Phenolic constituents of pulicaria gnaphaloides

Full text of DOI:10.1007/s10600-014-1068-8

Chemistry of Natural Compounds, Vol. 50, No. 4, September, 2014 [Russian original No. 4, July–August, 2014]
PHENOLIC CONSTITUENTS OF Pulicaria gnaphaloides
1*
2,3
2,3*
K. A. Eshbakova, A. Yili, and H. A. Aisa
In continuation of our research on the chemical constituents of Pulicaria gnaphaloides [1], we isolated eight phenolic
compounds (1–8) using column chromatography of EtOAc fractions and elution by CHCl and a CHCl –MeOH gradient (9:1
3
3
and 4:1).
The structures of the isolated compounds were elucidated using spectral data (PMR, C NMR, DEPT, HSQC, HMBC,
13
COSY) and comparisons with the literature in addition to direct comparison with authentic samples. They were identified as
p-hydroxybenzoic acid (1), 3,4-dihydroxybenzoic acid methyl ester (2), luteolin (3), quercetin (4), isoquercitrin (5), hyperoside
(6), rutin (7), and quercetin 3-rhamnosyl-(1ꢀ6)-galactoside (8).
p-Hydroxybenzoic acid (1), C H O , white crystals, mp 159.5°C. Compound 1 was identified as p-hydroxybenzoic
7
6 3
acid using spectral data [2].
3,4-Dihydroxybenzoic Acid Methyl Ester (2). C H O , white crystals, mp 137–138°C. Its spectral data agreed
8
8 4
with those published [2].
13
Luteolin (3). C H O , light-yellow powder, mp 328–330°C. PMR and C NMR spectra agreed with those
15 10
6
published [3].
Quercetin (4). C H O , light-yellow crystals, mp 305–307°C. Spectral data and a comparison with the literature
15 10
7
identified 4 as quercetin [2].
Isoquercitrin (5). C H O , yellow powder, mp 248–250ꢁC. H NMR spectrum (600 MHz, DMSO-d , ꢂ, ppm,
1
21 20 12
6
J/Hz): 7.58 (1Í, d, J = 1.8, H-2ꢃ), 7.57 (1Í, d, J = 9.0, Í-5ꢃ), 6.85 (1Í, dd, J = 1.8; 9.0, H-6ꢃ), 6.39 (1Í, d, J = 2.4, Í-8), 6.19 (1Í,
13
d, J = 2.4, Í-6), 5.46 (1Í, d, J = 7.8, Í-1ꢃ), 12.63 (1Í, 5-ÎÍ), 10.92 (1Í, 7-ÎÍ), 9.67 (1Í, 4ꢃ-ÎÍ), 9.41 (1Í, 3ꢃ-ÎÍ). C NMR
spectrum (150 MHz, DMSO-d , ꢂ, ppm): 156.29 (Ñ-2), 133.28 (Ñ-3), 177.38 (Ñ-4), 161.21 (Ñ-5), 98.65 (Ñ-6), 162.21 (Ñ-7), 93.47
6
(Ñ-8), 156.11 (Ñ-9), 103.90 (Ñ-10), 121.56 (Ñ-1ꢃ), 116.15 (Ñ-2ꢃ), 144.78 (Ñ-3ꢃ), 148.44 (Ñ-4ꢃ), 113.41 (Ñ-5ꢃ), 121.12 (Ñ-6ꢃ), 104.84
(Ñ-1ꢃꢃ), 74.07 (Ñ-2ꢃꢃ), 76.48 (Ñ-3ꢃꢃ), 70.91 (Ñ-4ꢃꢃ), 77.55 (Ñ-5ꢃꢃ), 60.95 (Ñ-6ꢃꢃ) [4]. Acid hydrolysis of 5 produced quercetin and
D-glucose.
Hyperoside (6). C H O , yellow powder, mp 231–232°C. Acid hydrolysis detected quercetin and D-galactose [1].
21 20 12
Rutin (7). C H O , yellow powder, mp 193–195°C. Acid hydrolysis of 7 produced quercetin, D-glucose, and
27 30 16
L-rhamnose [5].
1
Quercetin 3-rhamnosyl-(1ꢀ6)-galactoside (8). C H O , yellow powder, mp 186–188ꢁC. H NMR spectrum
27 30 16
(400 MHz, DMSO-d , ꢂ, ppm, J/Hz): 7.55 (2H, dd, J = 1.8, 8.5, H-2ꢃ, 6ꢃ), 6.84 (1H, d, J = 8.5, H-5ꢃ), 6.33 (1H, d, J = 2.0,
6
H-8), 6.14 (1H, d, J = 2.0, H-6), 5.33 (1H, d, J = 7.5, H-1ꢃꢃ), 4.39 (1H, s, H-1ꢃꢃꢃ), 1.01 (3H, d, J = 6.0, CH -6ꢃꢃꢃ), 3.04–3.40
3
13
galactose and rhamnose protons, 12.56 (1Í, s, 5-ÎÍ). C NMR spectrum (100 MHz, DMSO-d , ꢂ, ppm): 156.94 (Ñ-2),
6
133.62 (Ñ-3), 177.52 (Ñ-4), 161.55 (Ñ-5), 99.48 (Ñ-6), 165.21 (Ñ-7), 94.20 (Ñ-8), 156.74 (Ñ-9), 103.81 (Ñ-10), 121.99 (Ñ-1ꢃ),
116.52 (Ñ-2ꢃ), 145.24 (Ñ-3ꢃ), 149.07 (Ñ-4ꢃ), 115.63 (Ñ-5ꢃ), 121.43 (Ñ-6ꢃ), 101.79 (Ñ-1ꢃꢃ), 74.51 (Ñ-2ꢃꢃ), 76.29 (Ñ-3ꢃꢃ), 70.97
(Ñ-4ꢃꢃ), 76.87 (Ñ-5ꢃꢃ), 67.42 (Ñ-6ꢃꢃ), 101.17 (Ñ-1ꢃꢃꢃ), 70.77 (Ñ-2ꢃꢃꢃ), 70.39 (Ñ-3ꢃꢃꢃ), 72.26 (Ñ-4ꢃꢃꢃ), 68.66 (Ñ-5ꢃꢃꢃ), 18.17 (Ñ-6ꢃꢃꢃ) [6].
Acid hydrolysis of 8 produced quercetin, D-galactose, and L-rhamnose.
p-Hydroxybenzoic acid, 3,4-dihydroxybenzoic acid methyl ester, luteolin, quercetin, and quercetin 3-rhamnosyl-
(1ꢀ6)-galactoside were isolated for the first time from the genus Pulicaria; isoquercitrin and rutin, for the first time from
Pulicaria gnaphaloides.
1) S. Yu. Yunusov Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan,
Tashkent, e-mail: e_komila@yahoo.com; 2) Xinjiang Technical Institute of Physics and Chemistry, Central Asian Center of
Drug Discovery and Development, Chinese Academy of Sciences, 830011, Urumqi, P. R. China, e-mail: haji@ms.xjb.ac.cn;
3) Xinjiang Key Laboratory of Plant Resources and Natural Products Chemistry, XTIPC CAS, 830011, Urumqi, P. R. China.
Translated from Khimiya Prirodnykh Soedinenii, No. 4, July–August, 2014, p. 639. Original article submitted March 13, 2014.
©
0009-3130/14/5004-0737 2014 Springer Science+Business Media New York
737

ACKNOWLEDGMENT
The work was supported financially by programs for International Collaboration and Exchange of the National
Foundation for Natural Sciences of China (No. 31110103908) and International Scientific and Technical Collaboration of
Xinjiang-Uighur Autonomous Region (No. 20126023).
REFERENCES
1.
2.
3.
4.
5.
6.
K. A. Eshbakova, Med. Plants, 3 (2), 161 (2011).
K. A. Eshbakova, Bahang, and H. A. Aisa, Chem. Nat. Compd., 46, 974 (2011).
M. P. Yuldashev, Chem. Nat. Compd., 41, 99 (2005).
M. Moohammadnor, X. Tursun, M. Q. Ling, A. Sultan, and K. A. Eshbakova, Chem. Nat. Compd., 46, 799 (2010).
A. Sultan, Bahang, H. A. Aisa, and K. A. Eshbakova, Chem. Nat. Compd., 44, 366 (2008).
C. Di Giovane Costanzo, V. C. Fernandes, S. Zingaretti, R. O. Beleboni, A. M. S. Pereira, M. Marins,
S. H. Taleb-Contini, P. S. Pereira, and A. L. Fachin, Braz. J. Pharm. Sci., 49 (3), 559 (2013).
738