CN111825597A - Method for synthesizing procymidone - Google Patents
Method for synthesizing procymidone Download PDFInfo
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- CN111825597A CN111825597A CN202010733568.XA CN202010733568A CN111825597A CN 111825597 A CN111825597 A CN 111825597A CN 202010733568 A CN202010733568 A CN 202010733568A CN 111825597 A CN111825597 A CN 111825597A
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- CN
- China
- Prior art keywords
- procymidone
- water
- trichlorobenzene
- temperature
- synthesizing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- QXJKBPAVAHBARF-BETUJISGSA-N procymidone Chemical compound O=C([C@]1(C)C[C@@]1(C1=O)C)N1C1=CC(Cl)=CC(Cl)=C1 QXJKBPAVAHBARF-BETUJISGSA-N 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 12
- JLEJCNOTNLZCHQ-UHFFFAOYSA-N methyl 2-chloropropanoate Chemical compound COC(=O)C(C)Cl JLEJCNOTNLZCHQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000010992 reflux Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000007599 discharging Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- XKEFYDZQGKAQCN-UHFFFAOYSA-N 1,3,5-trichlorobenzene Chemical compound ClC1=CC(Cl)=CC(Cl)=C1 XKEFYDZQGKAQCN-UHFFFAOYSA-N 0.000 claims description 17
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- DZHFFMWJXJBBRG-UHFFFAOYSA-N 1-bromo-3,5-dichlorobenzene Chemical compound ClC1=CC(Cl)=CC(Br)=C1 DZHFFMWJXJBBRG-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 125000002524 organometallic group Chemical group 0.000 claims description 2
- UQRLKWGPEVNVHT-UHFFFAOYSA-N 3,5-dichloroaniline Chemical compound NC1=CC(Cl)=CC(Cl)=C1 UQRLKWGPEVNVHT-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 244000291564 Allium cepa Species 0.000 description 1
- 244000144730 Amygdalus persica Species 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- 240000008067 Cucumis sativus Species 0.000 description 1
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 1
- 235000016623 Fragaria vesca Nutrition 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- 235000011363 Fragaria x ananassa Nutrition 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 241000233639 Pythium Species 0.000 description 1
- 206010039509 Scab Diseases 0.000 description 1
- 241000221696 Sclerotinia sclerotiorum Species 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 241001052560 Thallis Species 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000002316 fumigant Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/52—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring condensed with a ring other than six-membered
Abstract
The invention discloses a method for synthesizing procymidone, which comprises the following specific steps: s1: adding methyl chloropropionate, ammonia water and a catalyst into a 500ml four-neck flask with a stirrer, and mixing and stirring for later use; s2: heating and refluxing for 4h, and controlling methyl chloropropionate to be less than 1% in the intermediate process; s3: when the temperature is raised to 60 ℃, adding water and 1,3, 5-sym-trichlorobenzene, carrying out heating reflux reaction, controlling the content of the 1,3, 5-sym-trichlorobenzene to be less than 0.5% in the middle process, and discharging when the temperature is raised to 60 ℃ to obtain a solid for later use; s4: washing the solid obtained after discharging twice with water, and then washing with alcohol for 1 time for later use; s5: and (3) drying the substance washed by the water for 2 times and the alcohol for 1 time to obtain the procymidone. The route of the invention does not select high-price raw material 3, 5-dichloroaniline, has the characteristics of less three wastes, high product yield and good quality, and has obvious economic and social benefits.
Description
Technical Field
The invention relates to the technical field of procymidone, in particular to a method for synthesizing procymidone.
Background
Procymidone is a systemic fungicide developed and produced by Sumitomo chemical industry Co. Can effectively inhibit the synthesis of triglyceride in the thalli, and has double functions of protection and treatment. Mainly acts on cell membranes, hinders the synthesis of normal cell walls at the top of hyphae, and inhibits the development of hyphae. The main control objects are sclerotinia sclerotiorum and gray mold, and the composition has good protection effect, long lasting period and can prevent the development of scabs. Is suitable for fruit trees such as corn, cucumber, tomato, scallion, rape, grape, strawberry, peach, cherry, etc. The main preparation types are: 50% of procymidone wettable powder, 30% of granular fumigant, 25% of flowable powder and colloidal suspension. According to data query, the technology for synthesizing procymidone mainly comprises the following steps: and (3) reacting methyl methacrylate with 3, 5-dichloroaniline to obtain the procymidone.
The 3, 5-dichloroaniline used as the raw material in the process is difficult to source and expensive, and a large amount of acidic wastewater and waste residues are generated during the production of the raw material; at present, the domestic procymidone is synthesized by adopting the process, and a plurality of environmental pollution factors and cost pressure exist.
Disclosure of Invention
The invention aims to provide a method for synthesizing procymidone, which comprises the following specific steps:
s1: adding methyl chloropropionate, ammonia water and a catalyst into a 500ml four-neck flask with a stirrer, and mixing and stirring for later use;
s2: heating and refluxing for 4h, and controlling methyl chloropropionate to be less than 1% in the intermediate process;
s3: when the temperature is raised to 60 ℃, adding water and 1,3, 5-sym-trichlorobenzene, carrying out heating reflux reaction, controlling the content of the 1,3, 5-sym-trichlorobenzene to be less than 0.5% in the middle process, and discharging when the temperature is raised to 60 ℃ to obtain a solid for later use;
s4: washing the solid obtained after discharging twice with water, and then washing with alcohol for 1 time for later use;
s5: and (3) drying the substance washed by the water for 2 times and the alcohol for 1 time to obtain the procymidone.
Preferably, the molar ratio of methyl methacrylate to ammonia is: 1:1.1-1.5.
Preferably, the catalyst is an organometallic complex of copper or antimony.
Preferably, the molar ratio of the methyl chloropropionate to the 1,3, 5-trichlorobenzene is 1.1-1.3: 1.
Preferably, the 1,3, 5-trichlorobenzene can be replaced by 1, 3-dichloro-5-bromobenzene.
Compared with the prior art, the invention has the beneficial effects that: the route of the invention does not select high-price raw material 3, 5-dichloroaniline, has the characteristics of less three wastes, high product yield and good quality, and has obvious economic and social benefits.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
56.8g of methyl chloropropionate, 22.8g of 35% ammonia water and 0.5g of catalyst are put into a 500ml four-neck flask with stirring, the temperature is raised and the reflux reaction is carried out for 4h, the content of the methyl chloropropionate is controlled to be less than 1%, the temperature is reduced to 60 ℃, 150g of water and 55.8g of 1,3, 5-trichlorobenzene are added, the temperature is raised and the reflux is carried out, the content of the 1,3, 5-trichlorobenzene is controlled to be less than 0.5%, the temperature is reduced to 60 ℃, the materials are discharged, the materials are washed twice, washed once with alcohol and dried, 842g of procymidone, the content is 98%, and the yield is 94.
Example 2
56.8g of methyl chloropropionate, 23.8g of 35% ammonia water and 0.5g of catalyst are put into a 500ml four-neck flask with stirring, the temperature is raised and the reflux reaction is carried out for 4h, the content of the methyl chloropropionate is controlled to be less than 1%, the temperature is reduced to 60 ℃, 150g of water and 55.8g of 1,3, 5-trichlorobenzene are added, the temperature is raised and the reflux is carried out, the content of the 1,3, 5-trichlorobenzene is controlled to be less than 0.5%, the temperature is reduced to 60 ℃, the materials are discharged, the materials are washed twice by water, washed by alcohol once and dried, thus 839g of procymidone, the content is 98.5% and the.
Example 3
57g of methyl chloropropionate, 22.8g of 35% ammonia water and 0.5g of catalyst are put into a 500ml four-neck flask with stirring, the temperature is raised and the reflux reaction is carried out for 4h, the methyl chloropropionate is controlled to be less than 1%, the temperature is increased to 60 ℃, 150g of water and 55.8g of 1,3, 5-trichlorobenzene are added, the temperature is raised and the reflux is carried out, the content of the 1,3, 5-trichlorobenzene is controlled to be less than 0.5%, the temperature is increased to 60 ℃, the materials are discharged, the water washing is carried out twice, the alcohol washing is carried out once, and the drying is carried out, thus obtaining 847g of procymidone, the content of.
Example 4
57g of methyl chloropropionate, 23g of 35% ammonia water and 0.5g of catalyst are put into a 500ml four-neck flask with stirring, the temperature is raised and the reflux reaction is carried out for 4h, the methyl chloropropionate is controlled to be less than 1%, the temperature is raised to 60 ℃, 150g of water and 55.8g of 1,3, 5-trichlorobenzene are added, the temperature is raised and the reflux is carried out, the content of the 1,3, 5-trichlorobenzene is controlled to be less than 0.5%, the temperature is raised to 60 ℃, the materials are discharged, the water washing is carried out twice, the alcohol washing is carried out once, and the drying is carried out, thus obtaining 843g of the procymidone.
Example 5
57.6g of methyl chloropropionate, 24.6g of 35% ammonia water and 0.5g of catalyst are put into a 500ml four-neck flask with stirring, the temperature is raised and the reflux reaction is carried out for 4h, the content of the methyl chloropropionate is controlled to be less than 1%, the temperature is reduced to 60 ℃, 150g of water and 55.8g of 1,3, 5-trichlorobenzene are added, the temperature is raised and the reflux is carried out, the content of the 1,3, 5-trichlorobenzene is controlled to be less than 0.5%, the temperature is reduced to 60 ℃, the materials are discharged, the materials are washed twice, washed once with alcohol and dried, and 852g of procymidone, the content of 98.3% and the yield of.
Example 6
56.4g of methyl chloropropionate, 23.6g of 35% ammonia water and 0.5g of catalyst are put into a 500ml four-neck flask with stirring, the temperature is raised and the reflux reaction is carried out for 4h, the content of the methyl chloropropionate is controlled to be less than 1%, the temperature is reduced to 60 ℃, 150g of water and 55.8g of 1,3, 5-trichlorobenzene are added, the temperature is raised and the reflux is carried out, the content of the 1,3, 5-trichlorobenzene is controlled to be less than 0.5%, the temperature is reduced to 60 ℃, the materials are discharged, the materials are washed twice, washed once with alcohol and dried, and the pythium procumbens 829g, the content is 98.9% and.
Example 7
57.2g of methyl chloropropionate, 23.5g of 35% ammonia water and 0.5g of catalyst are put into a 500ml four-neck flask with stirring, the temperature is raised and the reflux reaction is carried out for 4h, the content of the methyl chloropropionate is controlled to be less than 1%, the temperature is reduced to 60 ℃, 150g of water and 55.8g of 1,3, 5-trichlorobenzene are added, the temperature is raised and the reflux is carried out, the content of the 1,3, 5-trichlorobenzene is controlled to be less than 0.5%, the temperature is reduced to 60 ℃, the materials are discharged, the materials are washed twice by water, washed by alcohol once and dried, thus 839g of procymidone, the content is 98.6% and the.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (5)
1. A method for synthesizing procymidone, which is characterized by comprising the following steps: the method for synthesizing the procymidone comprises the following specific steps:
s1: adding methyl chloropropionate, ammonia water and a catalyst into a 500ml four-neck flask with a stirrer, and mixing and stirring for later use;
s2: heating and refluxing for 4h, and controlling methyl chloropropionate to be less than 1% in the intermediate process;
s3: when the temperature is raised to 60 ℃, adding water and 1,3, 5-sym-trichlorobenzene, carrying out heating reflux reaction, controlling the content of the 1,3, 5-sym-trichlorobenzene to be less than 0.5% in the middle process, and discharging when the temperature is raised to 60 ℃ to obtain a solid for later use;
s4: washing the solid obtained after discharging twice with water, and then washing with alcohol for 1 time for later use;
s5: and (3) drying the substance washed by the water for 2 times and the alcohol for 1 time to obtain the procymidone.
2. A method of synthesizing procymidone according to claim 1, wherein: the molar ratio of methyl methacrylate to ammonia water was: 1:1.1-1.5.
3. A method of synthesizing procymidone according to claim 1, wherein: the catalyst is an organometallic complex of copper or antimony.
4. A method of synthesizing procymidone according to claim 1, wherein: the molar ratio of methyl chloropropionate to 1,3, 5-sym-trichlorobenzene is 1.1-1.3: 1.
5. A method of synthesizing procymidone according to claim 1, wherein: the 1,3, 5-trichlorobenzene may be replaced by 1, 3-dichloro-5-bromobenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010733568.XA CN111825597A (en) | 2020-07-27 | 2020-07-27 | Method for synthesizing procymidone |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010733568.XA CN111825597A (en) | 2020-07-27 | 2020-07-27 | Method for synthesizing procymidone |
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| CN111825597A true CN111825597A (en) | 2020-10-27 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202010733568.XA Pending CN111825597A (en) | 2020-07-27 | 2020-07-27 | Method for synthesizing procymidone |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114671797A (en) * | 2020-12-24 | 2022-06-28 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of procymidone |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7409983A (en) * | 1969-03-19 | 1974-09-25 | ||
| JPS56169670A (en) * | 1980-06-02 | 1981-12-26 | Sumitomo Chem Co Ltd | Preparation of n-phenylcyclopropanecarboximide derivative |
| JPS572272A (en) * | 1980-06-04 | 1982-01-07 | Sumitomo Chem Co Ltd | Preparation of n-phenylcyclopropanedicarboxylic acid imide derivative |
| CN101906063A (en) * | 2010-08-13 | 2010-12-08 | 陕西亿农高科药业有限公司 | Scale synthesis process of procymidone original drug of efficient agricultural bactericide in two steps |
-
2020
- 2020-07-27 CN CN202010733568.XA patent/CN111825597A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7409983A (en) * | 1969-03-19 | 1974-09-25 | ||
| JPS56169670A (en) * | 1980-06-02 | 1981-12-26 | Sumitomo Chem Co Ltd | Preparation of n-phenylcyclopropanecarboximide derivative |
| JPS572272A (en) * | 1980-06-04 | 1982-01-07 | Sumitomo Chem Co Ltd | Preparation of n-phenylcyclopropanedicarboxylic acid imide derivative |
| CN101906063A (en) * | 2010-08-13 | 2010-12-08 | 陕西亿农高科药业有限公司 | Scale synthesis process of procymidone original drug of efficient agricultural bactericide in two steps |
Non-Patent Citations (1)
| Title |
|---|
| 沃解明: "新型农用杀菌剂——腐霉利", 《上海化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114671797A (en) * | 2020-12-24 | 2022-06-28 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of procymidone |
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Application publication date: 20201027 |