CN102516213B - Sesquiterpene compound and preparation method and application thereof - Google Patents
Sesquiterpene compound and preparation method and application thereof Download PDFInfo
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- CN102516213B CN102516213B CN2011103903478A CN201110390347A CN102516213B CN 102516213 B CN102516213 B CN 102516213B CN 2011103903478 A CN2011103903478 A CN 2011103903478A CN 201110390347 A CN201110390347 A CN 201110390347A CN 102516213 B CN102516213 B CN 102516213B
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Abstract
The invention discloses a sesquiterpene compound and a preparation method and application thereof. The molecular formula of the sesquiterpene compound is C15H18O4, and the preparation method of the sesquiterpene compound comprises the steps: adding a whole chloranthus henryi (Chlotanthushenryi Hemsl.) or tissue of the chloranthus henryi into an organic solvent to be leached to obtain a leaching solution, extracting the leaching solution by using ethyl acetate or chloroform, and concentrating, separating and purifying extraction liquid to obtain the sesquiterpene compound, wherein the organic solvent is one of or two of carbinol, ethanol, ethyl acetate and acetone. The sesquiterpene compound extracted and separated from the chloranthus henryi is provided with a novel structure, has good antioxidative activity, can be used for preparing antioxidant pharmaceuticals, antioxidant cosmetics and antioxidant health-care foods and has good developing prospect.
Description
Technical field
The present invention relates to the active components of plants field, relate in particular to a kind of sesquiterpenoid and its preparation method and application.
Background technology
Wide leaf Chloranthus spicatus (Chloranthus henryi Hemsl.) is Chloranthaceae (Chloranthaceae) Chloranthus (Chloranthus) plant, has another name called Herba Chloranthi Henryi (Herba Choranthi seu Lysimachiae), Four Heavenly Kings, great Ye and oneself, careless rhinoceros.Wide leaf Chloranthus spicatus is perennial herb or undershrub, high 40-65cm (even can up to 100cm), and root stock is sturdy, and chocolate has several elongated brown fibrous roots; Stem is upright, and joint obviously expands, and leaf, to life, is born in stem top for common 4, and idol has 6 (being verticillate shape) wide ellipse or obovate, long 9～18cm, and wide 5～9cm, give birth on inflorescence spike top and armpit is given birth to, common not tally or total shape branch, drupe is spherical; In 4～November of flowering fruit bearing stage, be born under hillside in dark and damp ground and the other thick grass of cheuch.Be distributed in the provinces and regions (Ye Guorong such as Jiangsu, Anhui, Jiangxi, Fujian, Hunan, Hubei, Guangdong, Guangxi, Sichuan, Guizhou, Zhejiang, Shaanxi, Gansu, Peng Dewei. the herbal textual of careless rhinoceros, CHINA JOURNAL OF CHINESE MATERIA MEDICA .2001,26 (3): 212-213.).Wide leaf Chloranthus spicatus have dispel the wind, dehumidify, invigorate blood circulation, the effect of stagnation resolvation, can be used for the treatment of arthralgia due to wind-cold-dampness pathogen BI syndrome, rheumatic numbness, pain, menoxenia, wound, cough due to wind and cold and carbuncle pyogenic infections from tumour or sore etc.
The research of Chloranthus plant chemical ingredient is more, is mainly sesquiterpenoid, has good prospect in medicine.As far back as 1978, the people such as Masaaki Uchida separate and obtain 2 ring eudesmane type sesquiterpene lactones from Herba Pileae Scriptae Chloranthus glaberMakino, called after chloranthalactone A and B (Uchida M, Kusano G, Kondo Y, Nozoe S, Takemoto T Two newsesquiterpenoids from Chloranthus glaber Makino.Heterocycles, 1978,9 (2): 139-44.).
Within 1979, with Jun Kawabata in 1981 etc., reported to separate from Herba chloranthi japonici to obtain 2 ring eudesmane type sesquiterpene shizukanolide A and dehydro-shizukanolide (shizukanolide B), wherein dehydro-shizukanolide is exactly the chloranthalactoneA of Masaaki Uchida report.The active testing result shows that dehydro-shizukanolide has medium anti-mycotic activity ((a) Kawabata J, Tahara S, Mizutani J, Furusaki A, Hashiba N, Matsumoto T.Shizukanolides, two sesquiterpenoids from Chloranthus japonicus (Chloranthaceae) .Agric.Biol.Chem., 1979, 43 (4): 885-887. (b) Kawabata J, Tahara S, Mizutani J.Isolation and structure elucidation of four sesquiterpenesfrom Chloranthus japonicus (Chloranthaceae) .Agric.Bioc.Chem., 1981, 45 (6): 1447-1453.).
Separating the Herba chloranthi japonici that the people such as Masaaki Uchida produce from Japan again and obtain 5 ring eudesmane type sesquiterpenes, is respectively chloranthalactone A-E.By degraded, the absolute configuration of measured ORD history estimating chloranthalactone A and B.Chloranthalactone A-C demonstrates stronger cytotoxicity, IC to mouse Lymphosarcima L-5178Y cell
50be respectively 2.5,1.0-2.5 and 20 μ g/mL (Uchida M, Koike Y, Kusano G, Kondo Y, Nozoe S, Kabuto C, Takemoto T.Studies on the constituents of Chloranthus spp.III.Sixsesquiterpenes from Chloranthus japonicus.Chem.Pharm.Bull., 1980,28 (1): 92-102.).
Summary of the invention
The invention provides a kind of sesquiterpenoid, this compound is to extract the natural active matter obtained in wide leaf Chloranthus spicatus plant, has anti-oxidant activity.
A kind of sesquiterpenoid, its structural formula is suc as formula shown in (I):
The invention provides the preparation method of described sesquiterpenoid, comprise the following steps:
(1) (Chloranthus henryi Hemsl.) the whole strain of wide leaf Chloranthus spicatus or its tissue are added to lixiviate in organic solvent, obtain vat liquor;
Wherein, described organic solvent is one or both in methyl alcohol, ethanol, ethyl acetate and acetone;
(2) ethyl acetate or chloroform extraction for vat liquor, extraction liquid, after concentrated, separation and purification, obtains sesquiterpenoid.
In step (1), the whole strain of described wide leaf Chloranthus spicatus or its tissue can be whole strain or its tissue of the Wild plant of self-sow; Can be also whole strain or its tissue of the plant through tissue culture, can think the tissue culture of wide leaf Chloranthus spicatus.The wide leaf Chloranthus spicatus tissue culture that the tissue-culturing quick-propagation of take obtains is sesquiterpenoid of the present invention as raw material extracts, and has the advantages such as the raw material culture cycle is short, steady sources.
Can prepare by the following method by described tissue culture: get stem apex, stem with bud or the leaf of wide leaf Chloranthus spicatus as explant, after sterilization, be inoculated in inducing culture, induce callus and bud clump; Be inoculated in subculture medium (MS+NAA 0.2, MS+6BA 0.02+NAA 0.5 or MS+6BA 2+NAA 0.2) and carry out multiplication culture; Transfer to root induction in root media after multiplication culture, obtain tissue culture.
Described tissue can be for wild or through root, stem, the leaf of the wide leaf Chloranthus spicatus of tissue culture.
The whole strain of described wide leaf Chloranthus spicatus or its tissue can directly add or add after crushed lixiviate in organic solvent, will carry out the leaching that lixiviate more is conducive to sesquiterpenoid after raw material pulverizing.
The weight ratio of the whole strain of described wide leaf Chloranthus spicatus or its tissue and organic solvent is preferably 1: 1-1: 8.
Described lixiviate can be cold soaking or thermal backflow extraction.
In step (2), described separation and purification can be: extraction liquid is carried out to the silica gel column chromatography separation, and the gained cut carries out recrystallization, anti-phase normal pressure chromatography or high performance liquid chromatography again to be separated.By the multistep separation and purification, can obtain the sesquiterpenoid that purity is higher.
Preferably, described silica gel column chromatography is separated into: one or more mixtures of take in sherwood oil, normal hexane, ethyl acetate, alcohol and water are eluent, and extraction liquid is carried out to gradient elution.
More preferably, described silica gel column chromatography is separated into: with the volume ratio petrol ether/ethyl acetate mixed solution of 9: 1,5: 1,1: 1,1: 3,1: 9 and ethyl acetate, extraction liquid is carried out to gradient elution successively; Perhaps, with the volume ratio n-hexane/ethyl acetate mixed solution of 9: 1,5: 1,1: 1,1: 3,1: 9, extraction liquid is carried out to gradient elution successively.
The present invention also provides the application of described sesquiterpenoid in preparing anti-oxidation medicine.This medicine be take sesquiterpenoid of the present invention as main active ingredient, adds acceptable auxiliary material on pharmaceutics and makes, and can make preparation according to the formulation preparation method of putting down in writing on pharmaceutics.Described preparation can be for injection liquid, drip liquid, powder injection, granule, tablet, electuary, powder, oral liquid, sugar coated tablet, film coated tablet, enteric coated tablet, suck agent, granule, pill, paste, sublimed preparation, sprays, pill, disintegrating agent, orally disintegrating tablet, micropill etc.
The present invention also provides the application of this sesquiterpenoid in preparing the antioxidation cosmetic product.These makeup be take sesquiterpenoid of the present invention as main active ingredient, add acceptable makeup auxiliary material and make.
The present invention also provides the application of this sesquiterpenoid in preparing antioxidant functional food.This protective foods be take sesquiterpenoid of the present invention as main active ingredient, adds acceptable protective foods auxiliary material and makes.
The polarity difference that the present invention utilizes sesquiterpene leniently extracts in leaf Chloranthus spicatus, separate and obtained a kind of sesquiterpenoid with novel structure, and the method is easy and simple to handle, extract that yield is high, product purity is high, is applicable to large-scale production.
Test by antioxidation in vitro, show that sesquiterpenoid provided by the invention has antioxygenation preferably, its IC
50value is 36 μ M, can be used for preparing anti-oxidation medicine, antioxidation cosmetic product or antioxidant functional food, has good DEVELOPMENT PROSPECT.
Embodiment
Tissue culture and the Fast-propagation of embodiment 1 wide leaf Chloranthus spicatus
Get the leaf of wide leaf Chloranthus spicatus (Chloranthus henryi Hemsl.) as explant, by follow procedure, carry out disinfection: slightly wash → 5% detergent solution rinsing 5min of draw materials → tap water → tap water rinses in 30min → 75% ethanol scrub surfaces → 0.1% mercuric chloride solution in 5min → 2% chlorine bleach liquor that sterilizes the 20min → aseptic water washing 4～6 times of sterilizing, and then explant is cut into to the long segment of 0.5～1.0cm in aseptic working platform; Be inoculated in inducing culture, the bud clump derived separated and cuts into to the stem section of 2cm, forward on the substratum (MS+6BA 2+NAA0.2) of new different hormone combinations and carry out succeeding transfer culture, give whole day illumination after inoculation, room temperature 20-28 ℃; After 3d, base portion all starts to expand, and after 1 week, axillalry bud starts to sprout, and the sprout tillers growth is very fast; When bud grows to 3～4cm, cut healthy and strong plant and forward on root media, all plant can normal growth, after cultivating one week, induces root, and after 10d, every strain can grow 3～5 roots, and root reaches 4～5cm; Cultivate again one week, robust plant, the leaf look dark green, then throws off the paper lid and practice seedling.
The preparation of embodiment 2 sesquiterpenoids
Get the wide leaf Chloranthus spicatus of 5kg, soak 2 weeks with methyl alcohol, soak solution is with 1L distilled water suspendible after concentrated, and aqueous suspension extracts by the 1L ethyl acetate, and acetic acid ethyl acetate extract is through the concentrated medicinal extract 110g that obtains; With silica gel, (100 orders, 100g) mix sample, carries out purification on normal-phase silica gel column chromatography for separation (200-300 order, 1kg; Silicagel column size L 500mm,
120mm), carry out gradient elution with the volume ratio petrol ether/ethyl acetate mixed solution of 9: 1,5: 1,1: 1,1: 3,1: 9 and ethyl acetate successively, each 5L; TLC detects cut; Use again recrystallizing methanol.
The preparation of embodiment 3 sesquiterpenoids
Get the wide leaf Chloranthus spicatus of 5kg, use the 5L alcohol reflux, extracting solution is concentrated, aqueous suspension 1L chloroform extraction, and chloroform extraction liquid is concentrated; With silica gel, (100 orders, 100g) mix sample, carries out purification on normal-phase silica gel column chromatography for separation (200-300 order, 1kg; Silicagel column size L 500mm,
120mm), carry out gradient elution with the volume ratio petrol ether/ethyl acetate mixed solution of 9: 1,5: 1,1: 1,1: 3,1: 9 and ethyl acetate successively, each 5L; TLC detects cut; Use again recrystallizing methanol.
The preparation of embodiment 4 sesquiterpenoids
Get the wide leaf Chloranthus spicatus after 5kg pulverizes, drying, extract by the 5L ethyl acetate backflow, and (100 orders, 100g) mix sample to the silica gel for extracting solution after separation, carries out purification on normal-phase silica gel column chromatography for separation (200-300 order, 1kg; Silicagel column size L 500mm,
120mm), carry out gradient elution with the volume ratio petrol ether/ethyl acetate mixed solution of 9: 1,5: 1,1: 1,1: 3,1: 9 successively, each 5L; TLC detects cut; Use again methyl alcohol/chloroform (volume ratio 3: 1) recrystallization.
The preparation of embodiment 5 sesquiterpenoids
Get the wide leaf Chloranthus spicatus after 5kg pulverizes, drying, by 5L acetone refluxing extraction, (100 orders, 100g) mix sample to the silica gel for extracting solution after separation, carries out purification on normal-phase silica gel column chromatography for separation (200-300 order, 1kg; Silicagel column size L 500mm,
120mm), carry out gradient elution with the volume ratio n-hexane/ethyl acetate mixed solution of 9: 1,5: 1,1: 1,1: 3,1: 9 successively, each 5L; TLC detects cut; Use again acetone/normal hexane (volume ratio 1: 1) recrystallization.
The preparation of embodiment 6 sesquiterpenoids
Get the wide leaf Chloranthus spicatus after 5kg pulverizes, extract with 5L methanol/ethanol mixed solution, extract is concentrated, with 100g diatomite, mixes sample, and the 5L ethyl acetate backflow, carry out purification on normal-phase silica gel column chromatography for separation (200-300 order, 1kg; Silicagel column size L 500mm,
120mm), carry out gradient elution with the volume ratio n-hexane/ethyl acetate mixed solution of 9: 1,5: 1,1: 1,1: 3,1: 9 successively, each 5L; TLC detects cut; Use again acetone/normal hexane (volume ratio 1: 1) recrystallization.
The preparation of embodiment 7 sesquiterpenoids
Get the wide leaf Chloranthus spicatus after 5kg pulverizes, extract with 5L methanol/ethanol mixed solution, extract is concentrated, with 100g diatomite, mixes sample, and the 5L ethyl acetate backflow, carry out purification on normal-phase silica gel column chromatography for separation (200-300 order, 1kg; Silicagel column size L 500mm,
120mm); After segmentation, with anti-phase normal pressure chromatography/high performance liquid chromatography, separate, eluent is that (1: 9-9: 1), the detection wavelength of high performance liquid chromatography is 210nm to methanol/water; Use recrystallizing methanol.
Wherein, in embodiment 2-7, thin-layer chromatography and column chromatography silica gel are that Haiyang Chemical Plant, Qingdao produces; RP-18 or RP-8 post for reverse phase silica gel; Chromatography is 60-90 ℃ with the sherwood oil boiling point.
The Structural Identification of embodiment 8 sesquiterpenoids
Adopt HPLC to carry out Purity to the compound made, purity is greater than 98% sample and uses mass spectrum and nuclear magnetic resonance technique to carry out Structural Identification, and nucleus magnetic resonance is measured with Bruker AVANCE DRX-500NMR Sectrometer, mark in TMS does; High resolution mass spectrum FTICRMS measures with Bruker ApexSpectrometer; Electrospray ionization mass spectrum ESI-MS measures with Bruker Esquire 3000plusSpectrometer.
The NMR analytical results that table 1 is compound, from results of structural analysis, this material is sesquiterpenoid, molecular formula is C
15h
18o
4, structure is as follows:
The NMR data of table 1 sesquiterpenoid
Embodiment 9 sesquiterpenoid anti-oxidant activities are analyzed
Get a certain amount of sample, be dissolved in dehydrated alcohol, be made into concentration 5mM solution; Successively dilute with dehydrated alcohol, dilute five times at every turn; Get 96 hollow plates, every hole adds ethanolic soln (150 μ M) the 180 μ l of DPPH; Then add successively the sample solution of 5 concentration, each concentration 4 ，Mei hole, hole adds 20 μ l; Rock a little 96 orifice plates, allow it mix; Be placed in thermostat container, 37 ℃ of standing 30min; Measure the OD value in every hole respectively at 517nm and 800nm by microplate reader; Sample concentration when by the Bliss method, obtaining the DPPH clearance rate and be 50%, half is removed experiment.
Remove experimental result by DPPH and know, the IC of this compound
50=36 μ M, show that this compound has antioxygenation preferably.
Embodiment 10 is containing the preparation of sesquiterpenoid dropping pill formulation
Get the 0.5g sesquiterpenoid and mix with the 10.5g PEG-4000, heating and melting, move to after material in the dripping pill drip irrigation, and liquid drops in 6～8 ℃ of whiterusss, and oil removing makes 300 of dripping pills.
Embodiment 11 is containing the preparation of sesquiterpenoid lyophilized injectable powder
Get sesquiterpenoid 0.5g, glucose 4.5g, Sulfothiorine 0.9g and distilled water 1000ml, after said components mixes, lyophilize, 400 of packing, obtain.
Claims (4)
1. a sesquiterpenoid, its structural formula is as shown in formula I:
2. the preparation method of sesquiterpenoid as claimed in claim 1, is characterized in that, comprises the following steps:
(1) the whole strain of wide leaf Chloranthus spicatus or its tissue are added to lixiviate in organic solvent, obtain vat liquor;
Wherein, described organic solvent is one or both in methyl alcohol, ethanol, ethyl acetate and acetone;
(2) ethyl acetate or chloroform extraction for vat liquor, extraction liquid, after concentrated, separation and purification, obtains sesquiterpenoid;
Described separation and purification is: extraction liquid is carried out to the silica gel column chromatography separation, and the gained cut carries out the recrystallization separation again,
Described silica gel column chromatography is separated into: with petrol ether/ethyl acetate mixed solution and the ethyl acetate of volume ratio 9:1,5:1,1:1,1:3,1:9, extraction liquid is carried out to gradient elution successively; Perhaps, with the n-hexane/ethyl acetate mixed solution of volume ratio 9:1,5:1,1:1,1:3,1:9, extraction liquid is carried out to gradient elution successively.
3. preparation method according to claim 2, is characterized in that, in step (1), the weight ratio of the whole strain of described wide leaf Chloranthus spicatus or its tissue and organic solvent is 1:1-1:8.
4. the application of sesquiterpenoid as claimed in claim 1 in preparing anti-oxidation medicine, antioxidation cosmetic product or antioxidant functional food.
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| CN105837592B (en) * | 2015-01-11 | 2018-05-25 | 复旦大学 | Phloroglucin a pair of horses going side by side abietane diterpene-kind compound and preparation method thereof and medicinal usage |
| CN105461763B (en) * | 2015-11-18 | 2018-07-06 | 浙江大学 | A kind of polyphenol disaccharide glycoside compound and its preparation method and application |
| CN105348333B (en) * | 2015-11-18 | 2018-07-06 | 浙江大学 | A kind of chavicol disaccharide glycoside compound and its preparation method and application |
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| CN101209952B (en) * | 2006-12-31 | 2010-07-14 | 中国科学院上海药物研究所 | Sesquiterpenoids, composition thereof, method for extracting the same from plants and application |
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