Rhododendron active ingredient of cough and asthma
【Abstract】 Objective To study the Rhododendron in the cough and asthma activity of chemical composition. Methods macroporous resin, silica gel column chromatography and other elements of modern chromatographic separation and, based on physical and chemical constants and spectral analysis for structural identification. Results from the Rhododendron has 7 kinds of isolated active compounds were Farrerol (farrerol), myricetin (myricetin), quercetin (quercetin), dihydro-
quercetin (taxifolin), umbelliferone ( umbelliferone), hyperin (hyperine), juniper brain (juniper camphor). Conclusions for further development of Rhododendron anti-cough and asthma drug
provides a reliable chemical-based, and the right to amend
previously thought Rhododendron herbs essential oil as the main component of the cuckoo-one to provide an experimental
basis for the idea.
Key words Rhododendron flavone flavanone coumarin volatile oil
Studies on the Active Compounds to Relieve Cough and
Dyspnea from Rhododendron dauricum
Abstract: ObjectiveTo study the natural products to treat cough and dyspnea from Rhododendron dauricum.MethodsActive compounds were isolated by macroporous absorption resin, silica gel columns and other modern chromatographic method.Seven chemical constituents were identified on the basis of chemical methods and spectral evidences. ResultsFrom this plant, seven active compounds were isolated. They were determined as farrerol, myricetin, quercetin, taxifolin,
umbelliferone, hyperin and juniper camphor. ConclusionThe results supplied the researching base to develop the effective
part of Folium Rhododendri Daurici as the new medicine.
Key words: Rhododendron dauricum L.; Flavone; Flavanone;
Coumarin; Volatile oil
Rhododendron Rhododendron dauricum L. as Rhododendron Rhododendron, medicinal its leaves [1]. With a cough, expectorant, asthma, high efficacy, side effects [2], mainly in the north-east. In order to develop an effective part of
Rhododendron as the material basis of traditional Chinese medicine efficacy of new drugs, this experiment Rhododendron in the chemical composition of Extraction, Isolation and structural identification. Through the use of solvent and a variety of modern chromatographic separation technique to the seven kinds of isolated compounds were Farrerol (farrerol), myricetin (myricetin), quercetin (quercetin), dihydro-
quercetin (taxifolin), umbrella Flower lactone
(umbelliferone), hyperin (hyperoside), juniper brain (juniper
camphor). In particular, through the development of the medicinal herbs in the high content of volatile oil constituents of crystallization separation, identification and determination of work on the amendment in the past that the
mountain is covered with red herbs essential oil as the main component of the cuckoo elements provide an experimental basis for the idea.
An apparatus and materials
1H-NMR and 13C-NMR spectra and two-dimensional NMR
spectroscopy using Burker Avance 400 MHz NMR spectrometer
determination; samples purified using Shimadzu LC-8A High
Performance Liquid Chromatography; XT5 melting point was determined with micro-melting point instrument (temperature uncorrected). Thin-layer chromatography with silica gel G,
silica gel chromatography (200 ~ 300 mesh) for Qingdao Marine Chemical Plant production; AB-8 macroporous adsorption resin,
Nankai University, Tianjin Chemical Plant production; thin-
layer chromatography with silica the plastic sheet for the inverting plate (RP-18F254) for German Merck products. 2004-09
herbs collected from Heilongjiang Province, Mudanjiang, Heilongjiang University of Chinese Medicine through the School of Pharmacy, Professor Wang Zhenyue identification.
2 Extraction and Separation of
Rhododendron appropriate crushing dry leaves by steam distillation to collect the total volatile oil, volatile oil by silica gel column chromatography, petroleum ether - ethyl
acetate gradient elution with some frozen precipitation of crystals obtained by ether compound repeated recrystallization ?. Ethanol extracted dry ingredients twice recovered after the solvent by adding chloroform and water layers to two-phase
return, sub-taking chloroform layer obtained Isolation and Identification of Compounds Compounds ? ~ ?, the remaining
water layer, vacuum concentration to the appropriate amount in order to AB-8 macroporous resin adsorption, the macroporous resin pre-finished, with 30% ethanol elution, eluate evaporated by the decompression after the recovery of isolated
compounds on the silica gel column ?.
3 Structure Identification
Compound ?: light yellow needle crystal, light yellow needle crystal, soluble in methanol, ether and dilute alkali solution, insoluble in water, with sodium tetrahydro-boron
reaction was purple, proved to be dihydro-flavonoids.
Molecular formula C17H16O5. 1H-NMR (DMSO-d6, 400 MHz) δ:
12.36 (1H, s, OH); 9.55 (2H, br.s, OH); 7.30 (2H, d, J = 8.8 Hz, H-2 ', H-6'), 6.78 (2H, d, J = 8.4 Hz, H-3 ', H-5'), 5.38
(1H, dd, J = 3.2Hz, J = 12.4 Hz, H-2) , 3.16 (1H, dd, J = 12.4
Hz, J = 17.2 Hz, H-3a), 2.72 (1H, dd, J = 3.2 Hz, J = 16.8 Hz, H-3b). 13C-NMR (DMSO-d6) δ: 197.5 (C = O), 162.9 (C-9), 158.9
(C-7), 158.1 (C-5), 157.9 (C-4 '), 129.9 (C - 1 '), 128.5 (C-
2', C-6 '), 115.7 (C-3', C-5 '), 103.8 (C-6), 103.07 (C-8),
102.3 (C-10) , 78.5 (C-2), 42.6 (C-3), 8.1,8.8 (2 × CH3).
Reported in the literature Farrerol with the corresponding data comparison [3] are basically the same, according to the above attribution and analysis for the identification of
compound ? Farrerol (farrerol).
Compounds ?: yellow needle crystal, mp 330 ?
(decomposition). Molecular formula C15H10O8. 1H-NMR (DMSO-d6,
400 MHz) δ: 12.51 (1H, s, OH), 10.74 (1H, s, OH), 9.23 (3H, m, OH), 8.83 (1H, s, OH), 7.23 (2H, s, H-2 'and 6'), 6.34 (1H,
d, J = 1.76 Hz, H -8), 6.17 (1H, d, J = 1.76 Hz, H -6). 13C-
NMR (DMSO-d6) δ: 178.9 (C-4), 163.4 (C-7), 161.3 (C-5), 156.7
(C-9), 146.2 (C-2), 145.0 (C-3 '), 144.9 (C-5'), 135.5 (C-3),
135.6 (C-4 ') 120.8 (C-1'), 108.2 (C-2 'and 6'), 103.5 (C-
10) , 98.0 (C-6), 93.7 (C-8). The above data and reported in the literature Myricetin match [4], and therefore compounds ?
is myricetin (myricetin).
Compound ?: light yellow powder, mp 225 ~ 227 ?. 1H-NMR
(DMSO-d6, 400 MHz) δ: 11.92 (1H, s, OH), 10.95 (1H, s, OH), 9.06 (1H, s, OH), 8.20 (1H, s, OH), 7.24 (1H, d, J = 1.8 Hz, H
-2 '), 7.11 (1H, dd, J = 8.2 Hz, 1.8Hz, H -6'), 7.05 (1H, d, J = 8.2 Hz, H-5 ') 5.96 (1H, d, J = 2.0 Hz, H-8), 5.92 (1H, d, J = 2.0 Hz, H-6), 5.22 ((1H, d, J = 12.0 Hz, H-2) , 4.67 (1H, d, J = 4.2 Hz, OH), 4.59 (1H, dd, J = 12.0 Hz, 4.2 Hz, H-3). 13C-
NMR (DMSO-d6) δ: 199.6 (C-4) , 165.7 (C-7), 165.3 (C-5),
164.7 (C-9), 146.2 (C-4 '), 145.8 (C-3'), 129.4 (C-1 '), 120.9
(C - 6 '), 116.3 (C-2'), 115.7 (C-5 '), 101.0 (C-10), 97.5 (C-
8), 96.1 (C-6), 84.4 (C-2), 73.0 ( C-3). The above figures reported in the literature dihydro-quercetin with the same [4], and therefore compounds ? is a dihydro-quercetin
(taxifolin).
Compounds ?: yellow needle-like crystals (MeOH), mp 313 ~ 314 ?. HCl-Mg reaction to red. 1H-NMR and 13C-NMR data
reported in the literature of quercetin in line [5], and therefore compounds ? of quercetin (quercetin). Reposted elsewhere in the paper for free download http://
Compound ?: light yellow crystal, molecular formula C9H6O3, the compound 1H-NMR, 13C-NMR and reported in the literature umbelliferone line [6], and therefore compounds ?
as umbelliferone (umbelliferone).
Compound ?: light yellow needle crystal (MeOH), mp 233 ~ 235 ?. HCl-Mg reaction of red, Molish reaction showed purple ring, indicating that the compound of flavonoid glycosides. The compounds were characterized by acid hydrolysis and thin
layer can only be detected after the D-galactose. 1H-NMR
(DMSO-d6, 400 MHz) δ: 7.65 (1H, dd, J = 6.8,2.0 Hz, H-6 '),
7.54 (1H, d, J = 2.0 Hz, H-2'), 6.83 (1H, d, J = 6.8 Hz, H-5
'), 6.18 (1H, d, J = 2.0 Hz, H-6), 6.38 (1H, d, J = 2.0 Hz, H-
8), 5.40 ( 1H, d, J = 7.0 Hz, H-1 "gal). 13C-NMR (DMSO-d6,
DEPT) 177.4 (C-4), 164.6 (C-7), 161.2 (C-5), 156.3 ( C-2),
156.2 (C-9), 148.5 (C-4 "), 144.8 (C-3 '), 133.5 (C-3), 122.0
(C-1'), 121.1 (C-6 ') , 116.0 (C-5 '), 115.2 (C-2'), 103.8 (C-
10), 101.9 (C-1 "), 98.8 (C-6), 93.6 (C-8), 75.8 (C - 5 "),
73.2 (C-3"), 71.2 (C-2 "), 67.9 (C-4"), 60.1 (C-6 ") 1H-NMR
and 13C-NMR data reported in the literature hypericin glycosides to compare the corresponding data [7,8] Both are basically the same, according to the above attribution and analysis for the identification of compounds ? hyperin
(Hyperin).
Compounds ?: colorless needle-like crystal (Et2O), mp:
164 ~ 166 ?, Molecular Formula: C15H26O. From the source and are given in 15 C-NMR carbon speculated that it might as sesquiterpene compounds. According to compounds 1H-NMR, 13C-
NMR and two-dimensional HH COSY, HSQC (see Table 1) and HMBC correlation chart (see Figure 1), the compound is connected to each carbon atom and the proton chemical shift for attribution . 1H-NMR (DMSO-d6, 400MHz) δ: 0.94 (3H, s ,15-
CH3); 1.04 (1H, m, H-1); 1.10 (1H, d, J = 3 Hz, H-8); 1.11
(3H, s, H-14); 1.13 (1H, bs, H-10); 1.29 (1H, m, H-6); 1.37
(1H, m, H-8); 1.40 (1H, m, H-1); 1.53 (2H, m, H-7); 1.62 (1H,
bs, H-4); 1.64 (3H, s ,13-CH3); 1.67 (3H, s ,12-CH3); 1.78
(1H, m, H-6); 1.88 (1H, t, J = 12Hz, H-2); 2.47 (1H, dt, J =
2.4 Hz, 12 Hz, H-2); 2.80 (1H, dd, J = 16 Hz, 2 Hz, H-4). 13C-
NMR (DMSO-d6) δ: 131.4 (C-3), 121.0 (C-11), 72.3 (C-5), 55.6
(C-10), 45.3 (C-1), 43.6 (C-6 ), 41.0 (C-8), 34.8 (C-9), 25.5
(C-2), 24.6 (C-4), 22.1 (C-14), 20.2 (C-7), 20.0 (C-12 and
13), 18.1 (C-15). Based on the above results show that the compound ? of juniper brain (juniper camphor). Table 1 juniper brain HSQC data map (omitted)
【References】
[1] Song Liren, Hong Xun. Dictionary of Modern Chinese medicine, the next book [M]. Beijing: People's Health Publishing House, 2001:2290.
[2] Institute of Materia Medica Chinese Academy of Sciences. Rhododendron treatment of chronic bronchitis in clinical and experimental research data (3 ~ 4) [J]. 1971:38.
[3] Liu Long, Yong-Fu Feng. Mountainsides red chemical
constituents of ? [J]. Chimica Sinica, 1976,34 (3): 223.
[4] Wang Yan, Li-Ling Zhou, Li Rui, et al. Ampelopsis
chemical constituents of [J]. Chinese herbal medicine, 2002,25 (4): 254.
[5] De-Quan Yu Yang Hill. NMR spectroscopy Handbook of Analytical Chemistry seventh volumes [M]. Beijing: Chemical Industry Press, 1999:820.
[6] SHI Yao, Li Ding Xiang, Min Zhi-Da, et al.
Heterophylla the chemical constituents of Zanthoxylum [J].
Chinese herbal medicine, 2006,37 (1): 13.
[7] Chang Chen. TCM Chemical Reference Work Manual [M]. Beijing: Chinese Medical Science and Technology Press, 1999:169.
[8] Hatano T, Yasuha T, Yoshihara R. Inhibitoty elects of galloylated lavonoids on santhine oxidese [J]. Planta Med, 1991,57:83. Reposted elsewhere in the paper for free download http://