A new chromene glycoside from tithonia diversifolia

Article abstract of DOI:10.1007/s10600-010-9567-8

A new chromene glycoside, 6-acetyl-2,2-dimethylchromene-8-O-β-D- glucoside, together with four known compounds were isolated from the aerial parts of Tithonia diversifolia. Their structures were established by ¹H, ¹³C NMR, and HMQC together with the other physical and chemical investigations.

Full text of DOI:10.1007/s10600-010-9567-8

Chemistry of Natural Compounds, Vol. 46, No. 2, 2010
A NEW CHROMENE GLYCOSIDE FROM Tithonia diversifolia
1,2
2,3
1
1,2
Hong-li Zhai, Gui-jun Zhao, Gen-jin Yang, He Sun,
UDC 547.972
1,2
1*
2*
Bo Yi, Lian-na Sun, Wan-sheng Chen,
and Shui-qing Zheng
1
A new chromene glycoside, 6-acetyl-2,2-dimethylchromene-8-O-ꢀ-D-glucoside, together with four known
compounds were isolated from the aerial parts of Tithonia diversifolia. Their structures were established by
1
13
H, C NMR, and HMQC together with the other physical and chemical investigations.
Keywords: Tithonia diversifolia, chromene, 6-acetyl-2,2-dimethylchromene-8-O-ꢀ-D-glucoside.
Tithonia diversifolia (Hemsl.) A. Gray (Compositae), known as Mexican sunflower, is native to Mexico and Central
America. Traditionally, T. diversifolia is used for the treatment of malaria [1] and other forms of fever. Presently, T. diversifolia
has been introduced into other countries for ornamental purposes or for their pharmacological action and is widespread in the
southern part of Asia, Africa, and the Pacific region. Now T. diversifolia is of particular interest for phytomedical and health
care research. The extract and compounds isolated from the plant showed anti-inflammatory, analgesic, antimycotic,
anti-HIV-1 [2], and antidiabetes mellitus properties [3]. Chemical studies on this species resulted in sesquiterpene lactones [4],
such as tagitinin A–C and F, diversifol and tithonine chromene, and flavone derivatives [5, 6]. Here we investigate the aerial
parts of T. diversifolia and report the isolation of one new natural compound, 6-acetyl-2,2-dimethylchromene-8-O-ꢀ-D-glucoside
(3), together with other four known chromenes, 6-acetyl-2,2-dimethylchromene (1) [7], 6-acetyl-8-hydroxy-2,2-dimethyl-
chromene (2) [8], 6-acetyl-7-hydroxy-2,2-dimethylchromene (4) [7], and 6-acetyl-7-methoxy-2,2-dimethylchromene (5) [9].
O
5
3
11
12
13
14
9
R
2
7
O
1
R
1
1 - 5
1: R = R = H; 2: R = OH, R = H
1
2
1
2
3: R = O-Glc, R = H; 4: R = H, R = OH
1
2
1
2
5: R = H, R = OCH
1
2
3
The new compound 3 was obtained as colorless crystals with melting point 148–150ꢁC and molecular formula
+
+
C H O , as established by HR-ESI-MS m/z at 403.1374 [M + Na] (C H O Na ); calcd for C H O : 380.3906,
19 24
8
19 24
8
19 24 8
13
which was supported by C NMR. The EI-MS m/z (I , %) 218 (40), 203 (100), 164 (35), 43 (60), showed the presence
rel.
of a sugar, and acid hydrolysis of 3 afforded D-glucose by GC analysis. The IR spectrum of compound 3 showed absorptions
–1
1
at 1676 and 1600 cm , suggesting the presence of the carbonyl and phenyl groups. The H NMR spectrum in MeOD
exhibited signals for two similar methyl groups (s, 1.46; s, 1.48) and one acetoxyl group (s, 2.53); two meta aromatic hydrogens
7.44 (d, J = 1.8), 7.67 (d, J = 1.8); an alkenyl group 5.80 (d, J = 10.2 Hz), 6.43 (d, J = 10.2 Hz) flanked by the aromatic ring.
1) Department of Pharmacognosy, School of Pharmacy, Second Military Medical University, Shanghai 200433, P. R.
China, fax: +86 021 25074574, e-mail: sssnmr@yahoo.com.cn; 2) Department of Pharmacy, the Affiliated Changzheng
Hospital of Second Military Medical University, Shanghai 200003, P. R. China, fax: +86 021 33100038, e-mail:
chenwanshengsmmu@yahoo.com.cn; 3) JilinAgricultural University, Changchun 130118, P. R. China. Published in Khimiya
Prirodnykh Soedinenii, No. 2, pp. 167–168, March–April, 2010. Original article submitted November 25, 2008.
198
0009-3130/10/4602-0198 02010 Springer Science+Business Media, Inc.

O
11
3
12
5
13
14
9
7
O
OH
1
O
O
OH
OH
1'
3
OH
Fig. 1. HMBC correlations of 3.
13
The C NMR spectrum exhibited one acetoxy (199.27, C-11) and six aromatic carbon atoms; one alkenyl attached to the
aromatic ring; one quaternary carbon (79.41, C-2) attached to oxygen. Based on the above spectral data, the skeleton of 3 was
a chromene. The sequence and linkage position of the glucose moiety was subsequently deduced from the correlation between
H-1ꢂ of glucose and C-8 in the HMBC experiment (Fig. 1), and the ꢀ-D-glucosidic bond was deduced from the H-1ꢂ (1H, d,
J = 7.80 Hz); also, the position of the acetoxyl group was confirmed by the correlation between H-5 and C-11; the correlations
between H-7 and C-9, C-11; H-4 and C-2 were also observed. Thus compound 1 was indentified as 6-acetyl-2,2-
dimethylchromene-8-O-ꢀ-D-glucoside.
EXPERIMENTAL
1
General Methods. NMR spectra were obtained on a Bruker DRX-500 spectrometer at 500 MHz for H and
13
125 MHz for C. Chemical shifts are expressed in ꢃ values with reference to DMSO-d as internal standard, and coupling
6
constants (J) are given in Hz; ESI-MS was recorded on a Varian MAT-212 mass spectrometer; melting point was measured on
a ZMD83-1 electrothermal melting point apparatus and uncorrected; IR was recorded on a Bruker Vector 22 spectrometer with
KBr pellet.
Plant Material. The aerial parts of Tithonia diversifolia (Hemsl.) A. Gray (Compositae) were collected in Mengzi,
Yunnan province, P. R. China in September 2004 and were identified by Prof. Wansheng Chen. A voucher specimen was
deposited in the Department of Pharmacognosy, Second Military Medical University, Shanghai, P. R. China.
Extraction and Isolation. The air-dried aerial parts of Tithonia diversifolia (70 kg) were percolated with 80% EtOH.
The EtOH extract was concentrated to an aqueous residue and then suspended with water. The water layer was extracted with
petroleum ether, CH Cl , EtOAc, and n-BuOH. The CH Cl -soluble part was evaporated to a black syrup (320 g), which was
2
2
2
2
subjected to silica gel column chromatography with petroleum ether–EtOAc. 6-Acetyl-2,2-dimethylchromene (1) (20 mg),
6-acetyl-7-methoxy-2,2-dimethylchromene (5) (80 mg), 6-acetyl-7-hydroxy-2,2-dimethylchromene (4) (230 mg), 6-acetyl-8-
hydroxy-2,2-dimethylchromene (2) (40 mg), and 6-acetyl-2,2-dimethylchromene-8-O-ꢀ-D-glucoside (3) (60 mg) were eluted
with (50:1, 15:1, 5:1, 3:1) and purified by reversed-phase (RP-18) chromatography using silica gel and Sephadex LH-20.
+
1
6-Acetyl-2,2-dimethylchromene (1), white powder, C H O . EI-MS m/z: 203 [M + H] . H NMR (CDCl , ꢃ,
13 14
2
3
ppm, J/Hz): 7.73 (1H, dd, J = 7.6, 1.8, H-7), 7.61 (1H, d, J = 7.6, H-8), 6.78 (1H, d, J = 1.8, H-5), 6.34 (1H, d, J = 10.2, H-4),
13
5.65 (1H, d, J = 10.2, H-3), 2.52 (3H, s, H-12), 1.45 (6H, s, H-13, 14); C NMR (CDCl , ꢃ): 196.6 (C-11), 157.4 (C-9), 131.2
3
(C-7), 129 (C-3), 126.9 (C-8), 120.6 (C-4), 113.9 (C-10), 99.6 (C-5), 76.8 (C-2), 28.3 (C-13,14), 26.2 (C-12).
+
1
6-Acetyl-7-hydroxy-2,2-dimethylchromene (2), white powder, C H O . EI-MS m/z: 219 [M + H] . H NMR
13 14
3
(CDCl , ꢃ, ppm, J/Hz): 7.31 (1H, s, H-8), 6.33 (1H, s, H-5), 6.27 (1H, d, J = 10.2, H-4), 5.57 (1H, d, J = 10.2, H-3), 2.54 (3H,
3
13
s, H-12), 1.45 (6H, s, H-13, 14); C NMR (CDCl , ꢃ): 203.1 (C-11), 160.7 (C-9), 129.7 (C-8), 129.1 (C-3), 121.4 (C-4), 114.6
3
(C-6), 165.1 (C-7), 114.0 (C-10), 104.5 (C-5), 78.2 (C-2), 28.4 (C-13, 14), 26.3 (C-12).
[ꢄ]2D0
6-Acetyl-2,2-dimethylchromene-8-O-ꢀ-D-glucoside (3), colorless crystals, mp 148–150ꢁC;
+20ꢁ (c 0.1,
–1
1
MeOH). UV (MeOH, ꢅ , nm): 266; IR (KBr,
, cm ): 3446, 2924, 1676, 1600, 1382, 1306, 1199, 1076. H NMR
max
max
(600 MHz, MeOD, ꢃ, ppm, J/Hz): 1.46 (3H, s, H-13), 1.48 (3H, s, H-14), 2.53 (3H, s, H-12), 5.80 (1H, d, J = 10.2, H-3), 6.43
(1H, d, J = 10.2, H-4), 7.44 (1H, d, J = 1.8, H-5), 7.67 (1H, d, J = 1.8, H-7), 4.94 (1H, d, J = 7.80, H-1ꢂ), 3.45 (1H, m, H-2ꢂ),
13
3.40 (1H, m, H-3ꢂ) , 3.29 (1H, m, H-4ꢂ), 3.49 (1H, m, H-5ꢂ), 3.83 (1H, dd, J = 12.0, H-6ꢂ); C NMR (150 MHz, MeOD, ꢃ):
26.4 (C-12), 28.2 (C-14), 28.4 (C-13), 79.41 (C-2), 119.46 (C-3), 122.72 (C-5), 122.78 (C-10), 131.16 (C-6), 132.81 (C-4),
199

147.62 (C-8), 149.51 (C-9), 199.27 (C-11), 103.13 (C-1ꢂ), 77.99 (C-2ꢂ), 78.40 (C-3ꢂ), 71.36 (C-4ꢂ),74.96 (C-5ꢂ), 62.50 (C-6ꢂ).
+
+
HR-ESI-MS m/z: 403.1374 [M + Na] (C H O Na ); calcd for C H O , 380.3906; EI-MS m/z (I , %): 218 (40), 203
19 24
8
19 24
8
rel.
(100), 164 (35), 43 (60).
+
1
6-Acetyl-8-hydroxy-2,2-dimethylchromene (4), white crystal, C H O . EI-MS m/z: 219 [M + H] . H NMR
13 14
3
(CDCl , ꢃ, ppm, J/Hz): 7.45 (1H, d, J = 1.8, H-7), 7.28 (1H, d, J = 1.8, H-5), 6.38 (1H, d, J = 10.2, H-4), 5.69 (1H, d, J = 10.2,
3
13
H-3), 2.55 (3H, s, H-12), 1.52 (6H, s, H-13, 14); C NMR (CDCl , ꢃ): 196.8 (C-11), 144.2 (C-6), 143.7 (C-8), 130.9 (C-3),
3
130.5 (C-9), 121.7 (C-4), 120.5 (C-10), 118.8 (C-5), 115.3 (C-7), 78.6 (C-2), 28.3 (C-13, 14), 26.3 (C-12).
+ 1
6-Acetyl-7-methoxy-2,2-dimethylchromene (5), white powder, C H O . EI-MS m/z: 221 [M + H] . H NMR
13 16
3
(CDCl , ꢃ, ppm, J/Hz): 7.53 (1H, s, H-5), 6.37 (1H, s, H-8), 6.29 (1H, d, J = 10.2, H-4), 5.51 (1H, d, J = 10.2, H-3), 3.87 (3H,
3
13
s, OMe), 2.55 (3H, s, H-12), 1.43 (6H, s, H-13, 14); C NMR (CDCl , ꢃ): 197.5 (C-11), 161.8 (C-7), 158.4 (C-9), 129
3
(C-5), 128.3 (C-3), 121.6 (C-4), 113.4 (C-10), 99.6 (C-8), 76.8 (C-2), 55.5 (OCH ), 28.3 (C-13, 14), 26.2 (C-12).
3
ACKNOWLEDGMENT
The work was supported by National Natural Science Foundation of China (20872177) and Program of Shanghai
Science and Technology Commission (08DZ1971503).
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