CN113666916B - Refining method of difenoconazole crude product - Google Patents
Refining method of difenoconazole crude product Download PDFInfo
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- CN113666916B CN113666916B CN202111067873.0A CN202111067873A CN113666916B CN 113666916 B CN113666916 B CN 113666916B CN 202111067873 A CN202111067873 A CN 202111067873A CN 113666916 B CN113666916 B CN 113666916B
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- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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Abstract
The invention discloses a refining method of a difenoconazole crude product, which adopts an extraction crystallization method to refine difenoconazole, wherein the difenoconazole is extracted firstly and then crystallized, strong acid and alkali liquor are not introduced in the whole refining process, and no waste salt is generated in the refining process; no rectification, no rectification residue and no high COD wastewater. The extraction mother liquor and the crystallization mother liquor are subjected to extraction solvent removal to obtain low-content difenoconazole with lighter color, 10% difenoconazole aqueous emulsion can be directly prepared, the quality of the aqueous emulsion is high, waste recycling is realized, and the utilization rate of a difenoconazole crude product reaches more than 98%.
Description
Technical Field
The invention relates to a refining method of a difenoconazole crude product, belonging to an organic chemical post-treatment technology.
Background
At present, the content of crude difenoconazole in industrial production is mostly 70-83%, and the common refining method comprises salifying by concentrated nitric acid or concentrated hydrochloric acid, obtaining high-content difenoconazole by alkaline hydrolysis extraction, and then recrystallizing to obtain the difenoconazole technical product. The method can generate a large amount of sodium nitrate or sodium chloride waste salt, thereby greatly increasing the environmental protection treatment cost; and the color of the mother liquor after alkaline hydrolysis extraction is darker, the mother liquor cannot be prepared into emulsion in water, the mother liquor cannot be utilized, and only a third party can be entrusted to carry out incineration and the like, so that resources are wasted, and the method is not beneficial to environmental protection.
For example, chinese patent CN110204534A discloses a refining method of difenoconazole, which discloses dissolving crude difenoconazole with toluene, promoting hydrochloride salt formation with hydrogen chloride, adding alkaline water for alkaline hydrolysis after salt formation, removing toluene, and crystallizing to obtain difenoconazole technical product. Although the process is optimized, the process is essentially the steps of salt formation, alkaline hydrolysis and crystallization, a large amount of waste salt is still generated, and difenoconazole contained in the alkaline water cannot be recovered, so that certain waste is caused.
Therefore, a technical solution is needed to solve the above technical problems.
Disclosure of Invention
The invention aims to provide a novel refining method without salification aiming at the defects of the existing difenoconazole refining process, and the method does not need to introduce strong acid or alkaline hydrolysis, does not generate a large amount of waste salt, and is environment-friendly.
The technical scheme adopted by the invention for solving the problems is as follows:
a refining method of a difenoconazole crude product comprises the steps of extraction and crystallization; the extraction steps are as follows: extracting the difenoconazole crude product for at least 1 time by using an extraction solvent to extract the difenoconazole to be crystallized; the crystallization step comprises the following steps: and mixing and fully dissolving difenoconazole to be crystallized and a crystallization solvent, and cooling and crystallizing to obtain the difenoconazole technical product.
Further, the extraction step specifically comprises: adding a difenoconazole crude product and an extraction solvent into a reaction container, heating to reflux and extracting for 0.5-1h, cooling to 70 ℃, performing phase splitting, and separating out the extraction solvent; and continuously adding an extraction solvent, carrying out second extraction, carrying out third extraction after the second extraction is finished, separating to obtain difenoconazole to be crystallized, and removing the extraction solvent from the extraction mother liquor to obtain the low-content difenoconazole. In the three extractions, the mass ratio of the extraction solvent added each time to the difenoconazole crude product is 4-6. The mass content of difenoconazole in the crude difenoconazole is 70-83%; the mass content of the difenoconazole to be crystallized is 96-97 percent; the mass content of the low content difenoconazole is 50-66.3%.
Further, the crystallization step specifically comprises: adding difenoconazole to be crystallized and a crystallization solvent into a crystallization container, mixing, heating to 60-70 ℃ for dissolution, cooling to-10-0 ℃ for crystallization for 6-8h after complete dissolution, and performing suction filtration and drying to obtain the difenoconazole technical product. The mass ratio of the crystallization solvent to difenoconazole to be crystallized is 1-1.2. The mass content of the difenoconazole technical material is 97-98%.
Further, the extraction solvent is n-heptane, mixed heptane, methylcyclohexane or cyclohexane.
Further, the crystallization solvent is 85-90% by mass of methanol, 95% by mass of ethanol or 98-99% by mass of isopropanol.
Further, the extraction mother liquor and the crystallization mother liquor are subjected to purification and crystallization solvent removal to obtain low-content difenoconazole which is used for preparing the difenoconazole water emulsion with the mass content of 10%.
Compared with the existing refining process, the invention has the beneficial effects that:
1) The difenoconazole is refined by adopting an extraction crystallization method, the difenoconazole is extracted and then crystallized, strong acid and alkali liquor are not introduced in the whole refining process, and no waste salt is generated in the refining process; no rectification, no rectification residue and no high COD waste water.
2) The extraction process is adopted to replace a salt forming process, strong acid is not needed, the extraction mother liquor and the crystallization mother liquor are subjected to extraction solvent removal to obtain low-content difenoconazole with lighter color, 10% difenoconazole water emulsion can be directly prepared, the quality of the water emulsion is high, no waste water is generated, waste recycling is realized, and the utilization rate of the difenoconazole crude product reaches more than 98%.
3) The invention adopts an extraction crystallization refining process, which is simple to operate and easy to control, greatly shortens the refining period, has high purification yield and low production cost, and is green and environment-friendly in the whole process.
Detailed Description
In order to make the objects, technical solutions and advantages of the technical solutions of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the specific embodiments of the present invention.
It should be noted that the described embodiments of the invention are only preferred ways of implementing the invention, and that all obvious modifications, which are within the scope of the invention, are all included in the present general inventive concept.
Example 1
100g of difenoconazole crude product with the mass content of 70 percent and 400g of cyclohexane are added into a reaction kettle, heating reflux extraction is carried out for 0.5-1h, the temperature is reduced to 70 ℃ for phase splitting, 400g of cyclohexane is continuously added for secondary extraction after the cyclohexane is separated out, 400g of cyclohexane is continuously added for third extraction after the secondary extraction is finished, the cyclohexane is removed completely to separate out the difenoconazole with the content of 96 percent to be crystallized, 44g of methanol with the mass concentration of 85-90 percent is added, the temperature is increased to 60-70 ℃ for dissolution, the temperature is reduced to-10-0 ℃ for crystallization for 6-8h after the dissolution is completely, suction filtration and drying are carried out to obtain 40g of 97 percent difenoconazole raw drug, and 3.9g of 53.8 percent difenoconazole is obtained by removing solvent from crystallization mother liquor. 56g of low-content difenoconazole with the concentration of 50.4 percent obtained by desolvation of the extraction mother liquor is combined with 3.9g of difenoconazole obtained by desolvation of the crystallization mother liquor, and a solvent, an emulsifier, water, an antifreeze agent and the like are added to prepare 10 percent difenoconazole water emulsion.
100g of 70% difenoconazole crude product is refined to obtain 40g of 97% difenoconazole crude drug, 53.8% of crystallization mother liquor is desolventized, 3.9g of low-content difenoconazole with the content of 50.4% is obtained, and therefore the utilization rate of the refined difenoconazole reaches 98.70%, the utilization rate is high, and no waste salt, waste residue and high-concentration COD wastewater is generated in the whole refining process.
Example 2
100g of crude difenoconazole with the mass content of 80 percent and 500g of n-heptane are added into a reaction kettle, the heating reflux extraction is carried out for 0.5-1h, the temperature is reduced to 70 ℃ for phase splitting, after the n-heptane is separated, 500g of n-heptane is continuously added for second extraction, after the second extraction is finished, 500g of n-heptane is continuously added for third extraction, the clean n-heptane is removed for separation to obtain 53.5g of difenoconazole to be crystallized with the content of 97 percent, 64.2g of ethanol with the mass concentration of 95 percent is added, the temperature is increased to 60-70 ℃ for dissolution, the temperature is reduced to-10-0 ℃ for crystallization for 6-8h after complete dissolution, the leaching is carried out, the drying is carried out to obtain 48.7g of 98 percent difenoconazole raw drug, and the clean solvent of crystallization mother liquor is removed to obtain 4.7g of 68.1 percent difenoconazole. And (3) desolventizing the extraction mother liquor to obtain 46.5g of low-content difenoconazole with the concentration of 60.4%, and adding a solvent, an emulsifier, water, an antifreezing agent and the like into the difenoconazole obtained by desolventizing the extraction mother liquor and the crystallization mother liquor to prepare 10% difenoconazole water emulsion. The utilization rate of the difenoconazole reaches 98.75 percent.
Example 3
100g of crude difenoconazole with the mass content of 83 percent and 600g of methylcyclohexane are added into a reaction kettle, heating reflux extraction is carried out for 0.5-1h, the temperature is reduced to 70 ℃ for phase splitting, 600g of methylcyclohexane is continuously added for secondary extraction after the methylcyclohexane is separated out, 600g of methylcyclohexane is continuously added for third extraction after the secondary extraction is finished, the decarburized methylcyclohexane is separated to obtain 56.0g of difenoconazole to be crystallized with the content of 96 percent, 61.6g of isopropanol with the mass concentration of 98-99 percent is added, the temperature is increased to 60-70 ℃ for dissolution, the temperature is reduced to-10-0 ℃ for crystallization for 6-8h after the dissolution is complete, suction filtration and drying are carried out to obtain 51.0g of difenoconazole raw drug with the mass content of 97.5 percent, and the crystallization mother solution is desolventized to obtain 4.9g of difenoconazole with the content of 63.3 percent. The extraction mother liquor is desolventized to obtain 44g of low-content difenoconazole with 66.3 percent, the extraction mother liquor and the crystallization mother liquor are combined to obtain the low-content difenoconazole after desolventization, and a solvent, an emulsifier, water, an antifreezing agent and the like are added into the mixture to prepare the difenoconazole water emulsion with 10 percent. The utilization rate of the difenoconazole reaches 98.80 percent.
Claims (8)
1. A refining method of a difenoconazole crude product is characterized by comprising the following steps: comprises the steps of extraction and crystallization;
the extraction comprises the following specific steps: adding a difenoconazole crude product and an extraction solvent into a reaction container, heating to reflux and extracting for 0.5-1h, cooling to 70 ℃, performing phase splitting, and separating out the extraction solvent; continuously adding an extraction solvent, carrying out second extraction, carrying out third extraction after the second extraction is finished, separating to obtain difenoconazole to be crystallized, and removing the extraction solvent from extraction mother liquor to obtain low-content difenoconazole, wherein the mass content of the difenoconazole in the difenoconazole crude product is 70-83%, and the extraction solvent is n-heptane, methylcyclohexane or cyclohexane;
the crystallization step is as follows: and mixing and fully dissolving difenoconazole to be crystallized and a crystallization solvent, and cooling and crystallizing to obtain the difenoconazole technical product.
2. The refining method of crude difenoconazole according to claim 1, which is characterized in that: in the three extractions, the mass ratio of the extraction solvent added each time to the crude difenoconazole is 4-6.
3. The refining method of crude difenoconazole according to claim 1, which is characterized in that: the mass content of difenoconazole to be crystallized is 96-97%; the mass content of the low-content difenoconazole is 50-66.3%.
4. The refining method of crude difenoconazole according to claim 3, which is characterized in that: the low-content difenoconazole is used for preparing the difenoconazole water emulsion with the mass content of 10%.
5. The refining method of crude difenoconazole according to claim 1, which is characterized in that: the crystallization step specifically comprises the following steps: adding difenoconazole to be crystallized and a crystallization solvent into a crystallization container, mixing, heating to 60-70 ℃ for dissolution, cooling to-10-0 ℃ for crystallization for 6-8h after complete dissolution, and performing suction filtration and drying to obtain a difenoconazole raw drug; and (3) removing the crystallization solvent from the crystallization mother liquor to obtain low-content difenoconazole, wherein the low-content difenoconazole is used for preparing 10% of difenoconazole water emulsion.
6. The refining method of crude difenoconazole according to claim 5, which is characterized in that: the mass ratio of the crystallization solvent to difenoconazole to be crystallized is 1-1.2.
7. The refining method of crude difenoconazole according to claim 5, which is characterized in that: the mass content of the difenoconazole technical material is 97-98%.
8. The refining method of crude difenoconazole according to any one of claims 1-7, characterized in that: the crystallization solvent is 85-90% by mass of methanol, 95% by mass of ethanol or 98-99% by mass of isopropanol.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898422A (en) * | 2012-10-12 | 2013-01-30 | 江苏七洲绿色化工股份有限公司 | Method for preparing difenoconazole |
| CN108341803A (en) * | 2018-03-21 | 2018-07-31 | 新沂市中诺新材料科技有限公司 | A kind of synthetic method of difenoconazole |
| CN109970722A (en) * | 2019-05-06 | 2019-07-05 | 长沙鑫本药业有限公司 | A kind of synthesis technology of difenoconazole |
| CN110204534A (en) * | 2019-05-30 | 2019-09-06 | 浙江禾本科技有限公司 | A kind of refining methd of difenoconazole |
| CN112300137A (en) * | 2020-08-24 | 2021-02-02 | 江苏禾本生化有限公司 | Synthetic method of high-purity difenoconazole |
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- 2021-09-13 CN CN202111067873.0A patent/CN113666916B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898422A (en) * | 2012-10-12 | 2013-01-30 | 江苏七洲绿色化工股份有限公司 | Method for preparing difenoconazole |
| CN108341803A (en) * | 2018-03-21 | 2018-07-31 | 新沂市中诺新材料科技有限公司 | A kind of synthetic method of difenoconazole |
| CN109970722A (en) * | 2019-05-06 | 2019-07-05 | 长沙鑫本药业有限公司 | A kind of synthesis technology of difenoconazole |
| CN110204534A (en) * | 2019-05-30 | 2019-09-06 | 浙江禾本科技有限公司 | A kind of refining methd of difenoconazole |
| CN112300137A (en) * | 2020-08-24 | 2021-02-02 | 江苏禾本生化有限公司 | Synthetic method of high-purity difenoconazole |
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