CN110563660A - Method for reducing 1,3, 4-triazole substituent in alkylation reaction process of 1,2, 4-triazole - Google Patents
Method for reducing 1,3, 4-triazole substituent in alkylation reaction process of 1,2, 4-triazole Download PDFInfo
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- CN110563660A CN110563660A CN201910861136.4A CN201910861136A CN110563660A CN 110563660 A CN110563660 A CN 110563660A CN 201910861136 A CN201910861136 A CN 201910861136A CN 110563660 A CN110563660 A CN 110563660A
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- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
Abstract
The invention relates to a method for reducing 1,3, 4-triazole substitutes in the alkylation reaction process of 1,2, 4-triazole, 1,2, 4-triazole and an alkylating reagent are subjected to alkylation reaction in the presence of alkali and a catalyst, and after the reaction is finished, the 1,2, 4-triazole substitutes are obtained through post-treatment, wherein the catalyst is one or a combination of more of polyethers, cyclic crown ethers, quaternary ammonium salts, quaternary phosphonium salts, quaternary ammonium bases and tertiary amines. The method has simple operation and wide application range, can reduce the content of the 1,3, 4-triazole substituent in the alkylation reaction process, improve the yield of the 1,2, 4-triazole substituent, shorten the reaction time, reduce the reaction temperature, reduce or avoid the use of solvents, improve the resource utilization rate, reduce three wastes, reduce the production cost and meet the requirements of green and environment-friendly processes.
Description
Technical Field
The invention particularly relates to a method for reducing 1,3, 4-triazole substitutes in the alkylation reaction process of 1,2, 4-triazole.
Background
The compound taking 1,2, 4-triazole as an active structural component has strong biological activity, is widely applied to the fields of pesticides and medicines, and in the field of pesticides, triazole pesticides not only show good bacteriostatic action, but also have physiological efficiency regulation and insecticidal and herbicidal activities for plants by changing binding groups.
The 1,2, 4-triazole substituent is generally obtained by alkylation reaction of 1,2, 4-triazole and an alkylating reagent, and the generation of the 1,3, 4-triazole substituent in the reaction process cannot be avoided, and the content of the 1,2, 4-triazole substituent is different according to different types of alkylating reagents. The 1,2, 4-triazole substituent and the 1,3, 4-triazole substituent have the following structures respectively:
In order to obtain a high purity 1,2, 4-triazole substituent, the 1,3, 4-triazole substituent is usually removed by crystallization or high temperature. The former requires a large amount of solvent for purification and has a large loss, and the latter requires high-temperature reaction conditions and has many side reactions and a low yield.
disclosure of Invention
The invention aims to provide a method for reducing 1,3, 4-triazole substitutes in the alkylation reaction process of 1,2, 4-triazole.
In order to solve the technical problems, the invention adopts the following technical scheme:
A method for reducing 1,3, 4-triazole substitutes in the alkylation reaction process of 1,2, 4-triazole comprises the steps of carrying out alkylation reaction on 1,2, 4-triazole and an alkylating reagent in the presence of alkali and a catalyst, and carrying out post-treatment after the reaction is finished to obtain the 1,2, 4-triazole substitutes, wherein the catalyst is one or more of polyethers, cyclic crown ethers, quaternary ammonium salts, quaternary phosphonium salts, quaternary ammonium bases and tertiary amines.
Preferably, the catalyst is one or more of triethyl benzyl ammonium chloride, tetramethyl ammonium chloride, tetrabutyl ammonium bromide, dodecyl trimethyl ammonium chloride, ethyl triphenyl phosphonium bromide, 18-crown-6, 15-crown-5, polyethylene glycol and polyethylene glycol dimethyl ether.
Preferably, the feeding mass ratio of the catalyst to the alkylating agent is 0.01-0.1: 1, more preferably 0.01-0.07: 1, and still more preferably 0.01-0.05: 1.
Preferably, the base is quaternary ammonium base, KOH, NaOH, K2CO3、Na2CO3And one or more of NaH, N-dimethylcyclohexylamine and dicyclohexylamine.
Preferably, the feeding molar ratio of the 1,2, 4-triazole to the alkali is 1: 1.01-1.2, and further preferably 1: 1.01-1.1.
preferably, the feeding molar ratio of the 1,2, 4-triazole to the alkylating agent is 1.01-1.3: 1, and further preferably 1.01-1.1: 1.
Preferably, the temperature of the alkylation reaction is 50-150 ℃, and further preferably 60-130 ℃.
Preferably, the alkylation reaction time is 1-3 h.
Preferably, the alkylation reaction is carried out in the absence of a solvent or in the presence of a small amount of a solvent, when the reaction is carried out in a small amount of a solvent, the mass ratio of the solvent to the alkylating reagent is 1: 5-20, and the solvent is one or more of N, N-Dimethylformamide (DMF), dimethyl sulfoxide, N-dimethylacetamide, N-methylpyrrolidone (NMP), toluene, methylcyclohexane and cyclohexane.
Preferably, the 1,2, 4-triazole substituent is one of tebuconazole, flutriafol, propiconazole, difenoconazole, epoxiconazole and cyproconazole.
Wherein, the alkylating reagent is different according to the 1,2, 4-triazole substituent to be prepared, and the specific alkylating reagent can be one or more combinations of alkylating reagents known in the art, such as halogenated hydrocarbon alkylating reagent, trifluoromethyl sulfonate alkylating reagent and methyl sulfonate alkylating reagent, preferably, the alkylating reagent for preparing tebuconazole is 2- (4-chlorophenylethyl) -2-tert-butyl oxirane, the alkylating reagent for preparing epoxiconazole is 2-bromomethyl-2- (4-fluorophenyl) -3- (2-chlorophenyl) -oxirane or 2-methyl-2- (4-fluorophenyl) -3- (2-chlorophenyl) -oxirane, the alkylating agent for preparing the difenoconazole is 2- (bromomethyl) -2- (2-chloro-4- (4-chlorophenoxy) phenyl) -4-methyl-1, 3-dioxolane, and the alkylating agent for preparing the propiconazole is 2-bromomethyl-2- (2, 4-dichlorophenyl) -4-propyl-1, 3-dioxolane.
Preferably, the post-treatment method comprises the following steps: adding water into the reaction solution after the reaction is finished for layering, and washing and desolventizing the organic phase to obtain the 1,2, 4-triazole substituent.
Due to the implementation of the technical scheme, compared with the prior art, the invention has the following advantages:
the invention provides a method for reducing 1,3, 4-triazole substituent in the alkylation reaction process of 1,2, 4-triazole, which is simple to operate and wide in application range, and can reduce the content of the 1,3, 4-triazole substituent in the alkylation reaction process, improve the yield of the 1,2, 4-triazole substituent, shorten the reaction time, reduce the reaction temperature, reduce or avoid the use of solvents, improve the utilization rate of resources, reduce three wastes, reduce the production cost and meet the requirements of green and environment-friendly processes.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that these embodiments are provided to illustrate the basic principles, essential features and advantages of the present invention, and the present invention is not limited by the following embodiments. The implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments. The contents are all mass contents.
Example 1
Synthesis of tebuconazole: putting 17.44g of 1,2, 4-triazole (252.5 mmol), 10.4g of sodium hydroxide (259.9 mmol), 2.8g of triethyl benzyl ammonium chloride and 10g of N, N-dimethylformamide into a reaction bottle, preheating to 80 ℃, then beginning to dropwise add 2- (4-chlorophenylethyl) -2-tert-butyl oxirane (59.1g, 247.5mmol), controlling the temperature to be less than or equal to 95 ℃ during dropwise adding, preserving the temperature for 2-3 h at 98-102 ℃ after dropwise adding is finished, adding water for layering after the heat preservation is finished, washing an organic layer with water until the pH value is less than 8, and obtaining 74.5g of finished tebuconazole with the content of 97.8% and the yield of 95.6% after negative pressure desolvation of the organic layer.
Comparative example 1
Synthesis of tebuconazole: putting 17.44g of 1,2, 4-triazole (252.5 mmol), 10.4g of sodium hydroxide (259.9 mmol) and 10g of N, N-dimethylformamide into a reaction bottle, preheating to 80 ℃, then beginning to dropwise add 2- (4-chlorophenylethyl) -2-tert-butyl oxirane (59.1g, 247.5mmol 1), controlling the temperature to be less than or equal to 95 ℃ during dropwise adding, preserving the temperature for 2-3 h at 98-102 ℃ after dropwise adding, adding water for layering after preserving the temperature, washing an organic layer with water until the pH value is less than 8, and obtaining 72.3g of finished tebuconazole with the content of 93.5% and the yield of 88.7% after desolventizing the organic layer under negative pressure.
Example 2
Synthesis of epoxiconazole: putting 2-bromomethyl-2- (4-fluorophenyl) -3- (2-chlorphenyl) -oxirane (58.1g, 170.02mmol), 1,2, 4-triazole (12.9g, 187.0mmol), sodium hydride (4.6g, 190.42mmol) and 2.3g tetramethylammonium chloride in a reaction bottle, heating to 70 ℃, stirring for reaction for 1-2 h, cooling to room temperature after complete reaction, adding water for layering, sequentially using water, saturated sodium chloride solution and water for washing and drying an organic layer, and performing decompression and desolventization to obtain 53.8g epoxiconazole with the content of 97.2% and the yield of 93.3%.
Comparative example 2
Synthesis of epoxiconazole: dissolving 2-bromomethyl-2- (4-fluorophenyl) -3- (2-chlorophenyl) -oxirane (58.1g, 170.02mmol), 1,2, 4-triazole (12.9g, 187.0mmol) and sodium hydride (4.6g, 190.42mmol) in 30g of DMF, heating to 70 ℃, stirring for reaction for 3-4 h, cooling to room temperature after complete reaction, adding water for layering, sequentially using water, a saturated sodium chloride solution and water for washing and drying an organic layer, and performing decompression and desolventization to obtain 54.0g of epoxiconazole with the content of 88.2% and the yield of 84.9%.
Example 3
Synthesis of epoxiconazole: dissolving 2-methyl-sulfonate-2- (4-fluorophenyl) -3- (2-chlorphenyl) -oxirane (69.31g, 194.3mmol), 1,2, 4-triazole (14.1g, 204.0mmol), sodium hydride (5.4g, 223.4mmol) and 1.2g of tetrabutylammonium bromide in 5g of DMF, heating to 60 ℃, stirring and reacting for 1-2 h, cooling to room temperature after complete reaction, adding water for layering, sequentially adding water, saturated sodium chloride solution and water to an organic layer, drying, and carrying out decompression and desolventization to obtain 60.8g of epoxiconazole with the content of 97.3% and the yield of 92.3%.
comparative example 3
Synthesis of epoxiconazole: dissolving 2-methanesulfonic acid methyl ester group-2- (4-fluorophenyl) -3- (2-chlorphenyl) -oxirane (69.31g, 194.3mmol), 1,2, 4-triazole (14.1g, 204.0mmol) and sodium hydride (5.4g, 223.4mmol) in 40g of DMF, heating to 60 ℃, stirring for reaction for 3-4 h, cooling to room temperature after complete reaction, adding water for layering, sequentially using water, a saturated sodium chloride solution and water for washing and drying an organic layer, and decompressing and desolventizing to obtain 58.3g of epoxiconazole with the content of 93.2% and the yield of 84.8%.
Example 4
Synthesis of difenoconazole: dissolving 2- (bromomethyl) -2- (2-chloro-4- (4-chlorophenoxy) phenyl) -4-methyl-1, 3-dioxolane (86.6g, 207.2mmol), 1,2, 4-triazole (15.4g, 223.7mmol), potassium hydroxide (13.6g, 242.4mmol) and 3.5g of dodecyl trimethyl ammonium chloride in 5g of NMP, heating to 130 ℃, reacting for 2-3 h, cooling to room temperature after complete reaction, adding water for layering, washing the organic layer for 2-3 times with water until the pH is less than 8, desolventizing the organic layer under negative pressure, and recrystallizing with toluene to obtain 73.3g of difenoconazole with the content of 95.3% and the yield of 83.0%.
Comparative example 4
Synthesis of difenoconazole: dissolving 2- (bromomethyl) -2- (2-chloro-4- (4-chlorophenoxy) phenyl) -4-methyl-1, 3-dioxolane (86.6g, 207.2mmol), 1,2, 4-triazole (15.4g, 223.7mmol) and potassium hydroxide (13.6g, 242.4mmol) in 50g of NMP, heating to 130 ℃, reacting for 4-5 h, cooling to room temperature after the reaction is completed, adding water for layering, washing an organic layer for 2-3 times with water until the pH value is less than 8, and recrystallizing the organic layer with toluene after negative pressure desolventization to obtain 68.5g of difenoconazole with the content of 95.1% and the yield of 77.4%.
Example 5
Synthesis of propiconazole: dissolving 2-bromomethyl-2- (2, 4-dichlorophenyl-4-propyl-1, 3-dioxolane (64.7g, 182.75mmol), 1,2, 4-triazole (13.6g, 197.36mmol), potassium carbonate (29.0g, 210.2mmol) and 2.5g of ethyl triphenyl phosphonium bromide in 5g of NMP, heating to 130 ℃, reacting for 2-3 h, cooling to room temperature after complete reaction, adding water for layering, washing an organic layer for 2-3 times with water until the pH value is less than 8, and obtaining 58.3g of propiconazole after negative pressure desolventization of the organic layer, wherein the content is 95.1%, and the yield is 88.6%.
Comparative example 5:
Synthesis of propiconazole: dissolving 2-bromomethyl-2- (2, 4-dichlorophenyl-4-propyl-1, 3-dioxolane (64.7g, 182.75mmol), 1,2, 4-triazole (13.6g, 197.36mmol) and potassium carbonate (29.0g, 210.2mmol) in 5g of NMP, heating to 130 ℃, reacting for 4-5 h, cooling to room temperature after complete reaction, adding water for layering, washing an organic layer for 2-3 times with water until the pH value is less than 8, and desolventizing the organic layer under negative pressure to obtain 57.1g of propiconazole with the content of 91.3% and the yield of 83.4%.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (10)
1. A method for reducing 1,3, 4-triazole substitutes in the alkylation reaction process of 1,2, 4-triazole, which is characterized by comprising the following steps: carrying out alkylation reaction on 1,2, 4-triazole and an alkylating reagent in the presence of alkali and a catalyst, and after the reaction is finished, carrying out post-treatment to obtain the 1,2, 4-triazole substituent, wherein the catalyst is one or a combination of more of polyethers, cyclic crown ethers, quaternary ammonium salts, quaternary phosphonium salts, quaternary ammonium bases and tertiary amines.
2. The method for reducing 1,3, 4-triazole substituents during an alkylation reaction of 1,2, 4-triazole according to claim 1, wherein the method comprises the following steps: the catalyst is one or more of triethyl benzyl ammonium chloride, tetramethyl ammonium chloride, tetrabutyl ammonium bromide, dodecyl trimethyl ammonium chloride, ethyl triphenyl phosphonium bromide, 18-crown-6, 15-crown-5, polyethylene glycol and polyethylene glycol dimethyl ether.
3. The method for reducing 1,3, 4-triazole substituents during the alkylation reaction of 1,2, 4-triazole according to claim 1 or 2, wherein the method comprises the following steps: the feeding mass ratio of the catalyst to the alkylating agent is 0.01-0.1: 1.
4. The method for reducing 1,3, 4-triazole substituents during an alkylation reaction of 1,2, 4-triazole according to claim 1, wherein the method comprises the following steps: the alkali is quaternary ammonium base, KOH, NaOH, K2CO3、Na2CO3And one or more of NaH, N-dimethylcyclohexylamine and dicyclohexylamine.
5. The method for reducing 1,3, 4-triazole substituents during the alkylation reaction of 1,2, 4-triazole according to claim 1 or 4, wherein the method comprises the following steps: the feeding molar ratio of the 1,2, 4-triazole to the alkali is 1: 1.01-1.2.
6. The method for reducing 1,3, 4-triazole substituents during an alkylation reaction of 1,2, 4-triazole according to claim 1, wherein the method comprises the following steps: the feeding molar ratio of the 1,2, 4-triazole to the alkylating agent is 1.01-1.3: 1.
7. The method for reducing 1,3, 4-triazole substituents during an alkylation reaction of 1,2, 4-triazole according to claim 1, wherein the method comprises the following steps: the temperature of the alkylation reaction is 50-150 ℃.
8. The method for reducing 1,3, 4-triazole substituents during an alkylation reaction of 1,2, 4-triazole according to claim 1, wherein the method comprises the following steps: the alkylation reaction is carried out in the absence of a solvent or in the presence of a small amount of a solvent, when the reaction is carried out in the presence of a small amount of a solvent, the mass ratio of the solvent to the alkylating reagent is 1: 5-20, and the solvent is one or a combination of more of N, N-dimethylformamide, dimethyl sulfoxide, N-dimethylacetamide, N-methylpyrrolidone, toluene, methylcyclohexane and cyclohexane.
9. The method for reducing 1,3, 4-triazole substituents during an alkylation reaction of 1,2, 4-triazole according to claim 1, wherein the method comprises the following steps: the 1,2, 4-triazole substituent is one of tebuconazole, flutriafol, propiconazole, difenoconazole, epoxiconazole and cyproconazole.
10. The method for reducing 1,3, 4-triazole substituents during an alkylation reaction of 1,2, 4-triazole according to claim 1, wherein the method comprises the following steps: the post-processing method comprises the following steps: adding water into the reaction solution after the reaction is finished for layering, and washing and desolventizing the organic phase to obtain the 1,2, 4-triazole substituent.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111253328A (en) * | 2020-03-26 | 2020-06-09 | 江苏七洲绿色化工股份有限公司 | Preparation method of tebuconazole |
| CN112279839A (en) * | 2020-08-24 | 2021-01-29 | 江苏禾本生化有限公司 | High-yield preparation method of propiconazole |
| CN113582979A (en) * | 2021-08-20 | 2021-11-02 | 浙江禾本科技股份有限公司 | Method for synthesizing propiconazole from isomers |
| CN114773324A (en) * | 2022-04-01 | 2022-07-22 | 山东潍坊双星农药有限公司 | Preparation method of difenoconazole |
| CN115260110A (en) * | 2022-08-12 | 2022-11-01 | 辽宁众辉生物科技有限公司 | Green and efficient synthesis method of tebuconazole |
| CN115594668A (en) * | 2022-12-16 | 2023-01-13 | 江苏七洲绿色化工股份有限公司（Cn） | Purification method of propiconazole 4-H isomer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435564A (en) * | 2013-08-22 | 2013-12-11 | 上虞颖泰精细化工有限公司 | Preparation method of tebuconazole |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103435564A (en) * | 2013-08-22 | 2013-12-11 | 上虞颖泰精细化工有限公司 | Preparation method of tebuconazole |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111253328A (en) * | 2020-03-26 | 2020-06-09 | 江苏七洲绿色化工股份有限公司 | Preparation method of tebuconazole |
| CN112279839A (en) * | 2020-08-24 | 2021-01-29 | 江苏禾本生化有限公司 | High-yield preparation method of propiconazole |
| CN113582979A (en) * | 2021-08-20 | 2021-11-02 | 浙江禾本科技股份有限公司 | Method for synthesizing propiconazole from isomers |
| CN113582979B (en) * | 2021-08-20 | 2023-02-24 | 浙江禾本科技股份有限公司 | Method for synthesizing propiconazole from isomers |
| CN114773324A (en) * | 2022-04-01 | 2022-07-22 | 山东潍坊双星农药有限公司 | Preparation method of difenoconazole |
| CN114773324B (en) * | 2022-04-01 | 2024-03-15 | 山东潍坊双星农药有限公司 | Preparation method of difenoconazole |
| CN115260110A (en) * | 2022-08-12 | 2022-11-01 | 辽宁众辉生物科技有限公司 | Green and efficient synthesis method of tebuconazole |
| CN115594668A (en) * | 2022-12-16 | 2023-01-13 | 江苏七洲绿色化工股份有限公司（Cn） | Purification method of propiconazole 4-H isomer |
| CN115594668B (en) * | 2022-12-16 | 2023-03-14 | 江苏七洲绿色化工股份有限公司 | Purification method of propiconazole 4-H isomer |
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