CN104031073B - A kind of preparation method of nimbin dry powder - Google Patents
A kind of preparation method of nimbin dry powder Download PDFInfo
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- CN104031073B CN104031073B CN201410275257.8A CN201410275257A CN104031073B CN 104031073 B CN104031073 B CN 104031073B CN 201410275257 A CN201410275257 A CN 201410275257A CN 104031073 B CN104031073 B CN 104031073B
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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Abstract
The preparation method that the present invention provides a kind of nimbin dry powder, by being stirred extraction neem oil with petroleum ether after being mixed by dry neem seed, by extracting, residue is air-dry is neem cake again, then it is stirred extracting with after methanol mixed, refilter collection filtrate and concentrate, then mix with distilled water concussion, mimbin extract is obtained with dichloromethane extraction, add polar organic solvent A dissolve and mix with solvent B, then solid precipitation is obtained through filtration under diminished pressure, with after solvent C drip washing, solid precipitation is dried, namely obtains nimbin dry powder.Method technique provided by the invention is simple, solvent recovering rate is high, nimbin active component content is high, less costly.Present invention, avoiding the cross-contamination of organic solvent, be beneficial to the recycling of solvent, reduce cost of material and decrease environmental pollution, it is adaptable to large-scale production.
Description
Technical field
The preparation method that the present invention relates to a kind of biological pesticide, the preparation method particularly relating to a kind of nimbin dry powder.
Background technology
Azadirachta Indica A. (AzadirachtaindicaA.Juss.) is Meliaceae melia plant, and containing 300 various active compositions, that wherein insecticidal activity is the highest is nimbin (Azadirachtin).Nimbin (C35H44O16) it is the highly oxidized tetracyclic triterpenoid of a class (limonin), there are seven kinds of molecular isomer of AzadirachtinA-G, AzadirachtinA is wherein content the highest nimbin compound the highest, active.Azadirachta Indica A. tree whole plant all containing nimbin, especially content the abundantest (0.2%～0.6%) in kernel.
200 various insects (including nearly all important agricultural, storage, sanitary insect pest) are had very strong biological activity by nimbin, simultaneously that higher mammal is harmless, and natural enemies of insects are safer, are study and apply and to obtain most commonly used biological pesticide at present.Azadirachta Indica A. seed, containing neem oil 40%, first removes neem oil with varsol and is conducive to the extraction of nimbin, and also useful milling process extracts the production technology of neem oil.Remove the neem cake organic solvent extraction nimbin of neem oil, the organic solvent generally adopted is methanol, nimbin raw medicine is obtained then through liquid-liquid extraction, this is a kind of leaching pasty masses containing nimbin, and the content of its nimbin is with the difference in extracting method, extraction process and Azadirachta Indica A. seeds source and difference to some extent.Containing a large amount of polar molecule compounds in mimbin extract, such as moisture, protein, saccharide etc., so viscosity is big, poor stability, it is unfavorable for storage and transport.Best mode is that mimbin extract is made nimbin dry powder, convenient storage, transport and utilization.
Chinese patent application CN1423938A relates to the preparation of high-content nimbin powder, neem seed is ground squeezing of shelling and obtains neem oil and neem cake, neem cake is processed again by solid phase extraction and Conventional solvents extraction method, obtain Azadirachta Indica A. extract, neem oil or Azadirachta Indica A. extract are joined in non-polar solven, the mass ratio of neem oil or Azadirachta Indica A. extract and non-polar solven is 1:3～15, filters or centrifugal collecting precipitate, obtains nimbin dry powder after drying.The method is extracted 5 hours at 60 DEG C and the process that extract heats 10 minutes in 50 DEG C of water-baths can be made heat-labile nimbin decomposed, is unfavorable for obtaining the nimbin dry powder of high-load, and does not mention the response rate situation of solvent in method.The preparation method that Chinese patent application CN1423939A discloses the nimbin dry powder without aflatoxin, its preparation process adds alkaline oxidiser, due to nimbin under the solutions of weak acidity of pH3～5 more stable, and unstable in alkaline environment, add alkaline oxidiser and the stability of nimbin is caused certain impact.
Summary of the invention
For solving the problems such as prior art gained nimbin dry powder is unstable, Azadirachtin Cotent is low, the preparation method that the present invention provides a kind of nimbin dry powder, can realize extracting nimbin dry powder rapidly, continuously.
The present invention is realized by following technical proposal: the preparation method of a kind of nimbin dry powder, it is characterised in that through following each step:
(1) after dry neem seed being mixed by the mass ratio of 1:1 ~ 3 with petroleum ether, it is stirred extracting neem oil, filter to get filtrate and filtering residue, the mass ratio pressing 1:1 ~ 3 in filtering residue adds petroleum ether continuation extraction neem oil, filter to get filtrate and filtering residue, merge secondary filtrate, after filtering residue is air-dry, be neem cake；
(2) after step (1) gained neem cake being mixed by the mass ratio of 1:1 ~ 3 with methanol, it is stirred extraction 2～5 minutes, filter to get filtrate and filtering residue, filtering residue is pressed the mass ratio of 1:1 ~ 3, stir extraction 2～5 minutes after adding methanol, so repeatedly extract three times, collect three filtrates, then filtrate is concentrated into routinely the 1/3～1/4 of filtrate volume, obtains concentrated solution；
(3) concentrated solution of step (2) is mixed with the concussion of isopyknic distilled water, add and extract with the isopyknic dichloromethane of this mixed liquor, stratification, collect the dichloromethane layer of lower floor, upper strata adds same volume dichloromethane extraction, stratification again, collects dichloromethane layer, merging dichloromethane layer the concentration and recovery dichloromethane of secondary, residue is mimbin extract；
(4) it is 1:3～9 by the mass ratio of mimbin extract Yu polar organic solvent A, with polar organic solvent A dissolving step (3) gained mimbin extract, it is 15～60:1 by the mass ratio of solvent B Yu mimbin extract again, mimbin extract after dissolving is joined in solvent B under stirring, obtains mixture；
(5) step (4) gained mixture is carried out filtration under diminished pressure, obtain solid precipitation and mixed solvent, then be 1:1～3 by the mass ratio of mimbin extract Yu solvent C, with solvent C drip washing solid precipitation, and collect leacheate, then solid precipitation is dried, namely obtains nimbin dry powder.
The secondary filtrate that described step (1) merges is after conventional recovered under reduced pressure petroleum ether, and residue is neem oil.
The polar organic solvent A of described step (4) is one or more in ethanol, methanol, ethyl acetate, acetone, chloroform, dichloromethane, and several ratios is arbitrary.
The solvent B of described step (4) is distilled water, mass concentration be 1% acetum, pH value be 4 acid calcium sulfate aqueous solution in one or more, and several ratios is arbitrary.
The stirring of described step (4) refers to the state that mixing speed is 180～1500 revs/min.
The mixed solvent that described step (5) obtains after conventional concentrating under reduced pressure, recycling design.
The solvent C of described step (5) is one or more in normal hexane, petroleum ether, ether, hexamethylene, and several ratios is arbitrary.
The leacheate that described step (5) is collected after concentrating under reduced pressure, recycling design C.
The present invention extracts the neem oil in neem seed and mimbin extract by method rapidly, continuously, mimbin extract is dissolved in organic solvent A, B, then this solution is added in solvent C, forms nimbin precipitation, drying precipitated after filtration, obtains nimbin dry powder.Method technique provided by the invention is simple, solvent recovering rate is high, nimbin active component content is high, less costly.Compared with prior art have the advantage that
1, avoiding the cross-contamination of organic solvent, be conducive to the recycling of solvent, the three wastes are less, thus considerably reducing cost, decreasing environmental pollution；
2, processing step is less, and process is simple, and equipment requirements is not high, it is simple to convert；
3, suitable in large-scale production, the development for neem biotic insecticide provides strong guarantee.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
(1) after dry neem seed 1kg being mixed with petroleum ether 1kg, it is placed in the Rapid Extraction device described in Chinese patent ZL200820080967.5 and is stirred extracting neem oil, filter to get filtrate and filtering residue, filtering residue adds petroleum ether 1kg continue to extract neem oil, filter to get filtrate and filtering residue, merge secondary filtrate, after filtering residue is air-dry, be neem cake 700g；The secondary filtrate merged, after recovered under reduced pressure petroleum ether, obtains neem oil 300g；
(2) after step (1) gained neem cake 700g being mixed with methanol 700g, it is placed in the Rapid Extraction device of step (1) and is stirred extracting 3 minutes, filter to get filtrate and filtering residue, after filtering residue adds methanol 700g mixing, stirring extracts 3 minutes, so repeatedly extracts three times, collects three filtrate 2100mL, then filtrate vacuum routinely is concentrated into the 1/4 of filtrate volume, obtains concentrated solution；
(3) concentrated solution of step (2) is mixed with the concussion of isopyknic distilled water, add and extract with the isopyknic dichloromethane of this mixed liquor, stratification, collect the dichloromethane layer of lower floor, the upper layer substance separated adds the dichloromethane extraction of same volume, stratification again, collects dichloromethane layer, merging dichloromethane layer the concentration and recovery dichloromethane of secondary, residue is mimbin extract 30g；
(4) 30g mimbin extract methanol 90g is dissolved, then by the mimbin extract after dissolving under the stirring of 1500 revs/min, join in the acid calcium sulfate aqueous solution of pH value=4 of 450g, obtain mixture；
(5) step (4) gained mixture is carried out filtration under diminished pressure, obtain solid precipitation and mixed solvent, then be 1:1 by the mass ratio of mimbin extract Yu solvent C, with normal hexane 30g drip washing solid precipitation, and collect leacheate, then solid precipitation is dried, namely obtains nimbin dry powder 21g, wherein, mixed solvent is after concentrating under reduced pressure, recycling design, leacheate, after concentrating under reduced pressure, reclaims normal hexane.Detecting through HPLC, in gained nimbin dry powder, the content of nimbin A is 14.6%.
And after above-mentioned dry neem seed being processed by prior art, in the nimbin dry powder obtained, the content of nimbin A is only 8%.
Embodiment 2
(1) after dry neem seed 100kg being mixed with petroleum ether 200kg, it is placed in the Rapid Extraction device described in Chinese patent ZL200820080967.5 and is stirred extracting neem oil, filter to get filtrate and filtering residue, filtering residue adds petroleum ether 200kg continue to extract neem oil, filter to get filtrate and filtering residue, merge secondary filtrate, after filtering residue is air-dry, be neem cake 70kg；The secondary filtrate merged, after recovered under reduced pressure petroleum ether, obtains neem oil 30kg；
(2) after step (1) gained neem cake 70kg being mixed with methanol 140kg, it is placed in the Rapid Extraction device of step (1) and is stirred extracting 3 minutes, filter to get filtrate and filtering residue, after filtering residue adds methanol 140kg mixing, stirring extracts 3 minutes, so repeatedly extracts three times, collects three filtrate 420L, then filtrate vacuum routinely is concentrated into the 1/3 of filtrate volume, obtains concentrated solution；
(3) concentrated solution of step (2) is mixed with the concussion of isopyknic distilled water, add and extract with the isopyknic dichloromethane of this mixed liquor, stratification, collect the dichloromethane layer of lower floor, the upper layer substance separated adds the dichloromethane extraction of same volume, stratification again, collects dichloromethane layer, merging dichloromethane layer the concentration and recovery dichloromethane of secondary, residue is mimbin extract 3kg；
(4) 3kg mimbin extract ethyl acetate 27kg is dissolved, then by the mimbin extract after dissolving under the stirring of 180 revs/min, join in the distilled water of 180kg, obtain mixture；
(5) step (4) gained mixture is carried out filtration under diminished pressure, obtain solid precipitation and mixed solvent, then be 1:3 by the mass ratio of mimbin extract Yu petroleum ether, with petroleum ether 9kg drip washing solid precipitation, and collect leacheate, then solid precipitation is dried, namely obtains nimbin dry powder 2kg, wherein, mixed solvent is after concentrating under reduced pressure, recycling design, leacheate, after concentrating under reduced pressure, reclaims petroleum ether.Detecting through HPLC, in gained nimbin dry powder, the content of nimbin A is 16.2%.
And after above-mentioned dry neem seed being processed by prior art, in the nimbin dry powder obtained, the content of nimbin A is only 7%.
Embodiment 3
(1) after dry neem seed 1kg being mixed with petroleum ether 3kg, it is placed in the Rapid Extraction device described in Chinese patent ZL200820080967.5 and is stirred extracting neem oil, filter to get filtrate and filtering residue, filtering residue adds petroleum ether 3kg continue to extract neem oil, filter to get filtrate and filtering residue, merge secondary filtrate, after filtering residue is air-dry, be neem cake 700g；The secondary filtrate merged, after recovered under reduced pressure petroleum ether, obtains neem oil 300g；
(2) after step (1) gained neem cake 700g being mixed with methanol 700g, it is placed in the Rapid Extraction device of step (1) and is stirred extracting 3 minutes, filter to get filtrate and filtering residue, after filtering residue adds methanol 700g mixing, stirring extracts 3 minutes, so repeatedly extracts three times, collects three filtrate 2100mL, then filtrate vacuum routinely is concentrated into the 1/4 of filtrate volume, obtains concentrated solution；
(3) concentrated solution of step (2) is mixed with the concussion of isopyknic distilled water, add and extract with the isopyknic dichloromethane of this mixed liquor, stratification, collect the dichloromethane layer of lower floor, the upper layer substance separated adds the dichloromethane extraction of same volume, stratification again, collects dichloromethane layer, merging dichloromethane layer the concentration and recovery dichloromethane of secondary, residue is mimbin extract 30g；
(4) 30g mimbin extract acetone 180g is dissolved, again by the mimbin extract after dissolving under the stirring of 1000 revs/min, join in the mixed solution of acid calcium sulfate aqueous solution of the acetum that mass concentration is 1% of 500g and pH value=4 of 400g, obtain mixture；
(5) step (4) gained mixture is carried out filtration under diminished pressure, obtain solid precipitation and mixed solvent, then be 1:2 by the mass ratio of mimbin extract Yu solvent C, with the mixture drip washing solid precipitation of 30g ether and 30g hexamethylene, and collect leacheate, then solid precipitation is dried, namely obtains nimbin dry powder 22g, wherein, mixed solvent is after concentrating under reduced pressure, recycling design, leacheate, after concentrating under reduced pressure, reclaims normal hexane.Detecting through HPLC, in gained nimbin dry powder, the content of nimbin A is 15.9%.
And after above-mentioned dry neem seed being processed by prior art, in the nimbin dry powder obtained, the content of nimbin A is only 8%.
Claims (3)
1. the preparation method of a nimbin dry powder, it is characterised in that through following each step:
(1) after dry neem seed being mixed by the mass ratio of 1:1 ~ 3 with petroleum ether, it is stirred extracting neem oil, filter to get filtrate and filtering residue, the mass ratio pressing 1:1 ~ 3 in filtering residue adds petroleum ether continuation extraction neem oil, filter to get filtrate and filtering residue, merge secondary filtrate, after filtering residue is air-dry, be neem cake；
(2) after step (1) gained neem cake being mixed by the mass ratio of 1:1 ~ 3 with methanol, it is stirred extraction 2～5 minutes, filter to get filtrate and filtering residue, filtering residue is pressed the mass ratio of 1:1 ~ 3, stir extraction 2～5 minutes after adding methanol, so repeatedly extract three times, collect three filtrates, then filtrate is concentrated into routinely the 1/3～1/4 of filtrate volume, obtains concentrated solution；
(3) concentrated solution of step (2) is mixed with the concussion of isopyknic distilled water, add and extract with the isopyknic dichloromethane of this mixed liquor, stratification, collect the dichloromethane layer of lower floor, upper strata adds same volume dichloromethane extraction, stratification again, collects dichloromethane layer, merging dichloromethane layer the concentration and recovery dichloromethane of secondary, residue is mimbin extract；
(4) it is 1:3～9 by the mass ratio of mimbin extract Yu polar organic solvent A, with polar organic solvent A dissolving step (3) gained mimbin extract, it is 15～60:1 by the mass ratio of solvent B Yu mimbin extract again, mimbin extract after dissolving is joined in solvent B under stirring, obtains mixture；
Described polar organic solvent A is one or more in ethanol, methanol, ethyl acetate, acetone, chloroform, dichloromethane, and several ratios is arbitrary；
Described solvent B is distilled water, mass concentration be 1% acetum, pH value be 4 acid calcium sulfate aqueous solution in one or more, and several ratios is arbitrary；
Described stirring refers to the state that mixing speed is 180～1500 revs/min；
(5) step (4) gained mixture is carried out filtration under diminished pressure, obtain solid precipitation and mixed solvent, then be 1:1～3 by the mass ratio of mimbin extract Yu solvent C, with solvent C drip washing solid precipitation, and collect leacheate, then solid precipitation is dried, namely obtains nimbin dry powder；Described solvent C is one or more in normal hexane, petroleum ether, ether, hexamethylene, and several ratios is arbitrary.
2. the preparation method of nimbin dry powder according to claim 1, it is characterised in that: the secondary filtrate that described step (1) merges is after conventional recovered under reduced pressure petroleum ether, and residue is neem oil.
3. the preparation method of nimbin dry powder according to claim 1, it is characterised in that: the leacheate that described step (5) is collected after concentrating under reduced pressure, recycling design C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410275257.8A CN104031073B (en) | 2014-06-19 | 2014-06-19 | A kind of preparation method of nimbin dry powder |
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| CN104031073B true CN104031073B (en) | 2016-06-29 |
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| CN104893576A (en) * | 2015-06-10 | 2015-09-09 | 中国林业科学研究院资源昆虫研究所 | Shellac varnish containing biological insect-resist agent azadirachtin and preparation method of shellac varnish |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1362020A (en) * | 2001-12-27 | 2002-08-07 | 海南英得利生物技术开发有限公司 | Nim mextractive producing process |
| CN1199980C (en) * | 2002-05-31 | 2005-05-04 | 云南中科生物产业有限公司 | Mtehod for microwave extracting nimbin from nim kernel |
| CN1423938A (en) * | 2002-12-02 | 2003-06-18 | 华南农业大学 | Preparation for high-content nimbin powder |
| CN101440099B (en) * | 2008-12-31 | 2010-08-18 | 牛赡光 | Industrial large scale extracting method for nimbin dry powder |
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