CN101838300A - Method for extracting residual abamectin - Google Patents
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- CN101838300A CN101838300A CN 201010192026 CN201010192026A CN101838300A CN 101838300 A CN101838300 A CN 101838300A CN 201010192026 CN201010192026 CN 201010192026 CN 201010192026 A CN201010192026 A CN 201010192026A CN 101838300 A CN101838300 A CN 101838300A
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Abstract
The invention relates to a method for extracting residual abamectin from crystallization mother liquor, which comprises the steps of removing ester impurities and further separating each component by using a C18 column or a silica gel column. The separation and extraction process is simple; the selected and used solvent is cheap, safe and environment-friendly, and meets the industrialized requirement; and the effective ingredient B1 has high yield and reaches about 90 percent.
Description
Technical field
[0001] the present invention relates to a kind of residual method that bioactive microbiotic component is arranged of from the microbiotic waste liquid, extracting, relate in particular to a kind of from the crystalline mother solution of Avrmectin the method for separation and Extraction active princlple B1 and relevant biological activity component.
Background technology
Avrmectin, English name Avermectins is to be had desinsection, killed ten hexa-atomic Macrocyclic lactone compounds of mite, eelworm-killing activity by university's big village intelligence in the Japanese north etc. and the class that U.S. Merck company at first develops.Avrmectin has been widely used in the control of animal parasitosis control and crop pests since coming out the beginning of the eighties.
Avrmectin comprises 8 component: A1a, A1b, A2a, A2b, B1a, B1b, B2a, B2b altogether, and mainly containing 4 kinds is A1a, A2a, B1a and B2a, and wherein the biological activity of avermectinB1a is the strongest.
The production process of Avrmectin is as follows: with preparing liquid spawn through preferred high yield slant strains, fermentation culture is about 260 hours then, fermentation ends, with fermented liquid through filter press, abandon filtrate, get the mycelium filter cake and use methanol extraction after drying, afterwards desolventizing and phase inversion dehydration dissolubility and part alcohol dissolubility impurity, add amount of methanol or ethanol then and carry out crystallization, can obtain Avrmectin crystallization (B1 component) and crystalline mother solution.
Residual homologue A1, A2, the B2 component that Avrmectin (B1) and Avrmectin are arranged in crystalline mother solution, also contain the lipid acid of 8～18 carbon and the Ester that forms with glycerine thereof in the mother liquor, shared per-cent consists of in the mother liquor of above component after purifying solvent: the B1 component accounts for about 5%; B2+A2+A1 accounts for about 40%; Ester class impurity accounts for about 50%.The B1 component is to be widely used in animal and plant present stage with pest control and parasitic component, and A1, A2, B2 component have insecticidal activity equally, are the components that awaits developing.Wherein the B2a component is a kind of one of active higher component of the underground nematode of plant that kills.Yet, from mother liquor, further adopt the crystalline method directly to separate wherein residual active constituent, almost be impossible, this is because the existence and the A component of a large amount of ester class impurity are difficult for due to the crystallization.
China began to produce Avrmectin annual production so far and has reached about 2000 tons from 1993, but in crystalline mother solution residual Avrmectin (accounting for the per-cent of total amount) about 15% is arranged since extract not come out and abandoned or crime of illegal selling or presenting cultural relics of private collection, still there are Avrmectin B2a, A2a, A1a isoreactivity composition all to remain in the mother liquor and, cause the environmental pollution and the wasting of resources not by rational Application.
Summary of the invention
The objective of the invention is the problem that is difficult to extract at present Avrmectin crystalline mother solution activeconstituents, a kind of method of extracting residual abamectin is provided, it by column chromatography under the control of suitable temperature, pressure, the active principle crystallization yield is reached more than 90%, thereby satisfied the needs of branch of industry, solved that people thirst for solving for a long time and the technical barrier of failing to succeed.
Above-mentioned technical purpose of the present invention is achieved by the following technical programs:
A kind of method of extracting residual abamectin may further comprise the steps:
A, crystalline mother solution distillation is removed solvent, obtain first oily liquid behind the desolventizing;
B, employing silica gel column chromatography method further separate first oily liquid: the stationary phase that column chromatography is used is a silica gel, moving phase is that volume ratio is 2/1 ethyl acetate/petroleum ether, carry out wash-out under 50 ℃～60 ℃ of column temperatures, post are pressed greater than the condition of 0.5MPa, effusive at first component is the ester solubility impurity; Flowing out back change single solvent ethyl acetate at the ester solubility impurity is moving phase, avermitilis strain B1, A1, B2, A2 four components wash-out from pillar are come out, then the elutriant distillation is removed ethyl acetate, obtain to contain second oily liquid of B1, A1, B2, A2 four components;
C, employing carbon octadecylsilane column chromatography method split B1, A1, B2, A2 four components in described second oily liquid: the stationary phase that column chromatography is used is C18, moving phase is that volume ratio is the methanol of (81～90)/(10～19), wash-out under 50 ℃～60 ℃ of column temperatures, post are pressed greater than the condition of 0.5MPa, effusive at first component is the ester solubility impurity, be followed successively by B2a, A2a, B1b, B1a, A1a thereafter, reclaim the elutriant that contains B2a, B1b and B1a respectively, last underpressure distillation removes solvent and obtains B1a, B1b, B2a.
Preferably, the volume ratio of described methanol moving phase is 85/17.
The present invention also provides a kind of method of extracting residual abamectin, may further comprise the steps:
A, crystalline mother solution distillation is removed solvent, obtain first oily liquid behind the desolventizing;
B, employing silica gel column chromatography method further separate first oily liquid: the stationary phase that column chromatography is used is a silica gel, moving phase is that volume ratio is 2/1 ethyl acetate/petroleum ether, carry out wash-out under 50 ℃～60 ℃ of column temperatures, post are pressed greater than the condition of 0.5MPa, effusive at first component is the ester solubility impurity; Flowing out back change single solvent ethyl acetate at the ester solubility impurity is moving phase, avermitilis strain B1, A1, B2, A2 four components wash-out from pillar are come out, then the elutriant distillation is removed ethyl acetate, obtain to contain second oily liquid of B1, A1, B2, A2 four components;
C, the employing silica gel column chromatography method splits the B1 in described second oily liquid, A1, B2, A2 four components: the stationary phase that column chromatography is used is a silica gel, moving phase is that volume ratio is ethyl acetate/trichloromethane/methylene chloride of 9/9/2/1, column temperature is 50 ℃～60 ℃, post is pressed and is maintained 0.5MPa～3MPa, effusive at first component is the elutriant that contains the A component, thereafter for containing the elutriant of B component, after the elutriant that will contain the B component then removes solvent with distillation method, dissolve 60 ℃～70 ℃ backflows with ethanol or methyl alcohol, under agitation condition, be cooled to 5 ℃～30 ℃ at last, separate out B1a.
In the modern high performance liquid chromatography, the separating effect quality depends on the selection of chromatograph packing material to a great extent.Chromatography utilizes different substances to distribute in the selectivity of different phases, with moving phase the mixture in the stationary phase is carried out wash-out, and materials different in the mixture can move along stationary phase with different speed, finally reach isolating effect.That the present invention selects is inexpensive, the moving phase of safety, environmental protection, cooperates stationary phase, under suitable temperature and pressure, according to the column chromatography principle effectively from the crystalline mother solution of Avrmectin separation and Extraction go out B1, A1, B2, A2 component.
The method of extraction residual abamectin provided by the invention, behind above-mentioned steps b, it is that C1 or C2 can isolate each component that two kinds of alternative steps are arranged.
Step C1:
Stationary phase: octadecylsilane (C18);
Moving phase: methanol=(81～90)/(10～19);
At 50～60 ℃,, adopt Ultraviolet Detector to carry out on-line monitoring greater than carrying out wash-out under 5 kilograms of pressure conditions.It flows out the component sequencing: B2a, A2a, B1b, B1a, A1a, and substep reclaims above-mentioned component; After part methyl alcohol was removed in the underpressure distillation of recovery liquid, active constituent can be separated out.With regard to B1a, being concentrated to B1a concentration is 5%～6% o'clock, can separate out in about 15 ℃.
Step C2:
Stationary phase still is a silica gel, moving phase is that volume ratio is ethyl acetate/trichloromethane/methylene chloride of 9/9/2/1,50 ℃～60 ℃, carry out column chromatography under greater than 5 kilograms of pressure, can be with A(A1+A2) and B(B1+B2) split, the component that promptly flows out post earlier is A1a and A2a mixture, and effusive afterwards component is the mixture of B1a and B2a.The latter, drops to 5 ℃～30 ℃ then and carries out crystallization 60 ℃～70 ℃ dissolvings that reflux with ethanol or methyl alcohol behind desolventizing, but the B1a major part crystallize out, crystallization yield reaches about 90% of theoretical yield.
Because the structure of A1a, A2a, B1a and B2a is very approximate, separate comparatively difficulty of above-mentioned four kinds of materials, the yield of conventional column chromatography extracting substance composition is generally at about 80% of theoretical yield, and the method yield of extraction residual abamectin provided by the invention can reach more than 90%, has obvious improvement, and simple to operate, cost is low.
In sum, the present invention has following beneficial effect:
1, solved the problem that prior art Avrmectin crystalline mother solution activeconstituents is difficult to extract, for from now on from the Avrmectin waste liquid effectively the separation and Extraction active ingredient opened up direction;
2, separation-extraction technology is simple;
3, the solvent of selecting for use is inexpensive, safety, environmental protection, meets the industrialization demand;
4, crystallization yield height, the active principle yield of separating out after concentrating reaches about 90% of theoretical yield.
Embodiment
Embodiment one:
(1) getting 14 kilograms of Avrmectin crystalline mother solutions, is to remove neat solvent under the 0.08MPa condition in 70 ℃, vacuum tightness, 10 kilograms of the oily liquids of winning.Analyze through high performance liquid chromatography HPLC, this oily liquid contains B1a5.5%, B2a16.7%, A2a14.2%, A1a11.1%;
(2) 10 liters of ethyl acetate of adding and 5 liters of sherwood oils are made moving phase in first oily liquid, and 60 ℃ of dissolvings that reflux are standby;
(3) with silicagel column with moving phase wash-out balance after, it is standby to make liquid level reduce to bed dignity;
(4) go up sample, to join slowly on the chromatography column bed surface with first oily liquid after the moving phase dissolving, pressurize afterwards and open the bottom eluent stream and export, after making sample liquid enter a body fully, close bottom eluent stream outlet, above the bed body, slowly fill it up with moving phase, and be tightly connected with the basin of contain moving phase; Open down spout, the normal pressure wash-out is pressurized to 0.5Mpa gradually after about 30 minutes, wash-out under 50 ℃ of conditions, when detecting after grease class impurity flows out fully, use ethyl acetate instead and be moving phase and under 60 ℃, 1.5MPa condition, continue wash-out, complete wash-out comes out with A1a, A2a, B1a, B2a, reclaim elutriant, vacuum distillation recovered solvent must contain second oily matter of A1a, A2a, B1a, B2a four components;
(5) employing carbon octadecylsilane column chromatography method splits B1, A1, B2, A2 four components in described second oily liquid:
Concrete operations are as follows: 1. with the second oily liquid dissolve with methanol, slowly join octadecylsilane post bed surface; 2. open down outlet, make enter a body fully after, under 50 ℃, 0.5Mpa, begin to carry out wash-out: be 90/10 methanol wash-out 10 minutes with ratio earlier with methanol moving phase, be 88/12 methanol wash-out 20 minutes with ratio afterwards, be that 85/15 methanol was carried out wash-out 15 minutes with ratio afterwards, employing can be carried out the online detection of Ultraviolet Detector of length scanning automatically, effusive at first component is a spot of impurity, flows out components such as B2a, A2a, B1b, B1a, A1a afterwards successively; 3. reclaim the elutriant that contains each component respectively, the elutriant that reclaims is distilled respectively except that methanol solvate, can obtain B2a, A2a, B1b, B1a, A1a each component, the B1a yield is 95.6%, and purity reaches 80%; The B2a yield is 94.7%, and purity reaches 80%.
Embodiment two:
(1) getting 14 kilograms of Avrmectin crystalline mother solutions, is to remove neat solvent under the 0.08MPa condition in 70 ℃, vacuum tightness, 10 kilograms of the oily liquids of winning.Analyze through high performance liquid chromatography HPLC, this oily liquid contains B1a5.5%, B2a16.7%, A2a14.2%, A1a11.1%;
(2) 14 liters of ethyl acetate of adding and 7 liters of sherwood oils are made moving phase in first oily liquid, and 50 ℃ of dissolvings that reflux are standby;
(3) with silicagel column with moving phase wash-out balance after, it is standby to make liquid level reduce to bed dignity;
(4) go up sample, to join slowly on the chromatography column bed surface with first oily liquid after the moving phase dissolving, pressurize afterwards and open the bottom eluent stream and export, after making sample liquid enter a body fully, close bottom eluent stream outlet, above the bed body, slowly fill it up with moving phase, and be tightly connected with the basin of contain moving phase; Open down spout, the normal pressure wash-out is pressurized to 1.5MPa after about 30 minutes gradually, wash-out under 60 ℃ of conditions, when detecting after grease class impurity flows out fully, use ethyl acetate instead and be moving phase and continue wash-out under 60 ℃, 2MPa condition, complete wash-out comes out with A1a, A2a, B1a, B2a, reclaims elutriant, vacuum distillation recovered solvent must contain the oily matter of A1a, A2a, B1a, B2a four components;
(5) employing carbon octadecylsilane column chromatography method splits B1, A1, B2, A2 four components in described second oily liquid:
Concrete operations are as follows: 1. with the second oily liquid dissolve with methanol, slowly join octadecylsilane post bed surface; 2. open down outlet, after making sample liquid enter a body fully, beginning with volume ratio under 60 ℃, 3Mpa is 85//17 methanol moving phase wash-out 30 minutes, employing can be carried out the online detection of Ultraviolet Detector of length scanning automatically, effusive at first component is a spot of impurity, flows out components such as B2a, A2a, B1b, B1a, A1a afterwards successively; 3. reclaim the elutriant contain each component respectively and the elutriant that reclaims is distilled respectively desolventize, can obtain B2a, A2a, B1b, B1a, A1a each component, the B1a yield is 94%, and purity reaches 92%; The B2a yield is 95%, and purity reaches 92%.
Embodiment three:
(1) getting among the embodiment 1 oily matter that contains A1a, A2a, B1b, B1a, B2a four components that (4) step obtained, is 2/1 ethyl acetate/methanol dissolving with volume ratio, must sample liquid;
(2) with silicagel column with the moving phase balance good after, above-mentioned sample liquid is joined the good silicagel column bed surface of balance, open down afterwards outlet, treat to begin wash-out with moving phase after sample liquid enters in the post bed fully, column temperature is 60 ℃, post is pressed is 3MPa, and moving phase is that volume ratio is ethyl acetate/trichloromethane/methylene chloride of 9/9/2/1; With the online detection of Ultraviolet Detector, effusive component is A component (A1a+A2a) earlier, be B component (B1a+B2a) afterwards, reclaim respectively that the elutriant underpressure distillation that will contain the B component removes neat solvent, add ethanol afterwards in 70 ℃ of dissolvings that reflux, cool to about 30 ℃ under agitation condition then, spend the night, B1a+B2a is crystallizable separating out, the B1a+B1b yield can reach about 90%, and purity reaches 90% (B1a+B1b).
Embodiment four:
(1) gets the oily matter that contains A1a, A2a, B1b, B1a, B2a four components that (4) step obtained among the embodiment 2, use acetic acid ethyl dissolution, get sample liquid;
(2) with silicagel column with the moving phase balance good after, sample liquid in above-mentioned (1) is joined the good silicagel column bed surface of balance, open down afterwards outlet, treat to begin wash-out with moving phase after sample liquid enters in the post bed fully, column temperature is 50 ℃, post is pressed is 0.5MPa, and moving phase is that volume ratio is ethyl acetate/trichloromethane/methylene chloride of 9/9/2/1; With the online detection of Ultraviolet Detector, effusive component is A component (A1a+A2a) earlier, be B component (B1a+B2a) afterwards, reclaim respectively that the elutriant underpressure distillation that will contain the B component removes neat solvent, add methyl alcohol afterwards in 60 ℃ of dissolvings that reflux, cool to about 5 ℃ under agitation condition then, spend the night, B1a+B2a is crystallizable separating out, the B1a+B2a yield can reach 91%, and purity reaches 85%(B1a+B2a).
Claims (3)
1. method of extracting residual abamectin may further comprise the steps:
A, crystalline mother solution distillation is removed solvent, obtain first oily liquid behind the desolventizing;
B, employing silica gel column chromatography method further separate first oily liquid: the stationary phase that column chromatography is used is a silica gel, moving phase is that volume ratio is 2/1 ethyl acetate/petroleum ether, carry out wash-out under 50 ℃～60 ℃ of column temperatures, post are pressed greater than the condition of 0.5MPa, effusive at first component is the ester solubility impurity; Flowing out back change single solvent ethyl acetate at the ester solubility impurity is moving phase, avermitilis strain B1, A1, B2, A2 four components wash-out from pillar are come out, then the elutriant distillation is removed ethyl acetate, obtain to contain second oily liquid of B1, A1, B2, A2 four components;
C, employing carbon octadecylsilane column chromatography method split B1, A1, B2, A2 four components in described second oily liquid: the stationary phase that column chromatography is used is C18, moving phase is that volume ratio is the methanol of (81～90)/(10～19), wash-out under 50 ℃～60 ℃ of column temperatures, post are pressed greater than the condition of 0.5MPa, effusive at first component is the ester solubility impurity, be followed successively by B2a, A2a, B1b, B1a, A1a thereafter, reclaim the elutriant that contains B2a, B1b and B1a respectively, obtain B1a, B1b, B2a after last underpressure distillation removes solvent.
2. the method for an extraction residual abamectin as claimed in claim 1 is characterized in that described methanol mobile phase volume ratio is 85/17.
3. method of extracting residual abamectin may further comprise the steps:
A, crystalline mother solution distillation is removed solvent, obtain first oily liquid behind the desolventizing;
B, employing silica gel column chromatography method further separate first oily liquid: the stationary phase that column chromatography is used is a silica gel, moving phase is that volume ratio is 2/1 ethyl acetate/petroleum ether, carry out wash-out under 50 ℃～60 ℃ of column temperatures, post are pressed greater than the condition of 0.5MPa, effusive at first component is the ester solubility impurity; Flowing out back change single solvent ethyl acetate at the ester solubility impurity is moving phase, avermitilis strain B1, A1, B2, A2 four components wash-out from pillar are come out, then the elutriant distillation is removed ethyl acetate, obtain to contain second oily liquid of B1, A1, B2, A2 four components;
C, the employing silica gel column chromatography method splits the B1 in described second oily liquid, A1, B2, A2 four components: the stationary phase that column chromatography is used is a silica gel, moving phase is that volume ratio is ethyl acetate/trichloromethane/methylene chloride of 9/9/2/1, column temperature is 50 ℃～60 ℃, post is pressed and is maintained 0.5～3MPa, effusive at first component is the elutriant that contains the A component, thereafter for containing the elutriant of B component, after the elutriant that will contain the B component then removes solvent with distillation method, dissolve 60 ℃～70 ℃ backflows with ethanol or methyl alcohol, under agitation condition, be cooled to 5 ℃～30 ℃ at last, separate out B1a.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977168A (en) * | 2012-12-17 | 2013-03-20 | 石家庄市兴柏生物工程有限公司 | Extraction and preparation method of abamectin B2a |
| CN102977167A (en) * | 2012-12-17 | 2013-03-20 | 石家庄市兴柏生物工程有限公司 | Abamectin active pharmaceutical ingredient and pesticide using same as active component |
| CN103011966A (en) * | 2012-12-21 | 2013-04-03 | 浙江建中竹业科技有限公司 | Method for producing organic fertilizer with plant charcoal and bamboo vinegar |
| CN103030675A (en) * | 2012-11-19 | 2013-04-10 | 河北威远生物化工股份有限公司 | Process of extracting abamectin components B1 and B2 step by step by utilizing crystallization method |
| CN103641873A (en) * | 2013-12-17 | 2014-03-19 | 华北制药集团爱诺有限公司 | Method for preparing high-purity Abamectin |
| CN105418708A (en) * | 2015-11-17 | 2016-03-23 | 石家庄市兴柏生物工程有限公司 | Method for extracting residual avermectin B1a from primary crystallization mother liquor of avermectin B1a |
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Cited By (13)
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| CN103030675B (en) * | 2012-11-19 | 2015-08-26 | 河北威远生化农药有限公司 | A kind of technique utilizing crystallization process step by step arithmetic AVERMECTIN B1 component and B2 component |
| CN103030675A (en) * | 2012-11-19 | 2013-04-10 | 河北威远生物化工股份有限公司 | Process of extracting abamectin components B1 and B2 step by step by utilizing crystallization method |
| CN102977167A (en) * | 2012-12-17 | 2013-03-20 | 石家庄市兴柏生物工程有限公司 | Abamectin active pharmaceutical ingredient and pesticide using same as active component |
| CN102977168B (en) * | 2012-12-17 | 2013-08-21 | 石家庄市兴柏生物工程有限公司 | Extraction and preparation method of abamectin B2a |
| WO2014094404A1 (en) * | 2012-12-17 | 2014-06-26 | 石家庄市兴柏生物工程有限公司 | Avermectin raw material and pesticide using same as active ingredient |
| CN102977167B (en) * | 2012-12-17 | 2014-11-05 | 石家庄市兴柏生物工程有限公司 | Abamectin active pharmaceutical ingredient and pesticide using same as active component |
| CN102977168A (en) * | 2012-12-17 | 2013-03-20 | 石家庄市兴柏生物工程有限公司 | Extraction and preparation method of abamectin B2a |
| CN103011966A (en) * | 2012-12-21 | 2013-04-03 | 浙江建中竹业科技有限公司 | Method for producing organic fertilizer with plant charcoal and bamboo vinegar |
| CN103011966B (en) * | 2012-12-21 | 2014-07-02 | 浙江建中竹业科技有限公司 | Method for producing organic fertilizer with plant charcoal and bamboo vinegar |
| CN103641873A (en) * | 2013-12-17 | 2014-03-19 | 华北制药集团爱诺有限公司 | Method for preparing high-purity Abamectin |
| CN103641873B (en) * | 2013-12-17 | 2015-10-28 | 华北制药集团爱诺有限公司 | A kind of preparation method of Avrmectin |
| CN105418708A (en) * | 2015-11-17 | 2016-03-23 | 石家庄市兴柏生物工程有限公司 | Method for extracting residual avermectin B1a from primary crystallization mother liquor of avermectin B1a |
| CN105418708B (en) * | 2015-11-17 | 2018-01-30 | 石家庄市兴柏生物工程有限公司 | A kind of method that residual abamectin B1a is extracted in the primary crystallization mother liquor from Avermectin B1a |
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| CN101838300B (en) | 2012-03-14 |
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