Chemical constituents of apocynum lancifolium flowers

Full text of DOI:10.1007/s10600-014-1009-6

Chemistry of Natural Compounds, Vol. 50, No. 3, July, 2014 [Russian original No. 3, May–June, 2014]
CHEMICAL CONSTITUENTS OF Apocynum lancifolium FLOWERS
1,2
1
1,3
1*
N. B. Begmatov, A. Yili, K. A. Eshbakova, and H. A. Aisa
The perennial plant Apocynum lancifolium (Apocynaceae) is broadly distributed in CentralAsia, western and eastern
Siberia, Mongolia, Iran, and China [1]. It flowers in June-July and fruits in August-September. It grows among bushes along
valleys and banks of rivers and lakes and occasionally in alkaline meadows.
Flowers of A. lancifolium are known in China as Luobuma and are used in Chinese folk and contemporary medicine
as a medicinal tea and effective treatment for hypertension and neurasthenia and possess hypolipidemic, hepatotropic, antioxidant,
antiviral, and nephritic activity. The flowers are popular in Japan as a health drink and are sold as rejuvenating food additives
in the battle with hypercholesterolemia and as antihypertensive sedative agents [2–5].
Ground air-dried flowers of A. lancifolium that were collected in Xinjiang A. R., PRC, were extracted with EtOH
(70%) at room temperature. The combined extract was evaporated in vacuo, diluted with H O (1:1), and extracted successively
2
with hexane, CHCl , EtOAc, and n-BuOH. The EtOAc extract was chromatographed over a column of silica gel using a
3
CHCl –MeOH gradient. Elution by CHCl –MeOH (50:1–1:1) isolated sterol and phenolic compounds 1–15. The structures
3
3
13
of the isolated compounds were elucidated using spectral data (PMR, C NMR, DEPT, HSQC, HMBC, COSY, and mass
spectrometry) and comparisons with the literature and authentic samples.
+
Ergost-5-en-3-ol (1), C H O, [M] 400.680. Identified by GC-MS: 39 (8), 41 (56), 43 (100), 55 (75), 57 (69), 69
28 48
(48), 77 (12), 79 (36), 81 (57), 95 (50), 97 (28), 99 (6), 107 (47), 119 (28), 133 (26), 145 (37), 159 (31), 173 (13), 187 (9), 199
(11), 213 (27), 231(14), 240 (7), 247 (5), 255 (18), 273 (15), 281 (6), 289 (29), 301 (5), 315 (25), 340 (6), 367 (21), 382 (25),
385 (18), 400 (43).
+
Lupeol (2), C H O, [M] 426. Identified by GC-MS: 41 (70), 43 (100), 55 (90), 57 (48), 68 (96), 77 (22), 81 (75),
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83 (22), 95 (75), 109 (70), 212 (58), 135 (50), 147 (38), 161 (30), 175 (25), 189 (52), 203 (25), 207 (55), 218 (46), 234 (20),
247 (12), 257 (16), 272 (10), 283 (8), 297 (6), 315 (7), 339 (6), 357 (5), 365 (4), 383 (4), 393 (4), 411 (10), 426 (25).
ꢀ-Sitosterol (3), C H O, mp 131–132°C. Identified by comparison with an authentic sample.
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p-Hydroxybenzoic acid (4), C H O , mp 159.5°C [6].
7
6 3
3,4-Dihydroxybenzoic acid methyl ester (5), C H O , mp 137–138°C [6].
8
8 4
1
Caffeic acid (6), C H O . Í NMR spectrum (400 MHz, ÑD OD, ꢁ, ppm, J/Hz): 7.53 (1Í, d, J = 16.9, H-8), 7.03
(1Í, d, J = 1.8, Í-2), 6.93 (1H, dd, J = 1.8, 8.0, Í-6), 6.77 (1Í, d, J = 8.0, Í-5), 6.21 (1H, d, J = 16.9, Í-7). C NMR spectrum
9
8
4
3
13
(100 MHz, ÑD OD, ꢁ, ppm): 127.79 (Ñ-1), 115.07 (Ñ-2), 146.79 (Ñ-3), 149.44 (Ñ-4), 116.47 (Ñ-5), 122.84 (Ñ-6), 115.51
3
(Ñ-7), 147.02 (Ñ-8), 171.09 (Ñ-9).
1
Esculetin (7), C H O , mp 268–270°C. Í NMR spectrum (400 MHz, DMSO-d , ꢁ, ppm, J/Hz): 7.87 (1Í, d,
9
6
4
6
J = 9.2, H-4), 6.97 (1Í, s, Í-5), 6.73 (1H, s, Í-8), 6.15 (1Í, d, J = 9.2, Í-3), 3.41 (1H, br.s, 6-ÎÍ), 9.80 (1H, br.s, 7-ÎÍ).
13
C NMR spectrum (100 MHz, DMSO-d , ꢁ, ppm): 160.76 (Ñ-2), 111.46 (Ñ-3), 144.42 (Ñ-4), 112.27 (Ñ-5), 142.85 (Ñ-6),
6
150.40 (Ñ-7), 102.61 (Ñ-8), 148.48 (Ñ-9), 110.71 (Ñ-10) [7].
ꢀ-Sitosterol-D-glucopyranoside (8), C H O , mp 275–277°C [6].
35 60
6
13
Kaempferol (9), C H O , yellow crystals, mp 276–277°C. PMR and C NMR spectra agreed with those published [6].
15 10
6
Quercetin (10), C H O , light-yellow crystals, mp 305–307°C. Spectral data and a comparison with the literature
15 10
7
identified 10 as quercetin [6, 8].
Quercetin was isolated earlier from A. lancifolium leaves [6, 9].
Astragalin (11), C H O , mp 209–211°C. Spectral data agreed with those published [9].
21 20 11
1) Xinjiang Technical Institute of Physics and Chemistry, Central Asian Drug Discovery and Development Center of
CAS, 830011, Urumqi, P. R. China, e-mail: haji@ms.xjb.ac.cn; 2) Graduate University of the Chinese Academy of Sciences,
100049, Beijing, P. R. China; 3) 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. Translated from Khimiya Prirodnykh Soedinenii, No. 3,
May–June, 2014, pp. 467–468. Original article submitted February 4, 2014.
©
0009-3130/14/5003-0541 2014 Springer Science+Business Media New York
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Isoquercitrin (12), C H O , mp 248–250°C [10]. Acid hydrolysis of 12 produced quercetin and D-glucose.
21 20 12
Hyperoside (13), C H O , mp 231–232°C [11]. Both quercetin and D-galactose were identified after acid
21 20 12
hydrolysis.
1
Nicotiflorin (14), light-yellow crystals, C H O , mp 182–186°C. Í NMR spectrum (400 MHz, DMSO-d , ꢁ,
27 30 15
6
ppm, J/Hz): 8.23 (2Í, dd, J = 8.4, 2.0, H-2ꢂ, 6ꢂ), 6.86 (2Í, dd, J = 8.4, 2.0, H-3ꢂ, 5ꢂ), 6.29 (1H, d, J = 1.8, Í-8), 6.10 (1Í, d,
J = 1.8, Í-6), 5.27 (1Í, d, J = 7.2, Í-1ꢂꢂ), 4.40 (1Í, br.s, Í-1ꢂꢂꢂ), 3.16–3.43 carbohydrate protons, 1.06 (3Í, d, J = 6.0, ÑÍ ),
3
12.57 (1H, br.s, 5-ÎÍ) [12].
Acid hydrolysis of 14 produced kaempferol, D-glucose, and L-rhamnose [9].
Rutin (15), C H O , mp 193–195°C [9]. Acid hydrolysis of 15 produced quercetin, D-glucose, and L-rhamnose.
27 30 16
Ergost-5-en-3-ol, caffeic acid, esculetin, and nicotiflorin were isolated for the first time from plants of the genus
Apocynum.
ACKNOWLEDGMENT
The work was supported by the Program for International Collaboration and Exchange of the National Foundation
for Natural Sciences of China (No. 31110103908) and the Foundation for International Scientific and Technical Collaboration
of Xinjiang-Uygur A. R. (No. 20126023).
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