CN113861079B - Preparation method of high-yield and high-purity pesticide diflubenzuron - Google Patents
Preparation method of high-yield and high-purity pesticide diflubenzuron Download PDFInfo
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- CN113861079B CN113861079B CN202111072483.2A CN202111072483A CN113861079B CN 113861079 B CN113861079 B CN 113861079B CN 202111072483 A CN202111072483 A CN 202111072483A CN 113861079 B CN113861079 B CN 113861079B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
- C07C273/1809—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety
- C07C273/1818—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety from -N=C=O and XNR'R"
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Abstract
The invention relates to a preparation method of high-yield and high-purity pesticide diflubenzuron, which comprises the following steps: mixing mixed xylene with 2, 6-difluorobenzamide, heating and refluxing to remove part of mixed xylene, dripping p-chlorophenyl isocyanate, carrying out heat preservation reaction after dripping, removing part of mixed xylene after reaction, and cooling to obtain the diflubenzuron. The preparation method of the high-yield and high-purity pesticide diflubenzuron adopts mixed xylene as a solvent, has low cost and high quality, ensures that the yield of the prepared diflubenzuron is more than 95 percent, ensures that the content of the diflubenzuron finished product is more than 99 percent, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of pesticide preparation, and particularly relates to a preparation method of high-yield and high-purity pesticide diflubenzuron.
Background
The diflubenzuron is a specific low-toxicity insect growth regulator, and belongs to the benzoic acid phenyl urea pesticide. The insecticidal mechanism is that the insect chitin synthesis is inhibited, so that the larvae can not form new epidermis and the insect bodies are malformed to die during molting. The composition is effective on lepidoptera pests, has no phytotoxicity on plants in effective amounts, and has no adverse effect on beneficial organisms such as birds, fish, shrimp, frog, bee, ladybug, parasitic wasp, etc.
The preparation method of diflubenzuron described in the prior art has the following disadvantages: (1) The process is complex, and the catalyst is unreasonable, so that the synthesis yield and purity are low, and the preparation cost is high; (2) The solvent used is unreasonable, so that the addition amount of raw materials is too large, and the addition amount cannot be ensured to reach the saturation degree of a reaction system.
Chinese patent CN201110083617.0 discloses a method for preparing pesticide diflubenzuron, using dimethylformamide and p-chloroaniline as starting materials, reacting under the action of phosgene, catalyst and cocatalyst to obtain a solution composed of p-chlorobenzenesulfonic acid isocyanate and aromatic compound solvent, and then adding the obtained p-chlorobenzenesulfonic acid isocyanate and aromatic compound solvent into the mixture of aromatic compound solvent and 2, 6-difluorobenzamide to obtain diflubenzuron; the improvement of the yield and the purity of the catalyst is realized by using two catalysts and cocatalysts, but the preparation cost is also increased, and in the process of dropwise adding the p-chlorophenyl isocyanate and the aromatic compound solvent into the mixture of the aromatic compound solvent and the 2, 6-difluorobenzamide, side reactions of moisture in the aromatic compound solvent and the like are not considered, so that the yield and the purity of the diflubenzuron are influenced.
Chinese patent CN202110074727.4 discloses a synthesis process and application of diflubenzuron, the synthesis process of diflubenzuron comprises: and mixing an aromatic hydrocarbon solvent and 2, 6-difluorobenzamide, heating to 130-145 ℃ for reflux dehydration, cooling, dropwise adding p-chlorophenyl isocyanate, heating to 130-145 ℃ for reaction after the dropwise adding is finished, and performing aftertreatment to obtain the diflubenzuron. The yield of the diflubenzuron is more than 92%, the purity is more than 97%, and a certain gap exists between the yield and the purity which is required to be higher than 98% in the market.
Disclosure of Invention
The invention aims to provide a preparation method of high-yield and high-purity pesticide diflubenzuron, which has the advantages of simple operation, low preparation cost and high yield and content of the prepared diflubenzuron, and is suitable for industrial production.
The invention solves the problems by adopting the following technical scheme: a preparation method of high-yield and high-purity pesticide diflubenzuron, which comprises the following steps:
mixing the mixed xylene with the 2, 6-difluorobenzamide, heating, refluxing, desolventizing, dropwise adding p-chlorophenyl isocyanate, carrying out heat preservation reaction after the dropwise adding is finished, removing the mixed xylene after the reaction is finished, and carrying out cooling post-treatment to obtain the diflubenzuron.
Preferably, the mixed xylenes are a mixture of para-xylene, ortho-xylene, meta-xylene, and ethylbenzene.
Preferably, the mass ratio of the 2, 6-difluorobenzamide, the p-chlorophenyl isocyanate and the mixed xylene is 1:1.02:5.
Preferably, the method specifically comprises the following steps: mixing mixed xylene and 2, 6-difluorobenzamide, heating to 140-145 ℃, refluxing to remove solvent, dropwise adding p-chlorophenyl isocyanate, carrying out heat preservation reaction at 140-145 ℃ after the dropwise adding is finished, removing mixed xylene after the reaction is finished, cooling to 10-15 ℃, and carrying out post-treatment to obtain the diflubenzuron.
Preferably, the p-chlorophenyl isocyanate is added dropwise within 2-2.5 hours.
Preferably, the heat preservation reaction time is 4-4.5 h.
Preferably, the mass of the mixed xylene removed before the reaction accounts for 10-15% of the total mass of the solvent.
Preferably, the mass of the separated mixed xylene after the reaction is finished accounts for 32-35% of the total mass of the solvent.
The reaction equation of the present invention is shown below:
compared with the prior art, the invention has the advantages that:
(1) The cost price of the mixed xylene is far lower than that of other aromatic hydrocarbon solvents with the boiling point of 130-140 ℃ as the solvent; the mixed xylene is removed before the reaction, so that free water in the system can be completely removed, in the post-treatment process, the dissolution amount of a finished product in a solvent can be reduced by removing part of mixed xylene again, the reaction yield is improved, and the main impurity 1, 3-bis (4-chlorophenyl) urea (easy to sublimate at high temperature) in the reaction is also removed from the system in the process of removing the mixed xylene, so that the product content is improved.
(2) Under the condition of ensuring the yield and content of the product, the mass ratio of the solvent to the reaction materials (the mass ratio of the 2, 6-difluorobenzamide, the p-chlorophenyl isocyanate to the mixed xylene is 1:1.02:5) is optimized, and the single kettle yield of the product is greatly improved; after removing part of mixed xylene after the reaction is finished, cooling to 10-15 ℃ for post-treatment, and reducing the solubility of the product in a solvent so as to improve the product yield.
(3) The invention limits the mass of the mixed xylene removed before the reaction to be 10-15% of the total mass of the solvent, and the mass of the mixed xylene removed after the reaction is over to be 32-35% of the total mass of the solvent, thereby ensuring that the reaction is complete, free water in the system is completely removed, and the yield is high, and specifically comprises the following steps: excessive solvent is removed before the reaction, the residual solvent cannot ensure the reactant to fully react, and if the solvent is removed too little, the free moisture in the system cannot be completely removed; after the reaction, too much solvent is removed, the viscosity of the system is increased, the material transferring difficulty is high, the solvent is too little, the dissolving amount of the product is relatively more, and the yield is lower.
(4) The synthesis process has the advantages of simple operation, low production cost, high product quality and economic benefit, the yield of the synthesized diflubenzuron is more than 95%, the content of the diflubenzuron finished product is more than 99%, the solvent can be recycled, and the synthesis process is more environment-friendly and safer and is more beneficial to industrial production.
Detailed Description
The present invention is described in further detail below with reference to examples.
Xylene is classified into three isomers of o-xylene, m-xylene and p-xylene according to the difference of the positions of two methyl groups. Industrially, xylene is a mixture of the above isomers and ethylbenzene, i.e., the solvent used in the present invention. In technical grade mixed xylene, the content proportion of the main components of paraxylene, metaxylene, orthoxylene and ethylbenzene in the xylene is 30%, 10%, 48% and 12%, respectively.
Example 1
187.5g of mixed xylene and 37.5g of 2, 6-difluorobenzamide are added into a 500mL four-necked flask, the mixture is stirred, the temperature of the system is raised to 145 ℃, the reflux state is maintained, and 19g of mixed xylene (carrying out all free moisture in the system) is removed; dripping 38.3g of p-chlorophenyl isocyanate, and continuously stirring at 145 ℃ for 4 hours after finishing dripping within 2 hours; after the reaction is finished, 62g of mixed xylene is removed; cooling the system to 10 ℃, filtering, taking cold mixed xylene (the temperature is 0-10 ℃, and the solubility of materials in the mixed xylene can be reduced), washing a filter cake, and drying to obtain the diflubenzuron finished product, wherein the content is 99.24%, and the yield is 95.57% (calculated by 2, 6-difluorobenzamide).
Example 2
220g of mixed xylene and 44.0g of 2, 6-difluorobenzamide are added into a 500mL four-necked flask, mixed and stirred, the temperature of the system is raised to 145 ℃, the reflux state is maintained, and 26g of mixed xylene (carrying out all free water in the system) is removed; 44.9g of p-chlorophenyl isocyanate is dripped, the dripping is completed within 2.5 hours, and the dripping is continued to be stirred for 4.5 hours at 145 ℃ under heat preservation; after the reaction is finished, 72g of mixed xylene is removed; cooling the system to 10 ℃, filtering, taking cold mixed xylene (the temperature is 0-10 ℃) to wash a filter cake, and drying to obtain a diflubenzuron finished product, wherein the content is 99.57%, and the yield is 96.10% (calculated by 2, 6-difluorobenzamide).
Example 3
220g of mixed xylene and 44.0g of 2, 6-difluorobenzamide are added into a 500mL four-necked flask, and mixed and stirred; heating the system to 145 ℃, maintaining a reflux state, and removing 26g of mixed xylene (taking out all free water in the system); 44.9g of p-chlorophenyl isocyanate is dripped, the dripping is completed within 2 hours, and the dripping is continued to be stirred for 4 hours at 145 ℃ under heat preservation; after the reaction is finished, 72g of mixed xylene is removed; and cooling the system to 10 ℃, filtering, taking a small amount of cold mixed xylene (the temperature is 0-10 ℃) to wash a filter cake, and drying to obtain the diflubenzuron finished product, wherein the content is 99.28%, and the yield is 96.08% (calculated by 2, 6-difluorobenzamide).
Comparative example 1
220g of toluene and 44.0g of 2, 6-difluorobenzamide are added into a 500mL four-necked flask, and mixed and stirred; heating the system to 110.6 ℃, maintaining a reflux state, and removing 26g of toluene (taking out all free water in the system); 44.9g of p-chlorophenyl isocyanate is dripped, the dripping is completed within 2 hours, and the dripping is continued to be stirred for 4 hours at 110.6 ℃ under heat preservation; after the reaction is finished, 72g of toluene is removed; cooling the system to 10 ℃, filtering, taking cold toluene (the temperature is 0-10 ℃) to wash a filter cake, and drying to obtain the diflubenzuron finished product, wherein the content is 98.75%, and the yield is 91.76% (calculated by 2, 6-difluorobenzamide).
Comparative example 2
220g of mixed xylene and 44.0g of 2, 6-difluorobenzamide are added into a 500mL four-necked flask, mixed and stirred, and the system is heated to 145 ℃; 44.9g of p-chlorophenyl isocyanate is dripped, the dripping is completed within 2 hours, and the dripping is continued to be stirred for 4 hours at 145 ℃ under heat preservation; after the reaction is finished, 72g of mixed xylene is removed; cooling the system to 10 ℃, filtering, taking cold mixed xylene (the temperature is 0-10 ℃) to wash a filter cake, and drying to obtain a diflubenzuron finished product, wherein the content is 95.69%, and the yield is 90.06% (calculated by 2, 6-difluorobenzamide).
Comparative example 3
220g of mixed xylene and 44.0g of 2, 6-difluorobenzamide are added into a 500mL four-necked flask, and mixed and stirred; heating the system to 145 ℃, maintaining a reflux state, and removing 26g of mixed xylene (taking out all free water in the system); 44.9g of p-chlorophenyl isocyanate is dripped, the dripping is completed within 2 hours, and the dripping is continued to be stirred for 4 hours at 145 ℃ under heat preservation; cooling the system to 10 ℃, filtering, taking cold mixed xylene (the temperature is 0-10 ℃) to wash a filter cake, and drying to obtain a diflubenzuron finished product, wherein the content is 96.72%, and the yield is 88.75% (calculated by 2, 6-difluorobenzamide).
Comparative example 4
220g of mixed xylene and 44.0g of 2, 6-difluorobenzamide are added into a 500mL four-necked flask, mixed and stirred, the temperature of the system is raised to 145 ℃, the reflux state is maintained, and 26g of mixed xylene (carrying out all free water in the system) is removed; 44.9g of p-chlorophenyl isocyanate is dripped, the dripping is completed within 2 hours, and the dripping is continued to be stirred for 4 hours at 145 ℃ under heat preservation; after the reaction is finished, 72g of mixed xylene is removed; cooling the system to 10 ℃, filtering, taking cold mixed xylene (the temperature is 0-10 ℃) to wash a filter cake, and drying to obtain the diflubenzuron finished product, wherein the content is 99.32%, and the yield is 95.53% (calculated by 2, 6-difluorobenzamide).
Comparative example 5
220g of mixed xylene and 44.0g of 2, 6-difluorobenzamide are added into a 500mL four-necked flask, mixed and stirred, the temperature of the system is raised to 145 ℃, the reflux state is maintained, and 10g of mixed xylene (carrying out all free water in the system) is removed; 44.9g of p-chlorophenyl isocyanate is dripped, the dripping is completed within 2 hours, and the dripping is continued to be stirred for 4 hours at 145 ℃ under heat preservation; after the reaction is finished, 72g of mixed xylene is removed; and cooling the system to 10 ℃, filtering, washing a filter cake by using cold mixed xylene (the temperature is 0-10 ℃), and drying to obtain a diflubenzuron finished product, wherein the content is 98.12%, and the yield is 95.10% (calculated by 2, 6-difluorobenzamide).
Comparative example 6
220g of mixed xylene and 44.0g of 2, 6-difluorobenzamide are added into a 500mL four-necked flask, mixed and stirred, the temperature of the system is raised to 145 ℃, the reflux state is maintained, and 26g of mixed xylene (carrying out all free water in the system) is removed; 44.9g of p-chlorophenyl isocyanate is dripped, the dripping is completed within 2 hours, and the dripping is continued to be stirred for 4 hours at 145 ℃ under heat preservation; after the reaction is finished, removing 36g of mixed xylene; cooling the system to 10 ℃, filtering, taking cold mixed xylene (the temperature is 0-10 ℃, and the solubility of materials in the mixed xylene can be reduced), washing a filter cake, and drying to obtain the diflubenzuron finished product, wherein the content is 98.53%, and the yield is 92.46% (calculated by 2, 6-difluorobenzamide).
In addition to the above embodiments, the present invention also includes other embodiments, and all technical solutions that are formed by equivalent transformation or equivalent substitution should fall within the protection scope of the claims of the present invention.
Claims (5)
1. A preparation method of pesticide diflubenzuron is characterized by comprising the following steps: the method comprises the following steps:
mixing mixed xylene and 2, 6-difluorobenzamide, heating to 140-145 ℃ to reflux and remove the mixed xylene, dropwise adding p-chlorophenyl isocyanate, carrying out heat preservation reaction at 140-145 ℃ after the dropwise adding is finished, removing the mixed xylene after the reaction is finished, cooling to 10-15 ℃ and carrying out post-treatment to obtain diflubenzuron;
the mass of the mixed xylene removed before the reaction accounts for 10-15% of the total mass of the solvent, and the mass of the mixed xylene removed after the reaction is over accounts for 32-35% of the total mass of the solvent.
2. The method for preparing pesticide diflubenzuron according to claim 1, which is characterized in that: the mixed xylene is a mixture of para-xylene, ortho-xylene, meta-xylene and ethylbenzene.
3. The method for preparing pesticide diflubenzuron according to claim 1, which is characterized in that: the mass ratio of the 2, 6-difluorobenzamide, the p-chlorophenyl isocyanate and the mixed xylene is 1:1.02:5.
4. The method for preparing pesticide diflubenzuron according to claim 1, which is characterized in that: and finishing the dropwise adding of the p-chlorophenyl isocyanate within 2-2.5 hours.
5. The method for preparing pesticide diflubenzuron according to claim 1, which is characterized in that: the heat preservation reaction time is 4-4.5 h.
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Citations (7)
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| US4117009A (en) * | 1977-06-09 | 1978-09-26 | Gaf Corporation | Method of making N-[4-chlorophenyl)amino]carbonyl)-2,6-difluorobenzamide |
| CN86108203A (en) * | 1985-12-09 | 1987-09-02 | 国际壳牌研究有限公司 | Process for preparing acyl ureas |
| CS32088A1 (en) * | 1988-01-18 | 1990-04-11 | Kalab Jiri | Method of 1(4-chlorophenyl)-3-(2,6-difluoro-benzoyl) ura preparation |
| CN101293858A (en) * | 2007-04-28 | 2008-10-29 | 金人宪 | Synthesis method of chlorbenzuron by using phosgene as raw material |
| CN102180813A (en) * | 2011-04-02 | 2011-09-14 | 连云港市金囤农化有限公司 | Method for preparing diflubenzuron serving as pesticide |
| CN112876384A (en) * | 2021-01-20 | 2021-06-01 | 安阳市安林生物化工有限责任公司 | Synthesis process and application of diflubenzuron |
| CN113368896A (en) * | 2021-06-11 | 2021-09-10 | 河北威远生物化工有限公司 | Catalyst for diflubenzuron synthesis and preparation method of diflubenzuron |
-
2021
- 2021-09-14 CN CN202111072483.2A patent/CN113861079B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4117009A (en) * | 1977-06-09 | 1978-09-26 | Gaf Corporation | Method of making N-[4-chlorophenyl)amino]carbonyl)-2,6-difluorobenzamide |
| CN86108203A (en) * | 1985-12-09 | 1987-09-02 | 国际壳牌研究有限公司 | Process for preparing acyl ureas |
| CS32088A1 (en) * | 1988-01-18 | 1990-04-11 | Kalab Jiri | Method of 1(4-chlorophenyl)-3-(2,6-difluoro-benzoyl) ura preparation |
| CN101293858A (en) * | 2007-04-28 | 2008-10-29 | 金人宪 | Synthesis method of chlorbenzuron by using phosgene as raw material |
| CN102180813A (en) * | 2011-04-02 | 2011-09-14 | 连云港市金囤农化有限公司 | Method for preparing diflubenzuron serving as pesticide |
| CN112876384A (en) * | 2021-01-20 | 2021-06-01 | 安阳市安林生物化工有限责任公司 | Synthesis process and application of diflubenzuron |
| CN113368896A (en) * | 2021-06-11 | 2021-09-10 | 河北威远生物化工有限公司 | Catalyst for diflubenzuron synthesis and preparation method of diflubenzuron |
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