A new benzophenone C-glycoside from Polygala telephioides Willd.

Article abstract of DOI:10.1016/j.cclet.2010.01.035

A new benzophenone C-glucoside, 3′-C-[4-O-(5-hydroxyferuloyl)-β-d-glucopyranosyl]-2′,4′,6′-trihydroxy-3,4-dimethoxy-benzophenone, named telephenone D, was isolated from the whole plants of Polygala telephioides, and its structure was determined by analysis of spectroscopic data.

Full text of DOI:10.1016/j.cclet.2010.01.035

Available online at www.sciencedirect.com
Chinese Chemical Letters 21 (2010) 584–586
www.elsevier.com/locate/cclet
A new benzophenone C-glycoside from Polygala telephioides Willd.
Ting Jun Ma a, Xi Cheng Shi b, Chang Xi Jia a,
*
a Department of Food Science, Beijing Agricultural College, Beijing 102206, China
b Research Insitute of Chemical Defense, Beijing 100083, China
Received 10 June 2009
Abstract
A new benzophenone C-glucoside, 30-C-[4-O-(5-hydroxyferuloyl)-b-D-glucopyranosyl]-20,40,60-trihydroxy-3,4-dimethoxy-
benzophenone, named telephenone D, was isolated from the whole plants of Polygala telephioides, and its structure was
determined by analysis of spectroscopic data.
# 2010 Chang Xi Jia. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
Keywords: Polygala telephioides; Benzophenone C-glucoside; Telephenone D
Polygala telephioides Willd. is widely distributed in southern China and has been used as a detoxification agent for
heroin poisoning in China. It was reported to contain oligosaccharide esters, benzophenone C-glucosides and the
flavone C-glucoside, telephioidin in the above mentioned plant [1–3]. Here, we report the isolation and structure
elucidation of a new benzophenone C-glucoside, telephenone D (1), from the whole plants of P. telephioides. Naturally
occurring benzophenone C-glucosides are very rare, and to our knowledge, only five compounds with this skeleton
have been reported from the plants of the genus Polygala [1,2,4,5].
The dried whole plants (18 kg) of P. telephioides were extracted twice with hot 95% ethanol for 2 h each time under
reflux. After removal of the solvent under reduced pressure at 60 8C, the residue (1.15 kg) was suspended in water and
defatted with petroleum ether. The aqueous layer was further extracted with ethyl acetate and n-butanol successively to
obtain the EtOAc extract (120 g) and n-butanol extract (680 g). A portion of n-butanol extract (600 g) was subjected to
D101 porous polymer resin and eluted with H2O, 20%, 50% and 70% aqueous EtOH successively. The 50% aqueous
EtOH eluate (140 g) was chromatographed on a silica gel (200–300 mesh, 1 kg) column using CHCl3–MeOH in a
gradient manner (10:1 ! 1:1) to afford nine fractions (A–I) on the basis of TLC analyses. Subfraction D (12.0 g) was
applied to a silica gel (200–300 mesh, 100 g) column, eluted with CHCl3–MeOH–H2O (20:1:0.1 ! 3:1:0.1) to give
six fractions based on TLC. Among them, Fr. 5 (20.3 g) was first subjected to silica gel CC using CHCl3/MeOH
(20:1 ! 1:1) as eluent, then purified by Sephadex LH-20 column chromatography to yield compound 1 (18 mg).
Compound 1 was obtained as a pale yellow powder, and its positive-ion ESI-TOF-MS exhibited quasi-molecular
ion peaks [M+H]+, [M+Na]+ and [M+K]+ at m/z 645.1, 667.0 and 683.0, respectively, indicating the molecular formula
to be C31H32O15. HRESIMS: m/z 645.1609[M+H]+ (Cacld. for C31H33O15, 645.1602). IR spectrum showed
* Corresponding author.
E-mail address: jcxbac@sohu.com (C.X. Jia).
1001-8417/$ – see front matter # 2010 Chang Xi Jia. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
doi:10.1016/j.cclet.2010.01.035

T.J. Ma et al. / Chinese Chemical Letters 21 (2010) 584–586
585
Table 1
1H NMR (500 MHz) and 13C NMR (125 MHz) data for compound 1 (in DMSO-d6).
Position
dC
dH
Position
dC
dH
1
132.4
111.1
152.2
148.0
110.4
123.8
106.0
158.9
103.6
160.4
94.9
3-OMe
4-OMe
55.9
55.6
3.77 s
3.81 s
2
7.26 d (2.1)
3
4
50-0H0 ydroxyferuloyl
5
6.98 d (8.1)
1000
124.4
103.4
148.5
137.1
144.9
110.2
55.4
6
7.22 dd (2.1, 8.1)
2000
10
20
30
40
50
60
3
4000
5000
6000
3000-OMe
5.98 s
3.79 s
157.7
195.4
74.4
a
b
114.6
145.6
165.9
6.39 d (15.9)
7.46 d (15.9)
C
O
Glc-100
200
4.62 d (6.0)
C O
71.4
3.90 m
300
400
76.0
3.47(overlapped)
4.80 t (8.0)
71.2
500
600
79.0
3.46(overlapped)
3.32 m, 3.48 m
60.7
absorptions due to hydroxyl (3305 cmꢀ1), carbonyl (1655 cmꢀ1), aromatic ring (1633, 1604, 1513, 1452 cmꢀ1). UV
(MeOH) lmax (log e): 315 (3.04), 213 (2.54) nm; UV(MeOH + NaOAC) lmax (log e): 375, 230 nm; acid hydrolysis of
compound followed by GC analysis showed the presence of a glucose. We favor its D absolute configuration by
comparison of its retention time (tR = 12.50 min) with that of authentic standard. The 1H NMR spectrum showed an
isolated aromatic proton at d 5.98 (s, 1H), ABX-system aromatic protons at d 7.26 (d, 1H, J = 2.1 Hz), 7.22 (dd, 1H,
J = 2.1, 8.1 Hz) and 6.98 (d, 1H, J = 8.1 Hz), a pair of E-olefinic protons at d 7.46 (d, 1H, J = 15.9 Hz) and 6.39 (d, 1H,
J = 15.9 Hz), two meta-aromatic protons at d 6.90 (d, 1H, J = 1.5 Hz) and 6.71 (d, 1H, J = 1.5 Hz), three methoxyl
protons at d 3.77 (s, 3H), 3.79 (s, 3H) and 3.81 (s, 3H), and a sugar unit with the anomeric H-atom resonated at d 4.62
(d, 1H, J = 6.0 Hz). The 13C NMR (Table 1) spectrum exhibited 31 signals in total, among which were presence of a 5-
1
1
hydroxyferuloyl in 1. All the H- and C-atoms were assigned by H, H-COSY, NOESY, HSQC and HMBC
Fig. 1. Key NOE and HMBC correlations of compound 1.

586
T.J. Ma et al. / Chinese Chemical Letters 21 (2010) 584–586
experiments, we deduced that the C-4 position of the Glc in 1 was esterified by a 5-hydroxyferulic acid. The HMBC
spectrum, as shown in Fig. 1, revealed that the 5-hydroxyferuloy residue was attached to the C-4 of the glucosyl
moiety, which showed a cross-peak between the proton signal at d 4.80 (H-4 of Glc) and the carbonyl carbon signal at d
165.9. From the above data, the structure of 1 was established to be 30-C-[4-O-(5-hydroxyferuloyl)-b-D-
glucopyranosyl]-20,40,60-trihydroxy-3, 4-dimethoxy benzophenone, named telephenone D.
Acknowledgments
This work was supported by the Beijing Nova Program (No. 2007B030) and the program for Agricultural products
processing technology and storage engineering in Beijing key construction disciplines (No. PXM2009-014207-
078172).
References
[1] J.C. Li, M. Ono, T. Nohara, Chem. Pharm. Bull. 48 (2000) 1223.
[2] J.C. Li, T. Nohara, Chem. Pharm. Bull. 48 (2000) 1354.
[3] J.K. Kumar, M.S. Rao, P.S. Rao, et al. Nat. Prod. Lett. 14 (1999) 35.
[4] Z.J. Wu, M.A. Ouyang, C.R. Yang, Yunnan Zhiwu Yanjiu 22 (2000) 482.
[5] Y. Jiang, P.F. TU, Chem. Pharm. Bull. 53 (2005) 1164.