Kaempferol and quercetin flavonoids from Rosa rugosa

Full text of DOI:10.1007/s10600-006-0267-3

Chemistry of Natural Compounds, Vol. 42, No. 6, 2006
KAEMPFEROL AND QUERCETIN FLAVONOIDS FROM Rosa rugosa
Z. P. Xiao,1,2 H. K. Wu,1,2 T. Wu,1,2 H. Shi,1,2 B. Hang,1 and H. A. Aisa1*
UDC 547.972
The Chinese plant
Thunb. is known to be an antioxidant and a good natural source of antioxidants [1].
Rosa rugosa
Therefore, we investigated the chemical composition of flowers of
(PRC).
Thunb. collected in Xinjiang Autonomous region
R. rugosa
Dry raw material (5 kg) was extracted with ethanol (70%). The alcohol extract was concentrated in vacuo and
fractionated over a column packed with large-pore ion-exchange resin with elution bywater and aqueous alcohol (25 and 50%).
The alcohol fractions were rechromatographed over polyamide, silica gel, and Sephadex LH-20 toafford 1-9, of which four were
kaempferol flavonoids, four were quercetin flavonoids, and one was a phenylethylglycoside. The aqueous fraction was extracted
with ethylacetate and chromatographed over silica gel to isolate two acidic phenolic compounds 10 and 11.
Kaempferol (1), yellowpowder (acetone), mp 278-279°C. UV spectrum (λ , MeOH, nm): 266, 322sh, 366; +AlCl :
3
max
270, 305sh, 350sh, 424; +AlCl /HCl: 270, 305sh, 347sh, 424.
3
PMR spectrum (400 MHz, acetone-d , δ, ppm, J/Hz): 8.16 (2H, d, J = 8.8, H-2′,6′), 7.03 (2H, d, J = 8.8, H-3′,5′), 6.54
6
(1H, d, J = 2.0, H-8), 6.27 (1H, d, J = 2.0, H-6).
13
C NMR spectrum (400 MHz, acetone-d , δ, ppm): 146.9 (C-2), 136.5 (C-3), 176.5 (C-4), 157.7 (C-5), 98.9 (C-6),
6
165.0 (C-7), 94.3 (C-8), 160.1 (C-9), 103.9 (C-10), 123.1 (C-1′), 130.3 (C-2′,6′), 116.1 (C-3′,5′), 161.9 (C-4′) [2].
Quercetin (2), yellow needles (acetone), mp >300°C. UV spectrum (λ , MeOH, nm): 256, 374; +AlCl : 271, 451;
3
max
+AlCl /HCl: 266, 302sh, 361sh, 427.
3
PMR spectrum (400 MHz, acetone-d , δ, ppm, J/Hz): 7.81 (1H, br.s, H-2′), 7.70 (1H, d, J = 8.0, H-6′), 6.99 (1H, d,
6
J = 8.0, H-5′), 6.53 (1H, br.s, H-8), 6.27 (1H, br.s, H-6) [2].
Juglanin (3), light yellow powder (MeOH), mp 229-230°C. UV spectrum (λ , MeOH, nm): 266, 350; +AlCl : 274,
3
max
304sh, 351sh, 399; +AlCl /HCl: 276, 302sh, 346sh, 397.
3
PMR spectrum (400 MHz, CD OD, δ, ppm, J/Hz): 7.87 (2H, d, J = 7.2, H-2′,6′), 6.84 (2H, d, J = 7.2, H-3′,5′), 6.32
3
(1H, d, J = 2.0, H-8), 6.12 (1H, d, J = 2.0, H-6), 5.38 (1H, br.s, H-1′), 3.37-4.23 (sugar protons).
13
C NMRspectrum (400 MHz, CD OD, δ, ppm): 158.5 (C-2), 134.9 (C-3), 179.9 (C-4), 163.1 (C-5), 99.9 (C-6), 166.0
3
(C-7), 94.8 (C-8), 159.5 (C-9), 105.7 (C-10), 122.8 (C-1′), 132.0 (C-2′,6′), 116.5 (C-3′,5′), 161.6 (C-4′), 109.6 (C-1″), 83.4
(C-2″), 78.6 (C-3″), 88.0 (C-4″), 62.4 (C-5″). Acid hydrolysis of 3 gave kaempferol and arabinose [3].
Avicularin (4), yellow powder (MeOH), mp 200-201°C. UV spectrum (λ , MeOH, nm): 257, 300, 356; +AlCl :
3
max
275, 335sh, 432; +AlCl /HCl: 270, 297sh, 364sh, 401.
3
PMR spectrum (400 MHz, DMSO-d , δ, ppm, J/Hz): 12.6 (1H, br.s, 5-OH), 7.56 (1H, dd, J = 8.4, 2.4, H-6′), 7.48 (1H,
6
d, J = 2.4, H-2′), 6.86 (1H, d, J = 8.4, H-5′), 6.42 (1H, d, J = 2.0, H-8), 6.20 (1H, d, J = 2.0, H-6), 5.57 (1H, d, J = 1.2, H-1″),
3.25-4.15 (sugar protons).
13
C NMR spectrum (400 MHz, DMSO-d , δ, ppm): 156.8 (C-2), 133.3 (C-3), 177.5 (C-4), 160.8 (C-5), 98.5 (C-6),
6
164.2 (C-7), 93.5 (C-8), 156.3 (C-9), 103.7 (C-10), 120.8 (C-1′), 115.4 (C-2′), 144.8 (C-3′), 148.2 (C-4′), 115.3 (C-5′), 121.6
(C-6′), 107.6 (C-1″), 81.8 (C-2″), 76.6 (C-3″), 85.6 (C-4″), 60.4 (C-5″). Acid hydrolysis of 4 gave quercetin and
arabinose [3].
Astragalin (5), yellow needles (MeOH), mp 219-220°C. UV spectrum (λ , MeOH, nm): 266, 300sh, 351; +AlCl :
3
max
274, 304sh, 351sh, 397; +AlCl /HCl: 275, 302sh, 346sh, 396.
3
1)XinjiangTechnicalInstituteofPhysicsandChemistry, CAS, Urumqi830011, China, tel:+08609913835679, e-mail:
haji@ms.xjb.ac.cn; 2) Graduate University of the Chinese Academy of Sciences, Beijing 100049, China. Translated from
Khimiya Prirodnykh Soedinenii, No. 6, pp. 600-601, November-December, 2006. Original article submitted September 22,
2006.
0009-3130/06/4206-0736 ©2006 Springer Science+Business Media, Inc.
736

PMR spectrum (400 MHz, DMSO-d , δ, ppm, J/Hz): 12.6 (1H, br.s, 5-OH), 10.9 (1H, br.s, 7-OH), 10.2 (1H, br.s,
6
4′-OH), 8.05 (2H, d, J = 7.2, H-2′,6′), 6.89 (2H, d, J = 7.2, H-3′,5′), 6.46 (1H, d, J = 2.0, H-8), 6.23 (1H, d, J = 2.0, H-6), 5.47
(1H, d, J = 7.6, H-1″), 3.07-3.58 (sugar protons).
13
C NMR spectrum (400 MHz, DMSO-d , δ, ppm): 156.1 (C-2), 133.1 (C-3), 177.3 (C-4), 160.8 (C-5), 98.4 (C-6),
6
163.8 (C-7), 93.5 (C-8), 156.3 (C-9), 103.9 (C-10), 120.8 (C-1′), 130.8 (C-2′,6′), 115.0 (C-3′,5′), 159.7 (C-4′), 100.6 (C-1″),
74.0 (C-2″), 76.1 (C-3″), 69.6 (C-4″), 77.3 (C-5″), 60.6 (C-6″). Acid hydrolysis of 5 gave kaempferol and glucose [4].
Hyperoside (6), light yellow powder (MeOH), mp 234-236°C. UV spectrum (λ , MeOH, nm): 257, 305sh, 361;
max
+AlCl : 275, 342sh, 434; +AlCl /HCl: 269, 300sh, 368sh, 404.
3
3
PMR spectrum (400 MHz, DMSO-d , δ, ppm, J/Hz): 12.6 (1H, s, 5-OH), 7.66 (1H, d, J = 8.4, H-6′), 7.54 (1H, br.s,
6
H-2′), 6.82 (1H, d, J = 8.4, H-5′), 6.42 (1H, br.s, H-8), 6.21 (1H, br.s, H-6), 5.37 (1H, d, J = 7.6, H-1″), 3.26-3.64 (sugar
protons).
13
C NMR spectrum (400 MHz, DMSO-d , δ, ppm): 156.1 (C-2), 133.4 (C-3), 177.3 (C-4), 160.8 (C-5), 98.5 (C-6),
6
163.9 (C-7), 93.4 (C-8), 156.2 (C-9), 103.7 (C-10), 121.0 (C-1′), 115.0 (C-2′), 144.5 (C-3′), 148.1 (C-4′), 115.7 (C-5′), 121.9
(C-6′), 101.6 (C-1″), 70.9 (C-2″), 72.9 (C-3″), 67.4 (C-4″), 75.6 (C-5″), 59.9 (C-6″). Acid hydrolysis of 6 produced quercetin
and galactose [2].
Kaempferol-3-O-(2 -O-β-D-glycopyranosyl)-β-D-glucopyranoside (7), yellow powder (MeOH), mp 234-235°C.
UV spectrum (λ , MeOH, nm): 266, 300sh, 350; +AlCl : 275, 304sh, 350sh, 396; +AlCl /HCl: 275, 302sh, 346sh, 395.
3
3
max
PMR spectrum (400 MHz, DMSO-d , δ, ppm, J/Hz): 12.6 (1H, br.s, 5-OH), 8.04 (2H, d, J = 7.2, H-2′,6′), 6.91 (2H,
6
d, J = 7.2, H-3′,5′), 6.40 (1H, d, J = 2.0, H-8), 6.16 (1H, d, J = 2.0, H-6), 5.69 (1H, d, J = 7.6, H-1″), 4.61 (1H, d, J = 8.0, H-1″),
3.04-3.67 (sugar protons).
13
C NMR spectrum (400 MHz, DMSO-d , δ, ppm): 156.3 (C-2), 132.7 (C-3), 177.1 (C-4), 160.8 (C-5), 98.7 (C-6),
6
164.0 (C-7), 93.6 (C-8), 155.2 (C-9), 103.8 (C-10), 120.9 (C-1′), 130.8 (C-2′), 115.1 (C-3′), 159.6 (C-4′), 115.1 (C-5′), 130.8
(C-6′), 97.8 (C-1″), 82.1 (C-2″), 76.2 (C-3″), 69.4 (C-4″), 76.3 (C-5″), 60.5 (C-6″), 103.4 (C-1″′), 74.1 (C-2″′), 77.3 (C-3″′),
69.2 (C-4″′), 76.8 (C-5″′), 60.2 (C-6″′). Acid hydrolysis of 7 produced kaempferol and glucose [4].
Quercetin-3-O-(2 -O-β-D-glucopyranosyl)-β-D-galactopyranoside (8), yellow powder (MeOH), mp 225-226 C.
UV spectrum (λ , MeOH, nm): 256, 356; +AlCl : 274, 339sh, 428; +AlCl /HCl: 270, 363sh, 399.
3
3
max
PMR spectrum (400 MHz, DMSO-d , δ, ppm, J/Hz): 12.7 (1H, br.s, 5-OH), 9.3 (1H, br.s, 3′-OH), 7.69 (1H, dd,
6
J = 8.8, 2.4, H-6′), 7.61 (1H, d, J = 2.4, H-2′), 6.86 (1H, d, J = 8.8, H-5′), 6.42 (1H, d, J = 2.0, H-8), 6.21 (1H, d, J = 2.0, H-6),
5.64 (1H, d, J = 7.6, H-1″), 4.57 (1H, d, J = 7.6, H-1″′), 3.07-3.80 (sugar protons).
13
C NMR spectrum (400 MHz, DMSO-d , δ, ppm): 155.3 (C-2), 133.0 (C-3), 177.3 (C-4), 160.8 (C-5), 98.4 (C-6),
6
163.8 (C-7), 93.4 (C-8), 156.1 (C-9), 103.7 (C-10), 121.0 (C-1′), 115.2 (C-2′), 144.6 (C-3′), 148.2 (C-4′), 115.7 (C-5′), 122.1
(C-6′), 98.3 (C-1″), 80.6 (C-2″), 73.1 (C-3″), 67.3 (C-4″), 75.7 (C-5″), 59.7 (C-6″), 74.1 (C-2″′), 76.6 (C-3″′), 69.2 (C-4″′), 76.2
(C-5″′), 60.4 (C-6″′). Acid hydrolysis of 8 produced quercetin and galactose [5].
13
Based on the PMR and C NMR data, 9-11 were identified as 2-phenylethyl-O-β-D-glucopyranoside (9),
protocatechuic acid (10), and gallic acid (11).
Thus, juglanin (3), avicularin (4), hyperoside (6), kaempferol-3-O-(2″-O-β-D-glucopyranosyl)-β-D-glucopyranoside
(7), quercetin-3-O-(2″-O-β-D-glucopyranosyl)-β-D-galactopyranoside (8), and protocatechuic acid (10) were isolated for the
first time from R. rugosa Thunb.
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