CN104031073A - Preparation method of azadirachtin dry powder - Google Patents
Preparation method of azadirachtin dry powder Download PDFInfo
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- CN104031073A CN104031073A CN201410275257.8A CN201410275257A CN104031073A CN 104031073 A CN104031073 A CN 104031073A CN 201410275257 A CN201410275257 A CN 201410275257A CN 104031073 A CN104031073 A CN 104031073A
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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 invention provides a preparation method of azadirachtin dry powder. The preparation method comprises the following steps of mixing dried azadirachtin seeds with petroleum ether, and then stirring to extract azadirachtin oil; drying extracting residues in air to obtain an azadirachtin cake; then, mixing the azadirachtin cake with methanol and then stirring and extracting, filtering to collect filtrate and concentrating, and then oscillating and mixing concentrate with distilled water; extracting by dichloromethane to obtain azadirachtin extract, adding a polar organic solvent A to dissolve and mix with a solvent B; and then filtering under reduced pressure to obtain solid precipitates, and drying the solid precipitates after eluting by a solvent C to obtain the azadirachtin dry powder. The method provided by the invention is simple in process, high in solvent recovery rate, high in azadirachtin active ingredient content and lower in cost. The preparation method disclosed by the invention avoids cross infection of the organic solvent, is beneficial to recycling the solvent, lowers material cost and reduces environment pollution, and is applicable to large-scale production.
Description
Technical field
The present invention relates to a kind of preparation method of biological pesticide, particularly relate to a kind of preparation method of nimbin dry powder.
Background technology
Printing chinaberry (Azadirachta indica A.Juss.) is Meliaceae Melia plant, contains 300 various active compositions, and that wherein insecticidal activity is the highest is nimbin (Azadirachtin).Nimbin (C
35h
44o
16) be the highly oxidized tetracyclic triterpenoid of a class (limonin), there are seven kinds of molecule isomer of Azadirachtin A-G, Azadirachtin A is the nimbin compound that wherein content is the highest, activity is the highest.Print the whole strain plant of chinaberry all containing nimbin, especially plant content the abundantest (0.2%～0.6%) in benevolence.
Nimbin has very strong biological activity to 200 various insects (comprising nearly all important agricultural, storage, sanitary insect pest), simultaneously harmless to higher animal, safer to natural enemies of insects, is to study at present and apply and to obtain biological pesticide the most widely.Print chinaberry seed containing nim oil 40%, first with varsol, remove the extraction that nim oil is conducive to nimbin, also useful milling process extracts the production technique of nim oil.Remove the neem cake organic solvent extraction nimbin of nim oil, conventionally the organic solvent adopting is methyl alcohol, through liquid-liquid extraction, obtain nimbin raw medicine again, this is a kind of paste substance that soaks that contains nimbin, and the content of its nimbin is difference to some extent with the difference of extracting method, extraction process and seal chinaberry provenance.In mimbin extract, contain a large amount of polar molecule compounds, as moisture, protein, carbohydrate etc., so viscosity is large, poor stability, is unfavorable for storing and transportation.Best mode is that mimbin extract is made to nimbin dry powder, convenient storage, transportation and utilization.
Chinese patent application CN1423938A relates to the preparation of high-content nimbin powder, neem seed is ground to the squeezing of shelling and obtain nim oil and neem cake, with solid phase extraction and conventional solvent-extraction process, process neem cake again, obtain printing chinaberry extract, nim oil or seal chinaberry extract are joined in non-polar solvent, the mass ratio of nim oil or seal chinaberry extract and non-polar solvent is 1:3～15, filters or centrifugal collecting precipitate, after being dried, obtains nimbin dry powder.The method is extracted 5 hours at 60 ℃ and process that extract is heated 10 minutes in 50 ℃ of water-baths can make heat-labile nimbin decomposed, is unfavorable for obtaining the nimbin dry powder of high-content, and in method, does not mention the rate of recovery situation of solvent.Chinese patent application CN1423939A has announced and has not contained the preparation method of the nimbin dry powder of aflatoxin, in its preparation process, added alkaline oxidiser, because nimbin is more stable under the solutions of weak acidity of pH3～5, and unstable in alkaline environment, add alkaline oxidiser to cause certain influence to the stability of nimbin.
Summary of the invention
For solving the problems such as prior art gained nimbin dry powder is unstable, Azadirachtin Cotent is low, the invention provides a kind of preparation method of nimbin dry powder, can realize and extract rapidly, continuously nimbin dry powder.
The present invention realizes by following technical proposal: a kind of preparation method of nimbin dry powder, is characterized in that through following each step:
(1) after dry neem seed is mixed by the mass ratio of 1:1 ~ 3 with sherwood oil, stir extraction nim oil, filter to get filtrate and filter residue, in filter residue, by the mass ratio of 1:1 ~ 3, add sherwood oil to continue extraction nim oil, filter to get filtrate and filter residue, merge secondary filtrate, after filter residue is air-dry, be neem cake;
(2) after step (1) gained neem cake is mixed by the mass ratio of 1:1 ~ 3 with methyl alcohol, stir extraction 2～5 minutes, filter to get filtrate and filter residue, in filter residue, press the mass ratio of 1:1 ~ 3, after adding methyl alcohol, stir extraction 2～5 minutes, so repeatedly extract three times, collect three times filtrate, then filtrate is concentrated into 1/3～1/4 of filtrate volume routinely, obtains concentrated solution;
(3) concentrated solution of step (2) is mixed with isopyknic distilled water concussion, add again with the isopyknic methylene dichloride of this mixed solution and extract, stratification, collect the dichloromethane layer of lower floor, upper strata adds same volume dichloromethane extraction again, and stratification is collected dichloromethane layer, the dichloromethane layer the concentration and recovery methylene dichloride that merge secondary, residuum is mimbin extract;
(4) by the mass ratio of mimbin extract and polar organic solvent A, be 1:3～9, with polar organic solvent A dissolving step (3) gained mimbin extract, by the mass ratio of solvent B and mimbin extract, be 15～60:1 again, mimbin extract after dissolving is joined in solvent B under whipped state, obtain mixture;
(5) step (4) gained mixture is carried out to filtration under diminished pressure, obtain solid precipitation and mixed solvent, then be 1:1～3 by the mass ratio of mimbin extract and solvent C, with solvent C drip washing solid precipitation, and collect leacheate, and then solid precipitation is dried, obtain nimbin dry powder.
The secondary filtrate that described step (1) merges is after conventional reclaim under reduced pressure sherwood oil, and residuum is nim oil.
The polar organic solvent A of described step (4) is one or more in ethanol, methyl alcohol, ethyl acetate, acetone, chloroform, methylene dichloride, and several ratios is arbitrarily.
The solvent B of described step (4) is one or more in acetum, pH value that distilled water, mass concentration the are 1% acid calcium sulfate aqueous solution that is 4, and several ratios is arbitrarily.
The whipped state of described step (4) refers to that stirring velocity is the state of 180～1500 revs/min.
The mixed solvent that described step (5) obtains, after conventional concentrating under reduced pressure, reclaims solvent.
The solvent C of described step (5) is one or more in normal hexane, sherwood oil, ether, hexanaphthene, and several ratios is arbitrarily.
The leacheate that described step (5) is collected, after concentrating under reduced pressure, reclaims solvent C.
The present invention extracts nim oil and the mimbin extract in neem seed by method rapidly, continuously, mimbin extract is dissolved in to organic solvent A, B, then this solution is added in solvent C, forms nimbin precipitation, drying precipitated after filtering, and obtains nimbin dry powder.Method technique provided by the invention is simple, solvent recovering rate is high, nimbin active component content is high, cost is lower.Compared with prior art have the following advantages:
1, avoided the crossed contamination of organic solvent, be conducive to the recycling of solvent, the three wastes are less, thereby significantly reduced cost, reduced environmental pollution;
2, processing step is less, and process is simple, and equipment requirements is not high, is convenient to transform;
3, be applicable to scale operation, for the development of neem biotic insecticide provides strong guarantee.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
(1) after dry neem seed 1kg is mixed with sherwood oil 1kg, the Rapid Extraction device being placed in described in Chinese patent ZL200820080967.5 stirs extraction nim oil, filter to get filtrate and filter residue, in filter residue, add sherwood oil 1kg to continue extraction nim oil, filter to get filtrate and filter residue, merge secondary filtrate, after filter residue is air-dry, be neem cake 700g; The secondary filtrate merging, after reclaim under reduced pressure sherwood oil, obtains nim oil 300g;
(2) after step (1) gained neem cake 700g is mixed with methyl alcohol 700g, the Rapid Extraction device that is placed in step (1) stirs extraction 3 minutes, filter to get filtrate and filter residue, after adding methyl alcohol 700g to mix in filter residue, stir extraction 3 minutes, so repeatedly extract three times, collect three times filtrate 2100mL, then by filtrate routinely vacuum concentration to 1/4 of filtrate volume, obtain concentrated solution;
(3) concentrated solution of step (2) is mixed with isopyknic distilled water concussion, add again with the isopyknic methylene dichloride of this mixed solution and extract, stratification, collect the dichloromethane layer of lower floor, in the upper layer substance separating, again add the dichloromethane extraction of same volume, stratification, collects dichloromethane layer, the dichloromethane layer the concentration and recovery methylene dichloride that merge secondary, residuum is mimbin extract 30g;
(4) 30g mimbin extract is dissolved with methyl alcohol 90g, then by the mimbin extract after dissolving under the whipped state 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 to filtration under diminished pressure, obtain solid precipitation and mixed solvent, then be 1:1 by the mass ratio of mimbin extract and solvent C, with normal hexane 30g drip washing solid precipitation, and collect leacheate, then solid precipitation is dried, obtains nimbin dry powder 21g, wherein, mixed solvent is after concentrating under reduced pressure, reclaim solvent, leacheate, after concentrating under reduced pressure, reclaims normal hexane.Through HPLC, detect, 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 obtaining, the content of nimbin A is only 8%.
Embodiment 2
(1) after dry neem seed 100kg is mixed with sherwood oil 200kg, the Rapid Extraction device being placed in described in Chinese patent ZL200820080967.5 stirs extraction nim oil, filter to get filtrate and filter residue, in filter residue, add sherwood oil 200kg to continue extraction nim oil, filter to get filtrate and filter residue, merge secondary filtrate, after filter residue is air-dry, be neem cake 70kg; The secondary filtrate merging, after reclaim under reduced pressure sherwood oil, obtains nim oil 30kg;
(2) after step (1) gained neem cake 70kg is mixed with methyl alcohol 140kg, the Rapid Extraction device that is placed in step (1) stirs extraction 3 minutes, filter to get filtrate and filter residue, after adding methyl alcohol 140kg to mix in filter residue, stir extraction 3 minutes, so repeatedly extract three times, collect three times filtrate 420L, then by filtrate routinely vacuum concentration to 1/3 of filtrate volume, obtain concentrated solution;
(3) concentrated solution of step (2) is mixed with isopyknic distilled water concussion, add again with the isopyknic methylene dichloride of this mixed solution and extract, stratification, collect the dichloromethane layer of lower floor, in the upper layer substance separating, again add the dichloromethane extraction of same volume, stratification, collects dichloromethane layer, the dichloromethane layer the concentration and recovery methylene dichloride that merge secondary, residuum is mimbin extract 3kg;
(4) by ethyl acetate 27kg dissolving for 3kg mimbin extract, then by the mimbin extract after dissolving, under the whipped state of 180 revs/min, join in the distilled water of 180kg, obtain mixture;
(5) step (4) gained mixture is carried out to filtration under diminished pressure, obtain solid precipitation and mixed solvent, then be 1:3 by the mass ratio of mimbin extract and sherwood oil, with sherwood oil 9kg drip washing solid precipitation, and collect leacheate, then solid precipitation is dried, obtains nimbin dry powder 2kg, wherein, mixed solvent is after concentrating under reduced pressure, reclaim solvent, leacheate, after concentrating under reduced pressure, reclaims sherwood oil.Through HPLC, detect, 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 obtaining, the content of nimbin A is only 7%.
Embodiment 3
(1) after dry neem seed 1kg is mixed with sherwood oil 3kg, the Rapid Extraction device being placed in described in Chinese patent ZL200820080967.5 stirs extraction nim oil, filter to get filtrate and filter residue, in filter residue, add sherwood oil 3kg to continue extraction nim oil, filter to get filtrate and filter residue, merge secondary filtrate, after filter residue is air-dry, be neem cake 700g; The secondary filtrate merging, after reclaim under reduced pressure sherwood oil, obtains nim oil 300g;
(2) after step (1) gained neem cake 700g is mixed with methyl alcohol 700g, the Rapid Extraction device that is placed in step (1) stirs extraction 3 minutes, filter to get filtrate and filter residue, after adding methyl alcohol 700g to mix in filter residue, stir extraction 3 minutes, so repeatedly extract three times, collect three times filtrate 2100mL, then by filtrate routinely vacuum concentration to 1/4 of filtrate volume, obtain concentrated solution;
(3) concentrated solution of step (2) is mixed with isopyknic distilled water concussion, add again with the isopyknic methylene dichloride of this mixed solution and extract, stratification, collect the dichloromethane layer of lower floor, in the upper layer substance separating, again add the dichloromethane extraction of same volume, stratification, collects dichloromethane layer, the dichloromethane layer the concentration and recovery methylene dichloride that merge secondary, residuum is mimbin extract 30g;
(4) 30g mimbin extract is dissolved with acetone 180g, again by the mimbin extract after dissolving under the whipped state of 1000 revs/min, in the mixing solutions of the acid calcium sulfate aqueous solution of the acetum that the mass concentration that joins 500g is 1% and pH value=4 of 400g, obtain mixture;
(5) step (4) gained mixture is carried out to filtration under diminished pressure, obtain solid precipitation and mixed solvent, then be 1:2 by the mass ratio of mimbin extract and solvent C, with the mixture drip washing solid precipitation of 30g ether and 30g hexanaphthene, and collect leacheate, then solid precipitation is dried, obtains nimbin dry powder 22g, wherein, mixed solvent is after concentrating under reduced pressure, reclaim solvent, leacheate, after concentrating under reduced pressure, reclaims normal hexane.Through HPLC, detect, 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 obtaining, the content of nimbin A is only 8%.
Claims (8)
1. a preparation method for nimbin dry powder, is characterized in that through following each step:
(1) after dry neem seed is mixed by the mass ratio of 1:1 ~ 3 with sherwood oil, stir extraction nim oil, filter to get filtrate and filter residue, in filter residue, by the mass ratio of 1:1 ~ 3, add sherwood oil to continue extraction nim oil, filter to get filtrate and filter residue, merge secondary filtrate, after filter residue is air-dry, be neem cake;
(2) after step (1) gained neem cake is mixed by the mass ratio of 1:1 ~ 3 with methyl alcohol, stir extraction 2～5 minutes, filter to get filtrate and filter residue, in filter residue, press the mass ratio of 1:1 ~ 3, after adding methyl alcohol, stir extraction 2～5 minutes, so repeatedly extract three times, collect three times filtrate, then filtrate is concentrated into 1/3～1/4 of filtrate volume routinely, obtains concentrated solution;
(3) concentrated solution of step (2) is mixed with isopyknic distilled water concussion, add again with the isopyknic methylene dichloride of this mixed solution and extract, stratification, collect the dichloromethane layer of lower floor, upper strata adds same volume dichloromethane extraction again, and stratification is collected dichloromethane layer, the dichloromethane layer the concentration and recovery methylene dichloride that merge secondary, residuum is mimbin extract;
(4) by the mass ratio of mimbin extract and polar organic solvent A, be 1:3～9, with polar organic solvent A dissolving step (3) gained mimbin extract, by the mass ratio of solvent B and mimbin extract, be 15～60:1 again, mimbin extract after dissolving is joined in solvent B under whipped state, obtain mixture;
(5) step (4) gained mixture is carried out to filtration under diminished pressure, obtain solid precipitation and mixed solvent, then be 1:1～3 by the mass ratio of mimbin extract and solvent C, with solvent C drip washing solid precipitation, and collect leacheate, and then solid precipitation is dried, obtain nimbin dry powder.
2. the preparation method of nimbin dry powder according to claim 1, is characterized in that: the secondary filtrate that described step (1) merges is after conventional reclaim under reduced pressure sherwood oil, and residuum is nim oil.
3. the preparation method of nimbin dry powder according to claim 1, it is characterized in that: the polar organic solvent A of described step (4) is one or more in ethanol, methyl alcohol, ethyl acetate, acetone, chloroform, methylene dichloride, and several ratios is arbitrarily.
4. the preparation method of nimbin dry powder according to claim 1, it is characterized in that: the solvent B of described step (4) is one or more in acetum, pH value that distilled water, mass concentration the are 1% acid calcium sulfate aqueous solution that is 4, and several ratios is arbitrarily.
5. the preparation method of nimbin dry powder according to claim 1, is characterized in that: the whipped state of described step (4) refers to that stirring velocity is the state of 180～1500 revs/min.
6. the preparation method of nimbin dry powder according to claim 1, is characterized in that: the mixed solvent that described step (5) obtains, after conventional concentrating under reduced pressure, reclaims solvent.
7. the preparation method of nimbin dry powder according to claim 1, is characterized in that: the solvent C of described step (5) is one or more in normal hexane, sherwood oil, ether, hexanaphthene, and several ratios is arbitrarily.
8. the preparation method of nimbin dry powder according to claim 1, is characterized in that: the leacheate that described step (5) is collected, after concentrating under reduced pressure, reclaims solvent C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1420121A (en) * | 2002-05-31 | 2003-05-28 | 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 |
| CN101440099A (en) * | 2008-12-31 | 2009-05-27 | 牛赡光 | Industrial large scale extracting method for nimbin dry powder |
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2014
- 2014-06-19 CN CN201410275257.8A patent/CN104031073B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1420121A (en) * | 2002-05-31 | 2003-05-28 | 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 |
| CN101440099A (en) * | 2008-12-31 | 2009-05-27 | 牛赡光 | Industrial large scale extracting method for nimbin dry powder |
Non-Patent Citations (2)
| Title |
|---|
| 段琼芬，等: "4种提取印楝素方法的比较", 《农药》, vol. 44, no. 10, 31 October 2005 (2005-10-31), pages 455 - 457 * |
| 王有琼，等: "快速浸出法提取印楝素浸膏", 《世界农药》, vol. 31, no. 3, 30 June 2009 (2009-06-30), pages 14 - 16 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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