CN110878084A - Preparation method of nicosulfuron original drug - Google Patents
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Abstract
The invention provides a preparation method of nicosulfuron technical, which comprises the following steps: the preparation method of the nicosulfuron technical comprises the following steps: synthesizing 2-isocyanatosulfonyl-N, N-dimethylnicotinamide 2-aminosulfonyl-N, N-dimethylnicotinamide, triphosgene and a deacidification agent, and reacting at 0-80 ℃ to synthesize 2-isocyanatosulfonyl-N, N-dimethylnicotinamide; the synthetic nicosulfuron original drug 2-isocyanatosulfonyl-N, N-dimethylnicotinamide and 2-amino-4, 6-dimethoxypyrimidine react at 0-100 ℃ to synthesize the nicosulfuron original drug. The method provided by the invention is a new synthesis method for synthesizing nicosulfuron technical by taking 2-chlorosulfonyl-N, N-dimethylnicotinamide, triphosgene, triethylamine and 2-amino-4, 6-dimethoxypyrimidine as main raw materials, and the obtained nicosulfuron has high purity and yield.
Description
Technical Field
The invention relates to the field of pesticide synthesis, in particular to a preparation method of a nicosulfuron original drug.
Background
The nicosulfuron technical has the chemical formula of 2- (4, 6-dimethylpyrimidine-2-pyrimidylaminocarbamoylsulfonyl) -N, N-dimethylnicotinamide, the molecular formula of C15H18N6O6S and the molecular weight of 410.40, and is a new generation of sulfonylurea systemic herbicide with broad spectrum, high efficiency, low degree, low residue and high selectivity developed by Nippon rock Producer and United nationality Dupont. The herbicide is mainly used for preventing and removing annual and perennial grassy weeds and part of broadleaf weeds in the corn fields, and becomes a main herbicide variety for the corn fields due to the characteristics of low field dosage, good weeding effect and safety for corn growth.
At present, the industrial production method of nicosulfuron mainly uses 2-amino-4, 6-dimethoxy pyrimidine as a raw material to synthesize 4, 6-dimethoxy-2-pyrimidine isocyanate, and then the 4, 6-dimethoxy-2-pyrimidine isocyanate is added with 2-aminosulfonyl-N, N-dimethylnicotinamide to obtain the nicosulfuron, and the specific synthetic route is as follows:
as can be seen from the above synthetic routes: the synthetic route has the advantages of troublesome operation, lower yield of nicosulfuron technical grade and higher cost.
Disclosure of Invention
In view of the above, there is a need to provide a method for preparing nicosulfuron technical product, so as to overcome the above problems.
Therefore, the invention provides a preparation method of nicosulfuron technical, which comprises the following steps:
synthesizing 2-isocyanatosulfonyl-N, N-dimethylnicotinamide 2-aminosulfonyl-N, N-dimethylnicotinamide, triphosgene and an acid-removing agent, wherein the acid-removing agent is triethylamine, sodium carbonate, potassium carbonate or sodium bicarbonate, and the triphosgene reacts at 0-80 ℃ to synthesize the 2-isocyanatosulfonyl-N, N-dimethylnicotinamide;
the synthetic nicosulfuron original drug 2-isocyanatosulfonyl-N, N-dimethylnicotinamide and 2-amino-4, 6-dimethoxypyrimidine react at 0-100 ℃ to synthesize the nicosulfuron original drug.
The route for synthesizing the nicosulfuron technical material by using the 2-aminosulfonyl-N, N-dimethylnicotinamide as the starting raw material is as follows:
based on the above, the step of synthesizing 2-isocyanatosulfonyl-N, N-dimethylnicotinamide includes: dissolving 2-chlorosulfonyl-N, N-dimethylnicotinamide, triphosgene and the acid-forming agent in a first solvent, dropwise adding the acid-forming agent at the temperature of 0-80 ℃, and reacting for 1-3 h to synthesize 2-isocyanatosulfonyl-N, N-dimethylnicotinamide; wherein the molar ratio of the 2-chlorosulfonyl-N, N-dimethylnicotinamide to the triphosgene to the acid-forming agent is 1: 1-2: 1-3, and the first solvent is dichloromethane, ethyl acetate, methyl chloride or acetone.
In the process of synthesizing 2-isocyanatosulfonyl-N, N-dimethylnicotinamide, the acid-forming agent is mainly used for neutralizing hydrochloric acid generated by the reaction of 2-chlorosulfonyl-N, N-dimethylnicotinamide and triphosgene and promoting the forward reaction. Because the reaction of hydrochloric acid and the acid-removing agent is violent, the acid-removing agent must be added dropwise for safety, otherwise, the addition of a large amount of the acid-removing agent at one time can cause violent reaction and increase unsafe factors. Preferably, the acid-addition agent is triethylamine.
Based on the above, the step of synthesizing the nicosulfuron technical material comprises the following steps: in the step of synthesizing 2-isocyanatosulfonyl-N, N-dimethylnicotinamide, the synthesized 2-isocyanatosulfonyl-N, N-dimethylnicotinamide directly reacts with 2-amino-4, 6-dimethoxypyrimidine at 0-100 ℃ for 1-3 h to synthesize nicosulfuron technical, wherein the molar ratio of 2-chlorosulfonyl-N, N-dimethylnicotinamide to 2-amino-4, 6-dimethoxypyrimidine is 1: 1.
based on the above, the step of synthesizing the nicosulfuron technical material further comprises: after the synthetic reaction of the nicosulfuron technical is finished, a technical mixed solution is obtained, the technical mixed solution is added into an alkaline aqueous solution for extraction, and an aqueous layer is obtained by separation; and adding the aqueous layer into an acidic aqueous solution, filtering, and recrystallizing with methanol to obtain the pure nicosulfuron technical product. The alkaline aqueous solution can be an alkaline solution such as a sodium hydroxide solution, a potassium hydroxide solution and the like, and preferably, the alkaline aqueous solution is a sodium hydroxide solution; the acidic aqueous solution may be a hydrochloric acid solution, a dilute sulfuric acid solution, etc., and preferably, the acidic aqueous solution is a hydrochloric acid solution.
Based on the above, the synthesis method of 2-aminosulfonyl-N, N-dimethylnicotinamide comprises the following steps: dissolving 2-chlorosulfonyl-N, N-dimethylnicotinamide in dichloroethane, adding ammonia water, reacting for 1-3 hours at 0-100 ℃, obtaining a product mixed solution after the reaction is finished, pouring the product mixed solution into water for extraction to obtain an organic layer, and removing the dichloroethane in the organic layer to obtain the 2-sulfamoyl-N, N-dimethylnicotinamide. After the reaction is finished, the product mixed liquor is poured into water for extraction so as to remove water-soluble impurities in the product mixed liquor, the product is dissolved in the organic layer, and the solvent in the product mixed liquor can be removed by adopting a reduced pressure distillation mode and the like.
Based on the above, the synthesis method of 2-chlorosulfonyl-N, N-dimethylnicotinamide comprises the following steps: dissolving 2-sulfydryl-N, N-dimethyl nicotinamide in 50-90% of acetic acid aqueous solution by mass, introducing chlorine, reacting for 1-3 hours at 0-100 ℃, and after the reaction is finished, purifying to obtain 2-chlorosulfonyl-N, N-dimethyl nicotinamide. The specific purification treatment method in this step may be a method of removing the solvent from the solution obtained after the reaction is completed by distillation under reduced pressure.
Based on the above, the synthesis method of 2-mercapto-N, N-dimethylnicotinamide comprises the following steps: adding 2-chloro-N, N-dimethylnicotinamide into a 10-40% sodium hydroxide aqueous solution, then adding sodium hydrosulfide and sulfur powder, reacting for 1-3 h at 0-100 ℃, and filtering after the reaction is finished to obtain 2-mercapto-N, N-dimethylnicotinamide; wherein the molar ratio of the 2-chloro-N, N-dimethylnicotinamide to the sodium hydrosulfide to the sulfur powder is 1: 1-3: 3-6.
The invention also provides a preparation method of the nicosulfuron technical, which comprises the following steps:
synthesizing 2-aminosulfonyl-N, N-dimethylnicotinamide by using 2-chloro-N, N-dimethylnicotinamide as a raw material to synthesize 2-aminosulfonyl-N, N-dimethylnicotinamide;
synthesizing 2-isocyanatosulfonyl-N, N-dimethylnicotinamide 2-aminosulfonyl-N, N-dimethylnicotinamide, triphosgene and an acid-removing agent at 0-80 ℃ to synthesize the 2-isocyanatosulfonyl-N, N-dimethylnicotinamide, wherein the acid-removing agent is triethylamine, sodium carbonate, potassium carbonate or sodium bicarbonate;
the synthetic nicosulfuron original drug 2-isocyanatosulfonyl-N, N-dimethylnicotinamide and 2-amino-4, 6-dimethoxypyrimidine react at 0-100 ℃ to synthesize the nicosulfuron original drug.
Based on the above, the step of synthesizing 2-aminosulfonyl-N, N-dimethylnicotinamide comprises: 2-sulfydryl-N, N-dimethyl nicotinamide is synthesized by taking 2-chlorine-N, N-dimethyl nicotinamide as a raw material, 2-chlorosulfonyl-N, N-dimethyl nicotinamide is synthesized by taking 2-sulfydryl-N, N-dimethyl nicotinamide as a raw material, and 2-chlorosulfonyl-N, N-dimethyl nicotinamide is synthesized by taking 2-chlorosulfonyl-N, N-dimethyl nicotinamide as a raw material.
Compared with the prior art, the preparation method of the nicosulfuron original drug provided by the invention is a new synthesis method for synthesizing the nicosulfuron original drug by taking 2-chlorosulfonyl-N, N-dimethylnicotinamide, triphosgene, the acid addition agent and 2-amino-4, 6-dimethoxypyrimidine as main raw materials; the synthesis reaction temperature is not more than 100 ℃, and the synthesis conditions are mild; the synthesis method combines purification treatment by using alkali water and acid water, so that the purity of the nicosulfuron technical product can reach 99 percent or even more, and the product yield can reach 98 percent.
Therefore, the preparation method of the nicosulfuron technical provided by the invention is simple and feasible, has high total yield and low cost, and can realize industrial production.
Detailed Description
The technical solution of the present invention is further described in detail by the following embodiments.
Example 1
The embodiment provides a preparation method of nicosulfuron technical material, which comprises the following steps:
synthesis of 2-mercapto-N, N-dimethylnicotinamide 8.77 g of 2-chloro-N, N-dimethylnicotinamide was added to a 20% aqueous solution of sodium hydroxide, 2.8 g of sodium hydrosulfide and 6.4g of sulfur powder were added to the reaction system, and the reaction was carried out at 80 ℃ for 3 hours, after the reaction was completed, 7.96 g of 2-mercapto-N, N-dimethylnicotinamide was obtained by filtration, with a yield of 90%.
Synthesis of 2-chlorosulfonyl-N, N-dimethylnicotinamide 7.96 g of 2-mercapto-N, N-dimethylnicotinamide was dissolved in 60% acetic acid aqueous solution, chlorine gas was introduced into the reaction system, reaction was carried out at 40 ℃ for 2 hours, and after the reaction was completed, the solvent was removed to obtain 10.07 g of 2-chlorosulfonyl-N, N-dimethylnicotinamide, with a yield of 92%.
Synthesis of 2-aminosulfonyl-N, N-dimethylnicotinamide 10.07 g of 2-chlorosulfonyl-N, N-dimethylnicotinamide was dissolved in dichloroethane, ammonia water was added, the reaction was carried out at 60 ℃ for 3 hours, after the reaction was completed, the reaction mixture was poured into clear water, and the organic layer was taken to remove the solvent to obtain 8.82 g of 2-aminosulfonyl-N, N-dimethylnicotinamide with a yield of 95%.
Synthesis of 2-isocyanatosulfonyl-N, N-dimethylnicotinamide 8.82 g of 2-chlorosulfonyl-N, N-dimethylnicotinamide and 12.17 g of triphosgene are dissolved in dichloromethane, 4.15 g of triethylamine is dropwise added at 30 ℃, and after reaction for 1 hour, a 2-isocyanatosulfonyl-N, N-dimethylnicotinamide system is synthesized.
The synthetic nicosulfuron original drug is added with 6.36 g of 2-amino-4, 6-dimethoxy pyrimidine into a 2-isocyanatosulfonyl-N, N-dimethyl nicotinamide system which is synthesized in the previous step, the reaction is carried out for 3h at 40 ℃, the reaction solution is added into a large amount of sodium hydroxide solution after the reaction is finished, a large amount of hydrochloric acid solution is added after a water layer is taken, and the filtration and recrystallization are carried out by methanol to obtain 15.01 g of nicosulfuron original drug with the yield of 95 percent and the purity of 98.5 percent. Wherein the product obtained in this step is subjected to nuclear magnetic resonance as 1H-NMR (400 MHz, CDCl3) < delta > 8.72 (m, 1H), 7.78 (m, 1H), 7.54 (m, 1H), 5.72 (s, 1H),3.94 (s, 6H),3.06 (s, 3H), 2.91 (s, 3H); therefore, the product prepared by the method is nicosulfuron technical.
Therefore, the synthetic route of the nicosulfuron technical material using 2-chloro-N, N-dimethylnicotinamide as the starting material provided in this example is as follows:
example 2
The embodiment provides a preparation method of nicosulfuron technical material, which comprises the following steps:
synthesizing 2-mercapto-N, N-dimethylnicotinamide 9.05 g of 2-chloro-N, N-dimethylnicotinamide is added into a 20% sodium hydroxide aqueous solution, 3.2 g of sodium hydrosulfide and 7.8 g of sulfur powder are added into a reaction system, the reaction is carried out for 3 hours at the temperature of 80 ℃, and after the reaction is finished, the 2-mercapto-N, N-dimethylnicotinamide 8.22 g is obtained by filtration, with the yield of 92%.
Synthesis of 2-chlorosulfonyl-N, N-dimethylnicotinamide 8.22 g of 2-mercapto-N, N-dimethylnicotinamide was dissolved in 60% acetic acid aqueous solution, chlorine gas was introduced into the reaction system, and the reaction was carried out at 40 ℃ for 2 hours, after the reaction was completed, the solvent was removed to obtain 10.8 g of 2-chlorosulfonyl-N, N-dimethylnicotinamide, with a yield of 90%.
Synthesis of 2-aminosulfonyl-N, N-dimethylnicotinamide 10.08 g of 2-chlorosulfonyl-N, N-dimethylnicotinamide was dissolved in dichloroethane, ammonia water was added, the reaction was carried out at 60 ℃ for 3 hours, after the reaction was completed, the reaction mixture was poured into clear water, and the organic layer was taken to remove the solvent, whereby 8.74 g of 2-aminosulfonyl-N, N-dimethylnicotinamide was obtained with a yield of 93%.
Synthesis of 2-isocyanatosulfonyl-N, N-dimethylnicotinamide 8.74 g of 2-chlorosulfonyl-N, N-dimethylnicotinamide and 18.23 g of triphosgene are dissolved in dichloromethane, 6.24 g of triethylamine is added dropwise at 25 ℃, and after reaction for 3 hours, a 2-isocyanatosulfonyl-N, N-dimethylnicotinamide system is synthesized.
The synthetic nicosulfuron original drug is added with 6.98 g of 2-amino-4, 6-dimethoxy pyrimidine into a 2-isocyanatosulfonyl-N, N-dimethyl nicotinamide system which is synthesized in the previous step, the reaction is carried out for 3h at the temperature of 40 ℃, the reaction solution is added into a large amount of sodium hydroxide solution after the reaction is finished, a large amount of hydrochloric acid solution is added after a water layer is taken, and the mixture is recrystallized by methanol after being filtered to obtain 15.28 g of nicosulfuron, wherein the yield is 98 percent, and the purity is 98.7 percent.
Example 3
The embodiment provides a preparation method of nicosulfuron technical material, which comprises the following steps:
synthesis of 2-mercapto-N, N-dimethylnicotinamide 8.86 g of 2-chloro-N, N-dimethylnicotinamide was added to a 20% aqueous solution of sodium hydroxide, 2.8 g of sodium hydrosulfide and 7.8 g of sulfur powder were added to the reaction system, and the reaction was carried out at 80 ℃ for 3 hours, after the reaction was completed, filtration was carried out to obtain 7.87 g of 2-mercapto-N, N-dimethylnicotinamide, with a yield of 90%.
Synthesizing 2-chlorosulfonyl-N, N-dimethylnicotinamide 7.87 g of 2-mercapto-N, N-dimethylnicotinamide is dissolved in 60% acetic acid aqueous solution, chlorine is introduced into the reaction system, the reaction is carried out for 2 h at 40 ℃, and after the reaction is finished, the solvent is removed to obtain 9.52 g of 2-chlorosulfonyl-N, N-dimethylnicotinamide, with the yield of 89%.
Synthesis of 2-aminosulfonyl-N, N-dimethylnicotinamide 9.52 g of 2-chlorosulfonyl-N, N-dimethylnicotinamide was dissolved in dichloroethane, ammonia water was added, the reaction was carried out at 60 ℃ for 3 hours, after the reaction was completed, the reaction mixture was poured into clear water, and the organic layer was taken to remove the solvent, whereby 8.08 g of 2-aminosulfonyl-N, N-dimethylnicotinamide was obtained with a yield of 92%.
Synthesis of 2-isocyanatosulfonyl-N, N-dimethylnicotinamide 8.08 g of 2-chlorosulfonyl-N, N-dimethylnicotinamide and 14.6 g of triphosgene are dissolved in dichloromethane, 5.63 g of triethylamine is dropwise added at 60 ℃, and after reaction for 1 hour, a 2-isocyanatosulfonyl-N, N-dimethylnicotinamide system is synthesized.
The synthetic nicosulfuron original drug is added with 6.2 g of 2-amino-4, 6-dimethoxy pyrimidine into a 2-isocyanatosulfonyl-N, N-dimethyl nicotinamide system which is synthesized in the previous step, the reaction is carried out for 1h at 80 ℃, the reaction solution is added into a large amount of sodium hydroxide solution after the reaction is finished, a large amount of hydrochloric acid solution is added after a water layer is taken, and the mixture is recrystallized by methanol after being filtered to obtain 13.29 g of nicosulfuron, wherein the yield is 92 percent, and the purity is 98.2 percent.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention and not to limit it; although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art will understand that: modifications to the specific embodiments of the invention or equivalent substitutions for parts of the technical features may be made; without departing from the spirit of the present invention, it is intended to cover all aspects of the invention as defined by the appended claims.
Claims (9)
1. A preparation method of nicosulfuron technical comprises the following steps:
synthesizing 2-isocyanatosulfonyl-N, N-dimethylnicotinamide 2-aminosulfonyl-N, N-dimethylnicotinamide, triphosgene and an acid-removing agent at 0-80 ℃ to synthesize the 2-isocyanatosulfonyl-N, N-dimethylnicotinamide, wherein the acid-removing agent is triethylamine, sodium carbonate, potassium carbonate or sodium bicarbonate;
the synthetic nicosulfuron original drug 2-isocyanatosulfonyl-N, N-dimethylnicotinamide and 2-amino-4, 6-dimethoxypyrimidine react at 0-100 ℃ to synthesize the nicosulfuron original drug.
2. The method for preparing nicosulfuron technical material as claimed in claim 1, wherein the step of synthesizing 2-isocyanatosulfonyl-N, N-dimethylnicotinamide comprises: dissolving 2-chlorosulfonyl-N, N-dimethylnicotinamide, triphosgene and the acid-forming agent in a first solvent, dropwise adding the acid-forming agent at the temperature of 0-80 ℃, and reacting for 1-3 h to synthesize 2-isocyanatosulfonyl-N, N-dimethylnicotinamide; wherein the molar ratio of the 2-chlorosulfonyl-N, N-dimethylnicotinamide to the triphosgene to the acid-forming agent is 1: 1-2: 1-3, and the first solvent is dichloromethane, ethyl acetate, methyl chloride or acetone.
3. The method for preparing a nicosulfuron technical material as claimed in claim 2, wherein the step of synthesizing the nicosulfuron technical material comprises: in the step of synthesizing 2-isocyanatosulfonyl-N, N-dimethylnicotinamide, the synthesized 2-isocyanatosulfonyl-N, N-dimethylnicotinamide directly reacts with 2-amino-4, 6-dimethoxypyrimidine at 0-100 ℃ for 1-3 h to synthesize nicosulfuron technical, wherein the molar ratio of 2-chlorosulfonyl-N, N-dimethylnicotinamide to 2-amino-4, 6-dimethoxypyrimidine is 1: 1.
4. the method for preparing a nicosulfuron technical material as claimed in claim 3, wherein the step of synthesizing the nicosulfuron technical material further comprises: after the synthetic reaction of the nicosulfuron technical is finished, a technical mixed solution is obtained, the technical mixed solution is added into an alkaline aqueous solution for extraction, and an aqueous layer is obtained by separation; and adding the aqueous layer into an acidic aqueous solution, filtering, and recrystallizing with methanol to obtain the pure nicosulfuron technical product.
5. The method for preparing nicosulfuron technical material as claimed in any one of claims 1 to 4, wherein the method for synthesizing 2-sulfamoyl-N, N-dimethylnicotinamide comprises the following steps: dissolving 2-chlorosulfonyl-N, N-dimethylnicotinamide in dichloroethane, adding ammonia water, reacting for 1-3 hours at 0-100 ℃, obtaining a product mixed solution after the reaction is finished, pouring the product mixed solution into water for extraction to obtain an organic layer, and removing the dichloroethane in the organic layer to obtain the 2-sulfamoyl-N, N-dimethylnicotinamide.
6. The method for preparing nicosulfuron technical material as claimed in claim 5, wherein the method for synthesizing 2-chlorosulfonyl-N, N-dimethylnicotinamide comprises the following steps: dissolving 2-sulfydryl-N, N-dimethyl nicotinamide in 50-90% of acetic acid aqueous solution by mass, introducing chlorine, reacting for 1-3 hours at 0-100 ℃, and after the reaction is finished, purifying to obtain 2-chlorosulfonyl-N, N-dimethyl nicotinamide.
7. The preparation method of nicosulfuron technical material as claimed in claim 6, wherein the synthesis method of 2-mercapto-N, N-dimethylnicotinamide comprises the following steps: adding 2-chloro-N, N-dimethylnicotinamide into a 10-40% sodium hydroxide aqueous solution, then adding sodium hydrosulfide and sulfur powder, reacting for 1-3 h at 0-100 ℃, and filtering after the reaction is finished to obtain 2-mercapto-N, N-dimethylnicotinamide; wherein the molar ratio of the 2-chloro-N, N-dimethylnicotinamide to the sodium hydrosulfide to the sulfur powder is 1: 1-3: 3-6.
8. A preparation method of nicosulfuron technical comprises the following steps:
synthesizing 2-aminosulfonyl-N, N-dimethylnicotinamide by using 2-chloro-N, N-dimethylnicotinamide as a raw material to synthesize 2-aminosulfonyl-N, N-dimethylnicotinamide;
synthesizing 2-isocyanatosulfonyl-N, N-dimethylnicotinamide 2-aminosulfonyl-N, N-dimethylnicotinamide, triphosgene and an acid-removing agent at 0-80 ℃ to synthesize the 2-isocyanatosulfonyl-N, N-dimethylnicotinamide, wherein the acid-removing agent is triethylamine, sodium carbonate, potassium carbonate or sodium bicarbonate;
the synthetic nicosulfuron original drug 2-isocyanatosulfonyl-N, N-dimethylnicotinamide and 2-amino-4, 6-dimethoxypyrimidine react at 0-100 ℃ to synthesize the nicosulfuron original drug.
9. The method for preparing nicosulfuron technical material as claimed in claim 8, wherein the step of synthesizing 2-sulfamoyl-N, N-dimethylnicotinamide comprises: 2-sulfydryl-N, N-dimethyl nicotinamide is synthesized by taking 2-chlorine-N, N-dimethyl nicotinamide as a raw material, 2-chlorosulfonyl-N, N-dimethyl nicotinamide is synthesized by taking 2-sulfydryl-N, N-dimethyl nicotinamide as a raw material, and 2-chlorosulfonyl-N, N-dimethyl nicotinamide is synthesized by taking 2-chlorosulfonyl-N, N-dimethyl nicotinamide as a raw material.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111925323A (en) * | 2020-09-01 | 2020-11-13 | 山东京博生物科技有限公司 | Synthetic method of 2-aminosulfonyl-N, N-dimethylnicotinamide |
| CN112479994A (en) * | 2020-12-18 | 2021-03-12 | 淄博新农基作物科学有限公司 | Preparation method of smoke sulfamide |
| CN113461667A (en) * | 2021-06-30 | 2021-10-01 | 淄博新农基作物科学有限公司 | Method for synthesizing nicosulfuron by hydrogen sulfide closed loop |
| CN114075137A (en) * | 2020-08-22 | 2022-02-22 | 江苏瑞邦农化股份有限公司 | A kind of preparation method of 2-aminosulfonyl-N,N-dimethylnicotinamide |
| CN114181140A (en) * | 2022-02-16 | 2022-03-15 | 安徽华星化工有限公司 | Method for preparing 2-mercapto-N, N-dimethylnicotinamide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5206372A (en) * | 1990-06-05 | 1993-04-27 | Shell Research Limited | Preparation of 2-chloropyridine derivatives |
| CN103319489A (en) * | 2013-07-12 | 2013-09-25 | 黑龙江大学 | Triazolopyrimidine sulfonamide compound, and synthetic method and application thereof |
| CN108017578A (en) * | 2016-10-31 | 2018-05-11 | 江苏丰山集团股份有限公司 | A kind of chloro- N of 2-, the preparation method of N- dimethyl nicotinamides |
-
2019
- 2019-11-18 CN CN201911126217.6A patent/CN110878084A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5206372A (en) * | 1990-06-05 | 1993-04-27 | Shell Research Limited | Preparation of 2-chloropyridine derivatives |
| CN103319489A (en) * | 2013-07-12 | 2013-09-25 | 黑龙江大学 | Triazolopyrimidine sulfonamide compound, and synthetic method and application thereof |
| CN108017578A (en) * | 2016-10-31 | 2018-05-11 | 江苏丰山集团股份有限公司 | A kind of chloro- N of 2-, the preparation method of N- dimethyl nicotinamides |
Non-Patent Citations (5)
| Title |
|---|
| XIAOHUI REN ET AL.: "Preparation of molecularly imprinted polymer coated quantum dots to detect nicosulfuron in water samples", 《ANAL BIOANAL CHEM》 * |
| 杨荣国: "超高效磺酰脲类除草剂烟嘧磺隆的合成研究", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》 * |
| 贾淑敏: "嘧啶磺酰脲除草剂的纯化与分析", 《中国优秀硕士学位论文全文数据库 农业科技辑》 * |
| 陆阳等: "二(三氯甲基)碳酸酯"一锅法"合成磺酰脲类除草剂", 《化工技术与开发》 * |
| 雷艳等: "磺酰脲类除草剂--烟嘧磺隆的合成", 《现代农药》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114075137A (en) * | 2020-08-22 | 2022-02-22 | 江苏瑞邦农化股份有限公司 | A kind of preparation method of 2-aminosulfonyl-N,N-dimethylnicotinamide |
| CN111925323A (en) * | 2020-09-01 | 2020-11-13 | 山东京博生物科技有限公司 | Synthetic method of 2-aminosulfonyl-N, N-dimethylnicotinamide |
| CN111925323B (en) * | 2020-09-01 | 2022-05-31 | 山东京博生物科技有限公司 | Synthetic method of 2-aminosulfonyl-N, N-dimethylnicotinamide |
| CN112479994A (en) * | 2020-12-18 | 2021-03-12 | 淄博新农基作物科学有限公司 | Preparation method of smoke sulfamide |
| CN113461667A (en) * | 2021-06-30 | 2021-10-01 | 淄博新农基作物科学有限公司 | Method for synthesizing nicosulfuron by hydrogen sulfide closed loop |
| CN113461667B (en) * | 2021-06-30 | 2022-03-22 | 淄博新农基作物科学有限公司 | Method for synthesizing nicosulfuron-methyl using hydrogen sulfide ring closure |
| CN114181140A (en) * | 2022-02-16 | 2022-03-15 | 安徽华星化工有限公司 | Method for preparing 2-mercapto-N, N-dimethylnicotinamide |
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