全 文 ： 336 Chin J Nat Med Sep. 2008 Vol. 6 No. 5 2008 年 9 月 第 6 卷 第 5 期

Chinese Journal of Natural Medicines 6 (2008) 0336−0338
doi: 10.3724/SP.J.1009.2008.00336
Chinese
Journal of
Natural
Medicines







A New Methyl Orsellinate Glycoside from the Aerial Parts
of Rhododendron primulaeflorum
LI Xue-Feng1,2, JIN Hui-Zi1, YANG Ming2, CHEN Gang1, ZHANG Wei-Dong1,3*
1School of Pharmacy, Shanghai Jiaotong University, Shanghai 200240;
2Jiangxi University of Traditional Chinese Medicine, Key Laboratory of Modern Chinese Preparation, Ministry of Education, Nanchang
330004;
3Department of Phytochemistry, Second Military Medical University, Shanghai 200433, China
Available online 20 Sep. 2008
【ABSTRACT】 AIM: To study the chemical constituents of the aerial parts of Rhododendron primulaeflorum Bur. et Franch.
METHODS: The solvent extraction, Sephadex LH-20, silica gel column chromatography and pre-HPLC were used to isolate and
purify the constituents. Structural identification of isolated compounds was based on physical properties and spectroscopic analysis.
RESULTS: A new methyl orsellinate glycoside, methyl 2-hydroxy-6-methyl benzoate 4-O-β-D-glucopyranoside (1) and a known
methyl orsellinate (2) were isolated from this plant. CONCLUSION: A new compound is isolated, and this study enriches the chemical
constituents of R. primulaeflorum.
【KEY WORDS】 Rhododendron primulaeflorum; Methyl 2-hydroxy-6-methyl benzoate 4-O-β-D-glucopyranoside; Methyl orselli-
nate; Chemical constituents
【CLC Number】 R284.1 【Document Code】 A 【Article ID】1672-3651(2008)05-0336-03

Rhododendron primulaeflorum (Ericaceae), is a shrub
mainly distributed in the southwest district of China, espe-
cially in Tibetan Autonomous Region, Yunnan and Sichuan
provinces[1]. Its leaves and sprouts are used as a traditional
Chinese folk drug for treating chronic tracheitis, relieving
cough and asthma[2]. No phytochemical investigation on this
plant has been documented. In our studies of the chemical
constituents from this plant, we described the isolation and
structure elucidation of a new methyl orsellinate glycoside (1)
and a known methyl orsellinate (2)(Fig. 1).



Fig. 1 Structures of compounds 1 and 2

【Received on】 2008-08-30
【Foundation Item】 This project was supported by Scientific
Foundation of Shanghai Commission of Science and Technology,
Shanghai, China (No.06DZ19717).
【*Corresponding author】Zhang Wei-Dong: Prof., Tel/Fax: 86-21-
34205989, E-mail: wdzhangy@hotmail.com
1 Results and Discussion
Compound 1 was obtained as white powder. Its molecu-
lar formula was determined as C15H20O9 on the basis of
HR-ESI-MS (C15H20O9Na requires m/z, 367.100 5, found
367.1006). The 13C NMR and DEPT spectra of 1 (Table 1)
gave 15 carbon signals, including one methyl, one methylene,
one methoxy, one keto, seven methines, four quaternary car-
bons. The 1H NMR spectrum (Table 1) of 1 contained signals
for one singlet methyl at δH 2.47 (3H, s), one methoxyl group
at δ 3.91 (3H, s), two meta-coupled aromatic protons at δ
6.48 (2H, d, J = 2.1 Hz). The 1H and 13C NMR spectral data
of 1 were similar to those of methyl orsellinate (2) except for
the presence of a β-D-glucopyranosyl unit: δH 4.96 (1H, d, J
= 8.0 Hz, H-1), δC 101.4 (C-1), 78.2 (C-5), 77.9 (C-3), 74.7
(C-2), 71.2 (C-4) and 62.4 (C-6). It was also confirmed by
TLC comparing the acid hydrolysate of 1 with glucose au-
thentic sample. The connectivity of the benzoate skeleton
with the glucose was established by HMBC experiment. In
the HMBC spectrum, long-range coupling was observed
between H-1 at δ 4.96 (1H, d, J = 8.0 Hz) and C-4 at δ 162.8,
suggesting that the glucose was connected to C-4. On the
basis of the above evidence, the structure of 1 was elucidated
to be 2-hydroxy-6-methyl benzoate 4-β-D-glucopyranoside.
Compound 2 was obtained as achromatous prisms. The
LI Xue-Feng, et al. /Chinese Journal of Natural Medicines 2008, 6(5): 336−338
2008 年 9 月 第 6 卷 第 5 期 Chin J Nat Med Sep. 2008 Vol. 6 No. 5 337

1H NMR spectrum (Table 1) of 2 contained signals for one
singlet methyl at δH 2.40 (3H, s), one methoxyl group at δH
3.86 (3H, s), two meta-coupled aromatic protons at δH 6.14
(1H, d, J = 2.1 Hz) and 6.17 (1H, d, J = 2.1 Hz). Altogether,
nine carbon signals were observed in the 13C NMR and
DEPT spectra (Table 1), including one methyl, one methoxyl,
two methines, and five quaternary carbons. Further studies on
the 1H and 13C NMR spectra of 2 revealed that these data
closely resembled those of methyl orsellinate[3]. Therefore, 2
was deduced as methyl orsellinate.
2 Methods and Materials
2.1 General Experimental Methods
Melting points were measured using X-4 micro melting
point apparatus (uncorrected). 1H (500 MHz) and 13C (125
MHz) NMR spectra were recorded on a Bruker DRX-500
instrument. IR spectra were measured on a Bruker Vector 22
IR spectrometer. ESI-MS were recorded on an Agilent 1100
series mass spectrometer. All solvents used were of analytical
grade (Shanghai Chemical Company, Ltd.) Sephadex LH-
20 (Pharmacia Biotech). Silica gel was used for column
chromatography, and precoated silica GF254 plates used for
TLC (Qingdao Haiyang Chemical Company, Ltd.).
2.2 Plant Material
The fresh samples of R. primulaeflorum Bur. et Franch.
were collected in Xianggelila, Geza, Yunnan Province in
China, in July, 2006. The plant material was identified by
Prof. Zheng Hanchen, Department of Phytochemistry, Sec-
ond Military Medical University. The voucher specimens
(collection No. SJTUYCDJ) are deposited at Herbarium of
School of Pharmacy, Shanghai Jiaotong University, Shanghai,
China.

Table 1 1H and 13C NMR spectral data of 1 and 2 in CD3OD (δ , J in Hz)
Compound 1 Compound 2
Position δC δH δC δH
1 108.9 106.0
2 165.0 163.9
3 102.8 6.48 (1H, d, J = 2.1 Hz) 101.9 6.14 (1H, d, J = 2.1 Hz)
4 162.8 166.4
5 112.8 6.48 (1H, d, J = 2.1 Hz) 112.7 6.17 (1H, d, J = 2.1 Hz)
6 143.9 144.8
7 172.9 173.6
8 23.9 2.47 s 24.5 2.40 s
9 52.3 3.91 s 52.3 3.86 s
1 101.4 4.96 (1H, d, J = 8.0 Hz)
2 74.7 3.45 m
3 77.9 3.41 m
4 71.2 3.39 m
5 78.2 3.28 m
6 62.4 3.88 (1H, br d, J = 12.0 Hz)
3.71 (1H, dd, J = 12.0, 5.0 Hz)

3 Extraction and Isolation
The air-dried and powdered aerial parts of R. primulae-
florum (15.0 kg) were extracted with 95% ethanol three times
at room temperature, each process lasting two hours. After
removal of the solvent by evaporation, methanol extract
(2 019.3 g) was afforded. Then the extract was suspended in
4 L aqueous and partitioned successively with petroleum
ether, chloroform, ethyl acetate and n-butanol, affording four
extracts 721.7 g, 1041.4 g, 17.5 g and 520.3 g, respectively.
Part of the n-butanol layer (230.0 g) was chromatographed on
a silica gel column with the gradient CH2Cl2 − MeOH (20 : 1,
10 : 1, 5 : 1, 1 : 1, MeOH) as eluents. The obtained fractions
were combined on the basis of silica gel TLC and 10 frac-
tions (Fr1-Fr10) were obtained. The Fr4 was subjected to
silica gel column (mesh 200-300) and Sephadex LH-20 to
afford compound 1 (24 mg). Part of the chloroform layer
(200.0 g) was subjected to chromatographic techniques, such
as silica gel column (mesh 200-300), Sephadex LH-20, com-
pound 2 (37 mg) was obtained.
References
[1] Li ZQ, Zhang WJ, Hu XJ, et al. Herbalogical textual re-
search on Tibetan medicine DaLi [J]. J Chin Med Mater,
1998, 21 (1): 39-40.
LI Xue-Feng, et al. /Chinese Journal of Natural Medicines 2008, 6(5): 336−338
338 Chin J Nat Med Sep. 2008 Vol. 6 No. 5 2008 年 9 月 第 6 卷 第 5 期

[2] Li ZQ, Zhang WJ, Hu XJ, et al. Pharmacognostic studies of
Tibetan medicine Da-Li [J]. J Chin Med Mater, 1997, 20(7):
332-335.
[3] Feng L, Shen YM. Chemical constituents from the stem bark
of Trewia nudiflora [J]. Nat Prod Res Dev, 2005, 17(3):
294-297.

樱草杜鹃中一个新的葡萄糖基苯甲酸酯类成分
李雪峰 1,2, 金慧子 1, 杨 明 2, 陈 刚 1, 张卫东 1,3*
1上海交通大学药学院, 上海 200240;
2江西中医学院现代中药制剂教育部重点实验室, 南昌 330004;
3第二军医大学药学院, 上海 200433
【摘 要】 目的：研究樱草杜鹃(Rhododendron primulaeflorum)的干燥地上部分的化学成分。方法：应用硅胶柱色谱, Sephadex
LH-20 柱色谱, 制备高效液相色谱等方法分离和纯化化合物, 通过光谱方法及理化性质鉴定化合物的结构。结果：从樱草杜鹃中
分离得到 1 个新化合物, 鉴定为 2-羟基-6-甲基苯甲酸甲酯 4-O-β-D-葡萄糖苷(1), 及苔色酸甲酯(2)。结论：从该植物中分得一个
新化合物, 丰富了樱草杜鹃的化学成分。
【关键词】 樱草杜鹃; 2-羟基-6-甲基苯甲酸甲酯 4-O-β-D-葡萄糖苷; 苔色酸甲酯; 化学成分

【基金项目】 上海市科委中药现代化专项重大项目(06DZ19717)

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