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Chinese Chemical Letters 22 (2011) 694696

www.elsevier.com/locate/cclet

Pyromeconic acid derivatives from Conyza canadnsis (L.) Cronq

Bai Lian Liu a,b, Guo Cai Wang a,b, Hong Li Liu a,b, Yi Dai a,b,
Wen Cai Ye a,b, Yao Lan Li a,b,*
a
b

Institute of Traditional Chinese Medicine & Natural Products, Jinan University, Guangzhou 510632, China
Guangdong Province Key Laboratory of Pharmacodynamic Constituents of TCM and New Drugs Research,
Jinan University, Guangzhou 510632, China
Received 30 August 2010

Abstract
A new pyromeconic acid derivative, pyromeconic acid-3-O-b-D-glucopyranoside-30 -(O-b-D-glucopyranoside)-60 -(O-400 -hydroxybenzoate) (1), along with two known ones, were isolated from the whole plants of Conyza canadensis. Their structures were
elucidated based on the analysis of their spectroscopic data. The in vitro antibacterial testing results showed that all of these three
compounds were inactive towards two bacterial strains, Escherichia coli and Staphyloccocus aureus.
# 2010 Yao Lan Li. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
Keywords: Conyza canadensis; Chemical constituents; Pyromeconic acid derivatives

Conyza canadnsis (L.) Cronq, widely distributed in China, has been medicinally used as a fever reducer and
detoxification [1]. However, there is a paucity of information relevant to the chemical constituents and biological
activities of C. canadnsis [2]. Our investigation on the constituents of C. canadnsis led to the isolation of three
pyromeconic acid derivatives (Fig. 1): pyromeconic acid-3-O-b-D-glucopyranoside-30 -(O-b-D-glucopyranoside)-60 (O-400 -hydroxybenzoate) (1), pyromeconic acid-3-O-b-D-glucopyranoside-60 -(O-400 -hydroxybenzoate) (2) [3], and
pyromeconic acid-3-O-b-D-glucopyranoside-60 -(O-400 -hydroxy-300 ,500 -dimethoxybenzoate) (3) [3]. Their in vitro
antibacterial activity was also evaluated. This letter describes the isolation, structural elucidation, and the antibacterial
determination of the pyromeconic acid derivatives 13.
The dried and powdered whole plants of C. canadnsis (20.0 kg) were percolated in 95% ethanol. The ethanolic
extract was subjected to column chromatography over macroporous resin, silica gel, ODS, and preparative HPLC to
afford one new compound 1 and two known pyromeconic acid derivatives.
Compound 1 was obtained as white needles, mp 162164 8C, a23
D 52.3 (c 1.85, CH3OH). Its HR-ESIMS gave a
quasi-molecular ion peak at m/z 579.1324 [M+Na]+ (calcd. for C24H28O15Na m/z 579.1328). This suggested its
molecular formula was C24H28O15, in agreement with its 1H and 13C NMR spectral data (Table 1). The absorption
bands in the IR spectrum of 1 suggested the presence of hydroxyl group (3389 cm1), carboxyl group (1699 cm1),
and aromatic ring (1609, 1514 cm1). Its 1H NMR spectrum showed three olefinic protons of a pyranone at dH 8.19 (d,
1H, J = 0.72 Hz), 8.00 (dd, 1H, J = 5.6, 0.72 Hz) and 6.46 (d, 1H, J = 5.6 Hz), and the protons of a 1,4-disubstituted

* Corresponding author at: Institute of Traditional Chinese Medicine & Natural Products, Jinan University, Guangzhou 510632, China.
E-mail address: tliyl@jnu.edu.cn (Y.L. Li).
1001-8417/$ see front matter # 2010 Yao Lan Li. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
doi:10.1016/j.cclet.2010.12.023

[()TD$FIG]

B.L. Liu et al. / Chinese Chemical Letters 22 (2011) 694696

R1

695

OH
R2
1 R1=H, R2=H, R3= -D-glucose
2 R1=H, R2=H, R3=H
3 R1=OCH3, R2=OCH3, R3=H

O
O
HO
R3O

O
O

OH
O
Fig. 1. Chemical structures of 13.

benzene ring at dH 7.84 (d, 2H, J = 8.8 Hz) and 6.81 (d, 2H, J = 8.8 Hz), and two anomeric protons of sugar residues at
dH 4.80 (d, 1H, J = 7.5 Hz) and 4.64 (1H, d, J = 7.6 Hz). Its 13C NMR spectrum displayed 22 carbon signals including
signals of a benzene ring at dC 121.4, 164.6, 132.9, 116.5, a carbonyl group at dC 167.9, a pyranone group at dC 146.6,
147.7, 175.9, 117.1, 157.9, and 2 anomeric carbons of sugar residues at dC 102.5 and 105.2 (Table 1). All the data
indicated that 1 was a derivative of pyromeconic acid, which had a benzene ring and two sugar residues.
The difference between molecular formula of 1 and that of the known compound pryomeconic acid-3-O-b-Dglucopyranoside-60 -(O-400 -hydroxybenzoate) (2) [3] was C6H10O5, revealing that 1 had two sugar residues.
Comparison of 1H, 13C NMR data of 1 (Table 1) with those of 2 [3] revealed that most of the signals of the two
compounds were similar except that 2 did not have the signals of glucose at dH/dC 4.64/105.2, 3.28/75.6, 3.33/78.1,
3.27/71.6, 3.39/77.8, and 3.88, 3.64/62.6. The carbon signal of C-30 in 1 downshifted from dC 74.7 to dC 86.0,
suggesting the additional glucose might locate at the position of C-30 . And this was confirmed by the HMBC
correlations (Fig. 2) between dH 4.64 (d, 1H, J = 7.6 Hz, H-1000 ) and dC 86.0 (C-30 ), between dH 3.69 (m, 1H, H-30 ) and
dC 105.2 (C-1000 ). Hydrolysis of 1 yielded D-glucose which was identified by comparing with an authentic sample on
GC analysis [4], and the coupling constants (J = 7.6, 7.5 Hz) of the anomeric protons of sugar residues indicated that

Table 1
NMR data of 1 (d, in CD3OD, J in Hz).
No.

dC

dH

2
3
4
5
6
10
20
30
40
50
60
100
200
300
400
500
600
700
1000
2000
3000
4000
5000
6000

146.6
147.7
175.9
117.1
157.9
102.5
74.2
86.0
70.3
75.5
64.6
121.4
116.5
132.9
164.6
132.9
116.5
167.9
105.2
75.6
78.1
71.6
77.8
62.6

8.19

6.46
8.00
4.80
3.71
3.69
3.56
3.80
4.67

6.81
7.84

7.84
6.81

4.64
3.28
3.33
3.27
3.39
3.88

HMBC
d (0.72)

d (5.6)
dd (5.6, 0.72)
d (7.5)
m
m
m
m
m, 4.38 m
br d (8.8)
br d (8.8)
br d (8.8)
br d (8.8)
d (7.6)
m
m
m
m
m, 3.64 m

C-3, C-4, C-6

C-3, C-4, C-6

C-2, C-4, C-5
C-3, C-20 , C-30
C-10 , C-30
C-20 , C-40 , C-50 , C-1000
C-30 , C-50 , C-60
C-40 , C-60
C-50 , C-700

C-300 , C-400 , C-100

C-200 , C-400 , C-100

C-600 , C-400 , C-100

C-500 , C-400 , C-100

C-2000 , C-3000 , C-30

C-1000 , C-3000 , C-4000
C-5000 , C-2000 , C-4000
C-3000 , C-5000 , C-6000
C-4000 , C-6000
C-4000 , C-5000

[()TD$FIG]
696

B.L. Liu et al. / Chinese Chemical Letters 22 (2011) 694696

OH
4''

7''

O
OH
6'''

HO
HO

4' 6'

OHO O

3'

1'''

OH

5'
2'

1'

OH
2

Fig. 2. Key HMBC correlations of 1.

Table 2
Antibacterial activities of compounds 13 expressed as minimum inhibition concentration (MIC).
Compounds
1
2
3
Ampicillin b
Gentamicin b
a
b
c

Escherichia coli (mg/mL)

Inactive
Inactive
Inactive
NDc
2.5

Staphyloccocus aureus (mg/mL)

Inactive
Inactive
Inactive
0.30
2.5

Means inactive up to the concentration of 5000 mg/mL.

Positive controls.
Means no determined.

the glucose was b-D-glucopyranose. Accordingly, 1 was elucidated as pyromeconic acid-3-O-b-D-glucopyranoside-30 (O-b-D-glucopyranoside)-60 -(O-400 -hydroxybenzoate).
It has been reported that some pyromeconic acids showed antibacterial activity [3]. Therefore, three pyromeconic
acid derivatives were submitted to in vitro antibacterial evaluation with the broth microdilution method [5]. However,
they did not show inhibitory activities against the two bacterial strains, Escherichia coli and Staphyloccocus aureus, at
the high concentration of 5.0 mg/mL (Table 2).
Acknowledgment
This work was supported by grants from the Team Project of Natural Science Foundation of Guangdong Province
(No. 8351063201000003).
References
[1] Editorial Board of State Administration of TCM, Zhong Hua Ben Cao (China Herbal), Shanghai Science and Technology Press, Shanghai, 1999,
pp. 788790.
[2] S. Shao, M.M. Yan, S.N. Bi, et al. Chin. Pharm. J. 44 (2009) 1053.
[3] A.A. Ahmed, E. Abou, T. Olga, et al. Plant. Med. 68 (2002) 664.
[4] T. Ikeda, H. Tsumagari, T. Nohara, Chem. Pharm. Bull. 48 (2000) 1062.
[5] C. Ling, W.Z. Shen, Y.L. Li, et al. J. Jinan Univ. (Med. Ed.) 22 (2001) 54.