CN103497226B - Refinement method of methylamino abamectin benzoate - Google Patents
Refinement method of methylamino abamectin benzoate Download PDFInfo
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Abstract
The invention relates to a refinement method of methylamino abamectin benzoate. The refinement method comprises the following steps: carrying out dissolved clarification on methylamino abamectin serving as a raw material in a polar solvent A, then adding phosphoric acid, devitrifying in methylbenzene so as to obtain methylamino abamectin phosphate, dissolving with water, adding an ester solvent B, adjusting the pH value, standing still, layering, carrying out vacuum concentration so as to obtain high-quality methylamino abamectin free alkali, salifying the high-quality methylamino abamectin free alkali and benzoic acid in a methyl tertiary-butyl ether, thus obtaining the high-content methylamino abamectin benzoate. The refinement method is simple in process and can be used for realizing industrial large-scale production; and the product has high purity and is used for preparing high-end preparations.
Description
Technical field
The present invention relates to a kind of process for purification of emamectin-benzoate, belong to pesticide material medicine technical field.
Background technology
Emamectin-benzoate (being called for short first dimension salt) is by the new and effective insecticidal/acaricidal agent of the synthetic one of Avrmectin, especially lepidoptera pest is had to high biological activity, there is the features such as toxicity is low, residual less, nuisanceless, thereby be widely used in agriculture production.
Chinese patent document CN103012525A provides a kind of method of synthesis of methylamines base abamectin benzoate, first Avrmectin is joined in dichloromethane solution, under-20 DEG C～-15 DEG C conditions, add combined oxidation reagent, the Simultaneous Oxidation product obtaining, adding heptamethyldisilazane, under 0～40 DEG C of condition, react 30min～90min, obtain C4 "=O is by the intermediate of selectivity imidization; Under-10 DEG C～0 DEG C condition, taking ethanol as solvent, sodium borohydride is reductive agent, and reaction 1～4h, obtains methylaminoabamectin; Finally add phenylformic acid salify to obtain first dimension salt.The method reaction times is short, easy to operate, and production cost is low, and first dimension salt productive rate is 41.1%～61.2%, and purity is 48.3-62.5%.
The domestic and international content control criterion of emamectin-benzoate raw material is substantially all below 70%, and product purity is lower, can not meet high-end preparation demand.While needing on a small quantity purity compared with high product, adopting silicagel column purifying, this purification process cost is high, and cannot realize a large amount of suitability for industrialized production.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of process for purification of emamectin-benzoate is provided, can obtain the emamectin-benzoate that cost is low, purity is high, solve the bottleneck problem of large-scale commercial production high purity emamectin-benzoate.
Term explanation:
HPLC: high performance liquid chromatography, product content measuring method, conventional being expressed as " HPLC content % ".
Technical scheme of the present invention is as follows:
A process for purification for emamectin-benzoate, comprises that step is as follows:
(1) 20 DEG C～25 DEG C of temperature, Affirm (Merck Co.) is added to solvent orange 2 A, stir molten clearly, drip the mixing solutions of phosphoric acid and solvent orange 2 A, stirring reaction 0.5～1h; Then add toluene stirring and crystallizing 1h; Be cooled to-5 DEG C～5 DEG C, stir 5～6h, centrifugal ,-5 DEG C～5 DEG C toluene wash for filter cake; Vacuum drying product, obtains Affirm (Merck Co.) phosphoric acid salt;
Wherein, Affirm (Merck Co.) raw material: solvent orange 2 A total amount: toluene mass ratio is 1:(3～6): (10～15), Affirm (Merck Co.) and phosphoric acid molar ratios are 1:(1～2);
Described solvent orange 2 A is one of methyl alcohol, ethanol, acetonitrile or combination.
(2) the Affirm (Merck Co.) phosphoric acid salt making in step (1) is added to the water to stirring and dissolving; Add solvent B to stir, sodium hydroxide solution adjust pH is 6～8, and static layering 1～3h separates organic phase, and 35～65 DEG C of vacuum concentration, obtain fine work Affirm (Merck Co.) free alkali;
Wherein, Affirm (Merck Co.) phosphoric acid salt: water: organic solvent mass ratio is 1:(10～15): (6～8);
Described solvent B is ethyl acetate, isopropyl acetate or butylacetate;
(3) the Affirm (Merck Co.) free alkali in step (2) is added in t-butyl methyl ether, stirring and dissolving, keeps 20～25 DEG C of temperature, adds phenylformic acid, stirring reaction 2～5h, in reaction solution, drip normal hexane, 2～3h dropwises, stirring reaction 2～3h, filter, normal hexane washing 1～2 time for filter cake, vacuum drying product, obtains emamectin-benzoate product;
Wherein, Affirm (Merck Co.) free alkali and phenylformic acid mol ratio are 1:(1.0～1.2), Affirm (Merck Co.) free alkali and t-butyl methyl ether, normal hexane mass ratio are 1:(4.5～5.5): (9～11).
Gained emamectin-benzoate product HPLC method of the present invention is measured content and is greater than 95%.Mass percent.
Preferably, the mass ratio 1:3-5 of Affirm (Merck Co.) and solvent orange 2 A in step (1).
Preferred according to the present invention, in step (1), Affirm (Merck Co.): solvent orange 2 A total amount: toluene mass ratio is 1:(4～4.5): 12.
Preferred according to the present invention, the solvent orange 2 A described in step (1) is acetonitrile.
Preferred according to the present invention, the Affirm (Merck Co.) in step (1) and the mol ratio of phosphoric acid are 1:1.2.
Preferred according to the present invention, in step (1), phosphoric acid concentration is 14-16wt%.
Preferred according to the present invention, the solvent B described in step (2) is ethyl acetate.
Preferred according to the present invention, in step (2), Affirm (Merck Co.) salt: water: solvent B mass ratio is 1:12:7.
Preferred according to the present invention, in step (2), the static layering time is 1h.
Preferred according to the present invention, in step (2), described vacuum concentration temperature is 50～55 DEG C.
Preferred according to the present invention, in step (3), Affirm (Merck Co.) free alkali and phenylformic acid mol ratio are 1:1.1.
Preferred according to the present invention, in step (3), Affirm (Merck Co.) free alkali and t-butyl methyl ether, normal hexane mass ratio are 1:5:10.
Preferred according to the present invention, described in step (1), (3), the temperature of vacuum drying product is 30 DEG C.
The present invention's Affirm (Merck Co.) raw material used is commercial raw material, or the Affirm (Merck Co.) crude product of preparing by prior art, and Affirm (Merck Co.) material content is generally at 50-68wt%.
According to the present invention, a preferred scheme is, a kind of process for purification of emamectin-benzoate, and step is as follows:
(1) 20 DEG C～25 DEG C of temperature, the Affirm (Merck Co.) 200kg of content 62-65wt% is joined in 800kg acetonitrile, stir molten clear; In reaction solution, drip the mixing solutions stirring reaction 0.5～1h of 17kg phosphoric acid and the preparation of 100kg acetonitrile.Add toluene 2400kg stirring and crystallizing 1h, be cooled to-5 DEG C～5 DEG C, stir 5～6h, centrifugal ,-5 DEG C～5 DEG C toluene wash for filter cake.30 DEG C of vacuum drying products, obtain Affirm (Merck Co.) phosphoric acid salt 161kg, HPLC content 90.3%.
(2) the Affirm (Merck Co.) phosphoric acid salt 161kg making in step (1) is added in 1932kg water to stirring and dissolving.Add ethyl acetate 1127kg to stir.With the sodium hydroxide solution adjust pH of concentration 30wt% be 6～8, static layering 1～3h, separate organic phase, 35～65 DEG C of vacuum concentration, obtain fine work Affirm (Merck Co.) free alkali 102kg, HPLC content 96.5%.
(3) the Affirm (Merck Co.) free alkali 102kg in step (2) is added to t-butyl methyl ether 510kg, stirring and dissolving, keep 20～25 DEG C of temperature, add phenylformic acid 15.45kg, stirring reaction 2～5h, in reaction, drip normal hexane 1020kg, 2～3h dropwises, stirring reaction 2～3h. centrifuging, normal hexane 200kg washing 2 times for filter cake, 30 DEG C of vacuum drying products, obtain emamectin-benzoate 109kg.HPLC content 97.6%.
The present invention is taking Affirm (Merck Co.) crude product as raw material, in the equal solvent of polar solvent A and toluene, refine as Affirm (Merck Co.) phosphoric acid salt, again taking water as solvent, after stirring and dissolving, add esters solvent B, Affirm (Merck Co.) is extracted to organic phase by adjust pH, and vacuum concentration obtains fine work Affirm (Merck Co.), finally again with phenylformic acid salify in methyl tertiary butyl ether, obtain the emamectin-benzoate sterling that content is higher.
Beneficial effect of the present invention:
1, in order to solve an industrial production difficult problem for high purity Affirm (Merck Co.) product in prior art, first the present invention has proposed a kind of process for purification of new emamectin-benzoate, present method can improve the purity of product greatly, gained emamectin-benzoate product HPLC content can reach more than 97%, is suitable for preparing high-end preparation.
2, process for purification of the present invention has adopted comparatively simple technique, greatly reduces lowly with respect to crossing silicagel column purification process cost, and can carry out easily large-scale industrial production.Good process repeatability, products obtained therefrom steady quality.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is further elaborated, described embodiment is just used for illustrating the present invention, and should not be considered to be limitation of the present invention.The Affirm (Merck Co.) raw material using in embodiment, content 64wt%, market is bought.Phosphoric acid concentration is 14.5wt%.
Embodiment 1
A process for purification for Affirm (Merck Co.), step is as follows:
(1) keep 20 DEG C～25 DEG C of temperature, Affirm (Merck Co.) 200kg is added in 800kg acetonitrile, stir molten clear.In reaction solution, drip the mixing solutions of 17kg phosphoric acid and the preparation of 100kg acetonitrile, stirring reaction 0.5～1h.Add toluene 2400kg stirring and crystallizing 1h, be cooled to-5 DEG C～5 DEG C, stir 5～6h, centrifugal ,-5 DEG C～5 DEG C toluene wash for filter cake.30 DEG C of vacuum drying products, obtain Affirm (Merck Co.) phosphoric acid salt 161kg, HPLC content 90.3%.
(2) the Affirm (Merck Co.) phosphoric acid salt 161kg making in step (1) is added in 1932kg water to stirring and dissolving.Add ethyl acetate 1127kg to stir.With the sodium hydroxide solution adjust pH of 30wt% concentration be 6.8, static layering 1.5h, separate organic phase, 35～65 DEG C of vacuum concentration, obtain fine work Affirm (Merck Co.) free alkali 102kg, HPLC content 96.5%.
(3) the Affirm (Merck Co.) free alkali 102kg in step (2) is added to t-butyl methyl ether 510kg, stirring and dissolving, keep 20～25 DEG C of temperature, add phenylformic acid 15.45kg, stirring reaction 2～5h, in reaction, drip normal hexane 1020kg, 2～3h dropwises, stirring reaction 2～3h. centrifuging, normal hexane 200kg washing 2 times for filter cake, 30 DEG C of vacuum drying products, obtain emamectin-benzoate 109kg.HPLC content 97.2%.
Embodiment 2
A process for purification for Affirm (Merck Co.), step is as follows:
(1) keep 20 DEG C～25 DEG C of temperature, Affirm (Merck Co.) 200kg is added in 600kg acetonitrile, stir molten clear.In reaction solution, drip the mixing solutions of 28.3kg phosphoric acid and the configuration of 100kg acetonitrile, stirring reaction 0.5～1h.Add toluene 2000kg stirring and crystallizing 1h, be cooled to-5 DEG C～5 DEG C, stir 5～6h, centrifugal ,-5 DEG C～5 DEG C toluene wash for filter cake.30 DEG C of vacuum drying products, obtain Affirm (Merck Co.) phosphoric acid salt 165kg, HPLC content 88.4%.
(2) the Affirm (Merck Co.) phosphoric acid salt 165kg making in step (1) is added in 1650kg water to stirring and dissolving.Add ethyl acetate 990kg to stir.The sodium hydroxide solution adjust pH of 30wt% concentration is 7, and static layering 1h separates organic phase, and 35～65 DEG C of vacuum concentration, obtain fine work Affirm (Merck Co.) free alkali 110kg, HPLC content 95.5%.
(3) the Affirm (Merck Co.) free alkali 110kg in step (2) is added to t-butyl methyl ether 495kg, stirring and dissolving, keep 20～25 DEG C of temperature, add phenylformic acid 14.0kg, stirring reaction 2～5h, in reaction, drip normal hexane 990kg, 2～3h dropwises, stirring reaction 2～3h. centrifuging, normal hexane 200kg washing 2 times for filter cake, 30 DEG C of vacuum drying products, obtain emamectin-benzoate 110kg.HPLC content 96.8%.
Embodiment 3
A process for purification for Affirm (Merck Co.), step is as follows:
(1) keep 20 DEG C～25 DEG C of temperature, Affirm (Merck Co.) 200kg is added in 1000kg acetonitrile, stir molten clear.In reaction solution, drip the mixing solutions of 14.2kg phosphoric acid and the configuration of 100kg acetonitrile, stirring reaction 0.5～1h.Add toluene 3000kg stirring and crystallizing 1h, be cooled to-5 DEG C～5 DEG C, stir 5～6h, centrifugal ,-5 DEG C～5 DEG C toluene wash for filter cake.30 DEG C of vacuum drying products, obtain Affirm (Merck Co.) phosphoric acid salt 158kg, HPLC content 90.4%.
(2) the Affirm (Merck Co.) phosphoric acid salt 158kg making in step (1) is added in 2370kg water to stirring and dissolving.Add ethyl acetate 1264kg to stir.The sodium hydroxide solution adjust pH of 30wt% concentration is 7.5, and static layering 2.5h separates organic phase, and 35～65 DEG C of vacuum concentration, obtain fine work Affirm (Merck Co.) free alkali 109kg, HPLC content 94.8%.
(3) the Affirm (Merck Co.) free alkali 109kg in step (2) is added to t-butyl methyl ether 599.5kg, stirring and dissolving, keep 20～25 DEG C of temperature, add phenylformic acid 16.8kg, stirring reaction 2～5h, in reaction, drip normal hexane 1199kg, 2～3h dropwises, stirring reaction 2～3h. centrifuging, normal hexane 200kg washing 2 times for filter cake, 30 DEG C of vacuum drying products, obtain emamectin-benzoate 112kg.HPLC content 95.5%.
Embodiment 4
A process for purification for Affirm (Merck Co.), step is as follows:
(1) keep 20 DEG C～25 DEG C of temperature, Affirm (Merck Co.) 200kg is added in 800kg methyl alcohol, stir molten clear.In reaction solution, drip the mixing solutions of 17kg phosphoric acid and the configuration of 100kg methyl alcohol, stirring reaction 0.5～1h.Add toluene 2400kg stirring and crystallizing 1h, be cooled to-5 DEG C～5 DEG C, stir 5～6h, centrifugal ,-5 DEG C～5 DEG C toluene wash for filter cake.30 DEG C of vacuum drying products, obtain Affirm (Merck Co.) phosphoric acid salt 163kg, HPLC content 91.2%.
(2) the Affirm (Merck Co.) phosphoric acid salt 163kg making in step (1) is added in 1932kg water to stirring and dissolving.Add isopropyl acetate 1127kg to stir.The sodium hydroxide solution adjust pH of 30wt% concentration is 7, and static layering 3h separates organic phase, and 35～65 DEG C of vacuum concentration, obtain fine work Affirm (Merck Co.) free alkali 105kg, HPLC content 95.5%.
(3) the Affirm (Merck Co.) free alkali 105kg in step (2) is added to t-butyl methyl ether 510kg, stirring and dissolving, keep 20～25 DEG C of temperature, add phenylformic acid 15.45kg, stirring reaction 2～5h, in reaction, drip normal hexane 1020kg, 2～3h dropwises, stirring reaction 2～3h. centrifuging, normal hexane 200kg washing 2 times for filter cake, 30 DEG C of vacuum drying products, obtain emamectin-benzoate 110kg.HPLC content 97.5%.
Embodiment 5
A process for purification for Affirm (Merck Co.), step is as follows:
(1) keep 20 DEG C～25 DEG C of temperature, Affirm (Merck Co.) 200kg is added in 800kg ethanol, stir molten clear.In reaction solution, drip the mixing solutions of 17kg phosphoric acid and the configuration of 100kg ethanol, stirring reaction 0.5～1h.Add toluene 2400kg stirring and crystallizing 1h, be cooled to-5 DEG C～5 DEG C, stir 5～6h, centrifugal ,-5 DEG C～5 DEG C toluene wash for filter cake.30 DEG C of vacuum drying products, obtain Affirm (Merck Co.) phosphoric acid salt 160kg, HPLC content 93.3%.
(2) the Affirm (Merck Co.) phosphoric acid salt 160kg making in step (1) is added in 1932kg water to stirring and dissolving.Add butylacetate 1127kg to stir.The sodium hydroxide solution adjust pH of 30wt% concentration is 7.5, and static layering 1.5h separates organic phase, and 35～65 DEG C of vacuum concentration, obtain fine work Affirm (Merck Co.) free alkali 102kg, HPLC content 95.6%.
(3) the Affirm (Merck Co.) free alkali 102kg in step (2) is added to t-butyl methyl ether 510kg, stirring and dissolving, keeps 20～25 DEG C of temperature, add phenylformic acid 15.45kg, stirring reaction 2～5h drips normal hexane 1020kg in reaction, 2～3h dropwises, stirring reaction 2.5h.Centrifuging, normal hexane 200kg washing 2 times for filter cake, 30 DEG C of vacuum drying products, obtain emamectin-benzoate 105kg.HPLC content 97.1%.
Claims (8)
1. a process for purification for emamectin-benzoate, comprises that step is as follows:
(1) 20 DEG C～25 DEG C of temperature, raw material Affirm (Merck Co.) is added to solvent orange 2 A, stir molten clearly, drip the mixing solutions of phosphoric acid and solvent orange 2 A, stirring reaction 0.5～1h; Then add toluene stirring and crystallizing 1h; Be cooled to-5 DEG C～5 DEG C, stir 5～6h, centrifugal ,-5 DEG C～5 DEG C toluene wash for filter cake; Vacuum drying product, obtains Affirm (Merck Co.) phosphoric acid salt;
Wherein, Affirm (Merck Co.) raw material: solvent orange 2 A total amount: toluene mass ratio is 1:3～6:10～15, Affirm (Merck Co.) and phosphoric acid molar ratios are 1:1～2;
Described solvent orange 2 A is one of methyl alcohol, ethanol, acetonitrile or combination.
(2) the Affirm (Merck Co.) phosphoric acid salt making in step (1) is added to the water to stirring and dissolving; Add solvent B to stir, sodium hydroxide solution adjust pH is 6～8, and static layering 1～3h separates organic phase, and 35～65 DEG C of vacuum concentration, obtain fine work Affirm (Merck Co.) free alkali;
Wherein, Affirm (Merck Co.) phosphoric acid salt: water: solvent B mass ratio is 1:10～15:6～8;
Described solvent B is ethyl acetate, isopropyl acetate or butylacetate;
(3) the Affirm (Merck Co.) free alkali in step (2) is added in t-butyl methyl ether, stirring and dissolving, keeps 20～25 DEG C of temperature, adds phenylformic acid, stirring reaction 2～5h, in reaction solution, drip normal hexane, 2～3h dropwises, stirring reaction 2～3h, filter, normal hexane washing 1～2 time for filter cake, vacuum drying product, obtains emamectin-benzoate product;
Wherein, Affirm (Merck Co.) free alkali and phenylformic acid mol ratio are 1:1.0～1.2, and Affirm (Merck Co.) free alkali and t-butyl methyl ether, normal hexane mass ratio are 1:4.5～5.5:9～11.
2. the process for purification of emamectin-benzoate as claimed in claim 1, is characterized in that, in step (1), and Affirm (Merck Co.): solvent orange 2 A total amount: toluene mass ratio is 1:4～4.5: 12.
3. the process for purification of emamectin-benzoate as claimed in claim 1, is characterized in that, the Affirm (Merck Co.) in step (1) and the mol ratio of phosphoric acid are 1:1.2.
4. the process for purification of emamectin-benzoate as claimed in claim 1, is characterized in that, in step (1), phosphoric acid solution concentration is 14-16wt%.
5. the process for purification of emamectin-benzoate as claimed in claim 1, is characterized in that, in step (2), and Affirm (Merck Co.) phosphoric acid salt: water: solvent B mass ratio is 1:12:7.
6. the process for purification of emamectin-benzoate as claimed in claim 1, is characterized in that, in step (2), described vacuum concentration temperature is 50～55 DEG C.
7. the process for purification of emamectin-benzoate as claimed in claim 1, it is characterized in that, in step (3), Affirm (Merck Co.) free alkali and phenylformic acid mol ratio are 1:1.1, and Affirm (Merck Co.) free alkali and t-butyl methyl ether, normal hexane mass ratio are 1:5:10.
8. the process for purification of emamectin-benzoate as claimed in claim 1, is characterized in that, step is as follows:
(1) 20 DEG C～25 DEG C of temperature, the Affirm (Merck Co.) 200kg of content 62-65wt% is joined in 800kg acetonitrile, stir molten clear; In reaction solution, drip the mixing solutions stirring reaction 0.5～1h of 17kg phosphoric acid and the preparation of 100kg acetonitrile; Add toluene 2400kg stirring and crystallizing 1h, be cooled to-5 DEG C～5 DEG C, stir 5～6h, centrifugal ,-5 DEG C～5 DEG C toluene wash for filter cake, 30 DEG C of vacuum drying products, obtain Affirm (Merck Co.) phosphoric acid salt 161kg, HPLC content 90.3%;
(2) the Affirm (Merck Co.) phosphoric acid salt 161kg making in step (1) is added in 1932kg water to stirring and dissolving.Add ethyl acetate 1127kg to stir; With the sodium hydroxide solution adjust pH of concentration 30wt% be 6～8, static layering 1～3h, separate organic phase, 35～65 DEG C of vacuum concentration, obtain fine work Affirm (Merck Co.) free alkali 102kg, HPLC content 96.5%;
(3) the Affirm (Merck Co.) free alkali 102kg in step (2) is added to t-butyl methyl ether 510kg, stirring and dissolving, keeps 20～25 DEG C of temperature, adds phenylformic acid 15.45kg, stirring reaction 2～5h, in reaction, drip normal hexane 1020kg, 2～3h dropwises, stirring reaction 2～3h, centrifuging, normal hexane 200kg washing 2 times for filter cake, 30 DEG C of vacuum drying products, obtain emamectin-benzoate 109kg.
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| CN104876990B (en) * | 2015-06-02 | 2017-11-14 | 宁夏泰瑞制药股份有限公司 | A kind of method for purifying emamectin benzoate crude product |
| US9409920B1 (en) * | 2015-06-08 | 2016-08-09 | Rotam Agrochem International Company Limited | Method for purifying emamectin benzoate and compositions comprising the same |
| US9643991B2 (en) * | 2015-06-08 | 2017-05-09 | Rotam Agrochem International Company Limited | Process for preparing a novel crystalline form of emamectin benzoate and use the same |
| CN106008628B (en) * | 2016-05-24 | 2018-11-27 | 宁夏泰益欣生物科技有限公司 | A kind of method of purification of emamectin benzoate |
| CN106797943A (en) * | 2016-12-23 | 2017-06-06 | 孙华飞 | A kind of emamectin-benzoate mite killing suspending agent with entrapping function and preparation method thereof |
| CN111748009B (en) * | 2020-07-22 | 2023-11-17 | 齐鲁晟华制药有限公司 | Crystal form of emamectin benzoate and preparation method thereof |
| CN112707939B (en) * | 2020-12-25 | 2022-06-24 | 河北威远生物化工有限公司 | Purification method of 4' -(s) -emamectin benzoate B2a |
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