Chemistry of Natural Compounds, Vol. 38, No. 6, 2002
FLAVONOIDS OF THE AERIAL PART OF Lycopus lucidus
A. Malik,1 M. P. Yuldashev,2 A. Obid,1
T. Ismoil,1 and L. Ya. Ping1
UDC 547.972
In continuation ofresearch on flavonoids of
L. plants, we studied the phenolic components of
Turcz.
L. lucidus
Lycopus
ex Benth (shinybugle weed). Chrysoeriol, luteolin, quercetin, cinaroside, andquercimeritrin havepreviouslybeen isolated from
the ethylacetate fraction of its aerial part [1].
Chromatography of the butanol fraction (42.0 g) over a silica-gel column using a CHCl —CH OH gradient (95:5-
3
3
80:20) produced luteolin, quercetin, cinaroside, and flavonoids 1-3. The isolated flavonoids were identified using UV, IR, mass
and PMR spectra in addition to chemical transformations and comparison with authentic samples.
Thermopsoside (1)(chrysoeriol-7-O-β-D-glucoside), C22H22O11, mp173-175°C. UVspectrum (EtOH, λmax, nm): 255,
269, 349. IR spectrum: 3460-3270 cm-1 (OH); 2930 (methoxy); 1665 (carbonyl γ-pyrone); 1615, 1505 (aromatic C=C); and
1090, 1035 (C–O glycoside).
PMR spectrum (300 MHz, DMSO-d + CCl , δ, ppm, J/Hz): 3.05-3.85 (sugar), 3.95 (3H, s, OCH ), 5.00 (1H, d,
6
4
3
J = 7.0, H-1″), 6.45 (1H, d, J = 2.0, H-6), 6.65 (1H, d, J = 2.0, H-8), 6.80 (1H, s, H-3), 6.95 (1H, d, J = 8.0, H-5′), 7.48 (1H, dd,
J = 2.0, J = 8.0, H-6′), 7.80 (1H, d, J = 2.0, H-2′), 9.25 (1H, br.s, 4′-OH), 12.85 (1H, s, 5-OH).
+
Acidhydrolysis of1 produced chrysoeriol (5,7,4′-trihydroxy-3′-methoxyflavone, C16H12O6, mp 335-337 C, [M] 300)
and D-glucose [2-4].
Isoquercitrin (2) (quercetin-3-O-β-D-glucoside), C21H20O12, mp 236-238°C. UV spectrum (EtOH, max, nm): 255,
265 sh, 360; +CH COONa, 272, 378; +CH COONa/H BO , 260, 374; +AlCl , 272, 434; +AlCl /HCl, 267, 402; +CH ONa,
3
3
3
3
3
3
3
271, 410.
IR spectrum: 3350, 3450 (OH); 1665 (carbonyl γ-pyrone); 1590, 1550, 1510 (aromatic C=C); and 1095, 1045, 1020
(C–O glycoside).
PMR spectrum (300 MHz, DMSO-d + CCl , δ, ppm, J/Hz): 3.05-3.90 (sugar), 5.15 (1H, d, J = 7.0, H-1″), 6.15 (1H,
6
4
d, J = 2.0, H-6), 6.35 (1H, d, J = 2.0, H-8), 6.85 (1H, d, J = 8.0, H-5′), 7.55 (2H, dd, J = 2.0, J = 8.0, H-2′, H-6′), 12.45 (1H, s,
5-OH).
+
Acid hydrolysis produced quercetin (3,5,7,3 ,4 -pentahydroxyflavone, C15H10O7, mp 312-314°C, [M] 302) and
D-glucose.
Acetylation of 2 by acetic anhydride in pyridine isolated the octaacetyl derivative with mp 200-202°C, the mass
spectrum of which contained a peak for the molecular ion with m/z 770 and strong peaks for fragment ions of the
tetraacetylhexose with m/z 331, 271, 229, and 169 [2, 3, 5].
Rutin (3) (quercetin-3-O-rutinoside), C27H30O16, mp 193-195°C. UV spectrum (EtOH, λmax, nm): 259, 267 sh, 360,
+CH COONa, 271, 390; +CH COONa/H BO , 260, 383; +AlCl , 273, 430; +AlCl /HCl, 270, 401; +CH ONa, 272, 411.
3
3
3
3
3
3
3
PMR spectrum (300 MHz, DMSO-d + CCl , , ppm, J/Hz): 1.12 (3H, d, J = 6.0, CH ), 3.00-4.20 (sugar), 5.03 (1H,
6
4
3
br.s, H-1″′), 5.23 (1H, d, J = 7.0, H-1″), 6.16 (1H, d, J = 2.0, H-6), 6.36 (1H, d, J = 2.0, H-8), 6.83 (1H, d, J = 8.0, H-5′), 7.53
(2H, dd, J = 2.0, J = 8.0, H-2′, H-6′), 12.46 (1H, s, 5-OH).
Acid hydrolysis of 3 produced quercetin, D-glucose, and L-rhamnose; partial hydrolysis (90% formic acid in
cyclohexanol), isoquercetin [2, 3, 5].
Flavonoids 1-3 were isolated from L. lucidus for the first time.
1) Xinjiang University, Urumchi, PRC; 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. Translated from Khimiya Prirodnykh Soedinenii,
No. 6, p. 486, November-December, 2002. Original article submitted December 16, 2002.
0009-3130/02/3806-0612$27.00 ©2002 Plenum Publishing Corporation
612
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