Fitoterapia 78 (2007) 506 509 www.elsevier.

com/locate/fitote

A new chromone glycoside from Polygonum capitatum

Xian Li a,, Ming Yu a , Dali Meng a , Zhanlin Li a , Liyan Zhang b
a

Research Department of Natural Medicine, Shenyang Pharmaceutical University, Shenyang 110016, PR China b Guizhou Warmen Pharmaceutical Co., Ltd., Guiyang, 550018, PR China Received 20 April 2005; accepted 15 May 2007 Available online 3 July 2007

Abstract A new chromone glycoside (1), 7-O-(6-galloyl)--D-glucopyranosyl-5-hydroxychromone was isolated from Polygonum capitatum. 2007 Elsevier B.V. All rights reserved.
Keywords: Polygonum capitatum; 7-O-(6-galloyl)--D-glucopyranosyl-5-hydroxy chromone; Spectroscopic methods

1. Introduction Polygonum capitatum is a perennial herb growing at 6003500 m above sea-level in China, India and Nepal. It distributes widely in the minority districts in southwest of China and is used as a folk medicine to treat many infectious diseases such as nephritis, cystitis, urethral [1,2]. The components in P. capitatum are mainly flavones [3] and gallic, vanillic, protocatechuic acids [4]. The isolation of a new chromone glycoside (1, Fig. 1), in addition to gallic acid, quercitrin, vanillic acid and protocatechuic acid. 2. Experimental 2.1. General Melting point: Yanaco-hot-stage. NMR: Bruker-AV-600. ESIMS: Finnigan LCQ. UV: Shimadzu UV-260 UV Vis. HPLC: HP 1100, Shimadzu Shim-pack PREP-ODS (i.d.4.6 mm 150 mm). 2.2. Plant P. capitatum Buch-Ham. ex D. Don (Poligonaceae), collected in Pan country, Gui Zhou province, China, in September 2003, was identified by Prof. Qishi Sun (Shenyang Pharmaceutical University). A voucher specimen

Corresponding author. Tel.: +86 24 23986476; fax: +86 24 23841116. E-mail address: proflixian@163.com (X. Li). 0367-326X/$ - see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.fitote.2007.05.003

X. Li et al. / Fitoterapia 78 (2007) 506509

507

Fig. 1. The structure of compound 1.

(No. 20040735) is deposited in the Research Department of Natural Medicine, Shenyang Pharmaceutical University. 2.3. Extraction and isolation Dried aerial parts of P. capitatum (8.0 kg) were extracted with 70% EtOH under reflux for three times. The extract was concentrated in vacuo and the extract (135 g) was subjected to Si-gel CC 200-300 mesh eluted with CHCl3/MeOH mixture leading to eluates 18. Gallic acid (0.8 g) was afforded from eluate 3 (24.0 g) after recrystallization with CHCl3/acetone. Eluate 4 (26.5 g) was rechromatographed on Silica gel eluted with petroleum ether (PE)/EtOAc (100:50) to give compound quercitrin (145.0 mg). Eluate 5 (15.2 g) was subjected to Si-gel CC eluted with PE/EtOAc (100: 6070) to give vanillic acid (25 mg). Eluate 6 (15.2 g) was further subjected to Si-gel CC, eluted with PE/EtOAc (100:55) and the eluate was recrystallized from EtOAc/MeOH to give compound 1 (18.0 mg). Eluate 7 was separated by Si-gel CC using PE/EtOAc (100: 80) to yield protocatechuic acid (26.0 mg).
Table 1 The 1H NMR and 13C NMR data for 1 (600 and 150 MHz, DMSOd6, J in Hz and in ppm) C 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 1 2, 6 3, 5 4 7 C 158.1 110.8 181.8 161.3 99.8 162.9 94.6 157.7 106.8 99.7 73.1 76.2 69.7 74.1 63.4 119.5 108.8 145.6 138.6 165.9 H 8.11(1H, d, J 6.0) 6.32(1H, d, J 6.0) 6.41(1H, d, J 1.8) 6.66 (1H, d, J 1.8) 5.12 (1H, d, J 7.8) 3.32 (1H, m) 3.34 (1H, m) 3.29 (1H, m) 3.81 (1H, m) 4.46, 4.20 (2H, m) 6.94 (2H, s) 9.24 (2H, s, OH) 9.00, (1H, s, OH)

508

X. Li et al. / Fitoterapia 78 (2007) 506509

Fig. 2. The main HMBC correlations of compound 1.

7-O-(6-Galloyl)--D-glucopyranosyl-5-hydroxychromone (1, Fig. 1). Yellow needles (EtOAc/MeOH), mp 186187 C. UV max (MeOH): 237 (log e 4.10), 256 (4.30), 276 (3.90) nm; 1H NMR (600 MHz, in DMSO-d6) and 13 C NMR (150 MHz, in DMSO-d6) see Table 1. 3. Results and discussion Compound 1 mp 186.0-187.0 C, gave positive response to the FeCl3/K3Fe(CN)6 and Molish reaction. After hydrolyzing in 4% H2SO4 for 4 h at 80 C, glucose was detected in the PC of the hydrolyzates, and gallic acid could be detected by HPLC [H2OMeOHTHF (60:20:20) + 0.5% HAc, UV 270 nm 1 ml/min] in the EtOAc extract of the hydrolyzates. The molecular formula was established to be C22H20O13 by negative ESIMS:m/z 491.3 [MH] along with 1H NMR and 13C NMR data. The negative ESIMS spectrum also showed the fragment peak at m/z 339.3, indicating the loss of one galloyl, and the peak of aglycone at m/z 178.8. Additionally, the typical 5, 7-dihydroxyl chromone absorption could be observed in the UV spectrum [UV max (MeOH): 237 (log E 4.10), 256 (4.30), 276 (3.90) nm] [5]. The 1H NMR spectrum gave the two ortho hydrogens of chromone at 8.11 and 6.32 and two meta-aromatic protons at 6.41 and 6.66. Furthermore compound 1 showed a remarkable downfield shift of the 5-OH at 12.64 associated with C-4 at 181.8. A pair of symmetrical aromatic protons at 6.94, three hydroxyl protons at 9.24 and 9.00, combined with one carbon signal at 165.9 and four symmetrical carbons at 145.6, 108.8 in the 13C NMR proved the existence of the galloyl group. Additionally, the aliphatic protons ranged from 5.52 to 3.80 in the 1H NMR spectrum, including the signal appeared at 5.12 with the characteristic coupling constant of -configuration, belonged to the protons of glucose. The 13C NMR spectrum presented 20 carbon signals, including two pairs of symmetrical carbons as mentioned above. In addition the signal of C-6 of the glucose was downfield shifted to 63.4, indicating the C-6 was acylated. The anomeric proton at 5.12 and the signals at 4.46 and 4.20 (H-6) were correlated with the C-7 ( 162.9) of the chromone skeleton and the C-7 (165.9) of galloyl group in the HMBC spectrum (Fig. 2), respectively. These two key long-range cross peaks fixed the glycosidation position of the chromone and the acylated position of the glucose in the structure. Therefore, the structure of compound 1 was elucidated as 7-O-(6-galloyl)--D-glucopyranosyl-5-hydroxy chromone. Acknowledgements We are grateful to the Analytical Detective Center, Shenyang Pharmaceutical University, for recording NMR and ESIMS spectra.

X. Li et al. / Fitoterapia 78 (2007) 506509

509

References
[1] [2] [3] [4] [5] Jiangsu New Medicinal College. Dictionary of Chinese herbal medicine, vol. 1. Shanghai: Shanghai People's Publishing House; 1977. p. 611. Guanyou Ren, Fenggang Chang, Sulin Lu, Hengliang Zhong, Guilin Zhang. China J Chin Mater Med 1995;2:107. Yongjun Li, Hongfeng Luo, Yonglin Wang, Wanyun Shang, Changqi Hu. Chin Pharm J 2000;5:300. Naiju Wu, Deren Wang. Chin Trade Herb Drugs 1985;4:6. Liang Huang, Dequan Yu. The applications of UV spectrum in the organic chemistry, vol. 2. Beijing: Scientific Publishing House; 1988. p. 277.