, 2]. Previously several alkaloids were isolated from its subterranean part [2, 3].
Ground air-dried raw material (1.4 kg) collected during flowering (June 1981) in Kugart (Fergana range, Dzhalalabad
District, Republic of Kyrgyzstan) was exhaustively extracted with ethanol at room temperature. The combined extracts were
evaporated in vacua. The condensed residue was treated with water and then worked up with CHCl and ethylacetate. Solvents
3
were evaporated to yield 28.0 g (CHCl ) and 20.0 g (ethylacetate) of solid.
3
The ethylacetate fraction was chromatographed over a silica-gel column using gradient elution by CHCl —CH OH
3
3
(
97:3-85:15). Compounds 1-3 were isolated. They were identified using UV, mass, and PMR spectra in addition to chemical
transformations and comparison with authentic samples.
Isorhamnetin (1). (3,5,7,4 -tetrahydroxy-3 -methoxyflavone) C H O (M 316), mp 305-307 C, UV spectrum
+
o
1
6 12 7
(EtOH, max, nm): 256, 266, 372.
PMR spectrum (100 MHz, C D N, , ppm, J/Hz): 3.87 (3H, s, OCH ), 6.09 (1H, d, J = 2.5, H-6), 6.44 (1H, d, J = 2.5,
5
5
3
H-8), 6.85 (1H, d, J = 8.5, H-5 ), 7.55 (1H, d, J = 2.5, H-2 ), 7.62 (1H, dd, J = 2.5, J = 8.5, H-6 ) [4, 5].
o
Limocitrin-7-O- -D-(6 -O-acetyl)glucoside (2). C H O , mp 231-233 C, UV spectrum (EtOH, max, nm): 260,
2
5 26 14
-1
2
76 sh, 338 sh, 379. IR spectrum (cm ): 3360-3600 (OH), 2936 (OCH ), 1734 (ester carbonyl), 1654 ( -pyrone carbonyl), 1606,
3
1
564, and 1523 (aromatic C C), 1104-1005 (glycoside C–O).
PMR spectrum (100 MHz, C D N, , ppm, J/Hz): 2.05 (3H, s, OCOCH ), 3.84 (3H, s, OCH ), 4.01 (3H, s, OCH ),
5
5
3
3
3
3.90-4.30 (sugar protons), 5.66 (1H, d, J = 7.5, H-1 ), 7.06 (1H, s, H-6), 7.25 (1H, d, J = 8.0, H-5 ), 8.20 (1H, br.s, H-2 ), 8.25
(
1H, dd, J = 2.0, J = 8.0, H-6 ).
Acid hydrolysis of 2 afforded limocitrin (3,5,7,4 -tetrahydroxy-8,3 -dimethoxyflavone) and D-glucose.
o
Acetylation of 2 by acetic anhydride in pyridine gave a heptaacetyl derivative with mp 113-115 C, the mass spectrum
of which gave a molecular ion with m/z 760 [M - 42] and strong peaks for fragments of tetraacetylhexoses with m/z 331, 271,
29, and 169 [6].
Haploside C (3) (7-O-[ -L-rhamnopyranosyl(1 2)- -D-(6 -O-acetyl)-glucopyranosyl)]-3,5,4 -trihydroxy-8,3 -
2
o
dimethoxyflavone): C H O , mp 142-144 C, UV spectrum (EtOH, max, nm): 260, 275 sh, 384.
3
1 36 18
PMR spectrum (100 MHz, C D N, , ppm, J/Hz): 1.75 (3H, d, J = 6.0, CH ), 2.03 (3H, s, OCOCH ), 3.76-4.95 (sugar
5
5
3
3
protons), 3.88 (3H, s, OCH ), 4.13 (3H, s, OCH ), 5.63 (1H, d, J = 7.0, H-1 ), 6.96 (1H, s, H-6), 7.30 (1H, d, J = 8.5, H-5 ),
3
3
8
.22 (1H, br.s, H-2 ), 8.26 (1H, dd, J = 2.0, J = 8.5, H-6 ).
Acid hydrolysis of 3 gave limocitrin, D-glucose, and L-rhamnose.
o
Acetylation of 3 by acetic anhydride in pyridine gave a nonoacetyl derivative with mp 191-194 C, the mass spectrum
+
of which gave a molecular ion with m/z 990 [M - 42] and strong peaks for fragments of acylated biose with m/z 561 and
terminal rhamnose with m/z 273, 213, and 153 [7].
Flavonoids 1-3 from H. foliosum were isolated for the first time.
The dried and ground subterranean part (0.9 kg) of H. pedicellatum Bunge collected at the start of flowering (June 10,
1
980) near Bairamali, Republic of Turkmenistan [1, 2], was exhaustively extracted with ethanol (95%). The alcohol was
evaporated in vacua. The aqueous residue was purified of lipophilic substances by treatment with CHCl . Flavonoids were
3
extracted with ethylacetate to yield 35.0 g of product that was separated on a silica-gel column with gradient elution by
CHCl —CH OH (97:3-85:15). Compounds 4 and 5 and haploside C were isolated.
3
3
S. Yu. Yunusov Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan,
Tashkent, fax (99871) 120 64 75. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 245-246, May-June, 2001.
Original article submitted July 2, 2001.
©
0
009-3130/01/3703-0288$25.00 2001 Plenum Publishing Corporation
2
88

o
Haploside A (4) [haplogenin-7-O- -D-(6 -O-acetyl)-glucoside], C H O , mp 193-195 C, UV spectrum (EtOH,
2
4 24 14
-1
max, nm): 262, 280 sh, 343, 387. IR spectrum (cm ): 3210-3540 (OH), 1725 (ester carbonyl), 1653 ( -pyrone carbonyl), 1615,
608, 1565, and 1514 (aromatic C C), and 1094, 1047, 1025, and 1000 (glycoside C–O).
1
4
PMR spectrum (100 MHz, C D N, , ppm, J/Hz): 1.94 (3H, s, OCOCH ), 3.70 (3H, s, OCH ), 3.72-4.93 (glucose),
5
5
3
3
.42-4.88 (m, Jgem = 12.0, 2H-6 ), 5.53 (1H, d, J = 7.0, H-1 ), 7.08 (1H, s, H-6), 7.17 (1H, d, J = 8.0, H-5 ), 8.24 (1H, dd,
J = 2.5, J = 8.0, H-6 ), 8.25 (1H, br.s, H-2 ).
Acid hydrolysis of 4 gave haplogenin (3,5,7,8,4 -pentahydroxy-3 -methoxyflavone) and D-glucose; alkaline hydrolysis,
haploside B [8].
o
Haploside B (5) (haplogenin-7-O- -D-glucoside), C H O , mp 212-213 C, UV spectrum (EtOH, max, nm): 261,
2
2 22 13
2
80 sh, 392. PMR spectrum (100 MHz, C D N, , ppm, J/Hz): 3.72 (3H, s, OCH ), 3.79-4.30 (glucose protons), 5.62 (1H, d,
5 5 3
J = 7.5, H-1 ), 6.95 (1H, s, H-6), 7.09 (1H, d, J = 8.5, H-5 ), 8.22 (1H, dd, J = 2.5, J = 8.5, H-6 ), 8.23 (1H, br.s, H-2 ).
Acid hydrolysis of 5 gave haplogenin and D-glucose [9].
Haplosides A, B, and C from H. pedicellatum were isolated for the first time.
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