CN115772090B - Synthesis method of chlorantraniliprole key intermediate - Google Patents
Synthesis method of chlorantraniliprole key intermediate Download PDFInfo
- Publication number
- CN115772090B CN115772090B CN202211629594.3A CN202211629594A CN115772090B CN 115772090 B CN115772090 B CN 115772090B CN 202211629594 A CN202211629594 A CN 202211629594A CN 115772090 B CN115772090 B CN 115772090B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- amino
- chlorantraniliprole
- key intermediate
- nano iron
- 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.)
- Active
Links
- 239000005886 Chlorantraniliprole Substances 0.000 title claims abstract description 14
- PSOVNZZNOMJUBI-UHFFFAOYSA-N chlorantraniliprole Chemical compound CNC(=O)C1=CC(Cl)=CC(C)=C1NC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl PSOVNZZNOMJUBI-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000001308 synthesis method Methods 0.000 title claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 17
- KOPXCQUAFDWYOE-UHFFFAOYSA-N 2-amino-5-chloro-3-methylbenzoic acid Chemical compound CC1=CC(Cl)=CC(C(O)=O)=C1N KOPXCQUAFDWYOE-UHFFFAOYSA-N 0.000 claims abstract description 15
- WOBVZGBINMTNKL-UHFFFAOYSA-N 2-amino-5-chloro-n,3-dimethylbenzamide Chemical compound CNC(=O)C1=CC(Cl)=CC(C)=C1N WOBVZGBINMTNKL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 10
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- LFETXMWECUPHJA-UHFFFAOYSA-N methanamine;hydrate Chemical compound O.NC LFETXMWECUPHJA-UHFFFAOYSA-N 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 claims description 3
- HVENHVMWDAPFTH-UHFFFAOYSA-N iron(3+) trinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HVENHVMWDAPFTH-UHFFFAOYSA-N 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 abstract description 12
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 239000000243 solution Substances 0.000 abstract description 7
- 239000007864 aqueous solution Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000011112 process operation Methods 0.000 abstract description 3
- 230000003113 alkalizing effect Effects 0.000 abstract 2
- 238000011085 pressure filtration Methods 0.000 abstract 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 8
- 239000000543 intermediate Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- -1 amide compounds Chemical class 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000005711 Benzoic acid Substances 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000010933 acylation Effects 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical group NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000007098 aminolysis reaction Methods 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The invention relates to a method for synthesizing a key intermediate of chlorantraniliprole, which takes 2-amino-3-methyl-5-chlorobenzoic acid and aqueous solution of methylamine as raw materials, takes load type nano iron particles as a catalyst, takes TBHP as an additive, reacts in a solvent for 2-8 hours at normal temperature and normal pressure, recovers the catalyst after the reaction is finished, and introduces the reaction solution into an alkalizing kettle, and obtains 2-amino-5-chloro-N, 3-dimethylbenzamide through alkalizing, pressure filtration and drying. The catalyst recovered by the invention is washed by absolute methanol and dried, the activity of the catalyst is not obviously reduced after the catalyst is repeatedly used for 5 times, the synthesis process is environment-friendly, the economy is high, no byproducts are generated, the reaction selectivity is good, the process operation is simple and convenient, the atom economy is high, the catalyst is environment-friendly, the requirement of green chemistry is met, and the catalyst is suitable for industrial production.
Description
Technical Field
The invention relates to a method for synthesizing a key intermediate of chlorantraniliprole, and particularly belongs to the technical field of organic synthesis.
Background
Chlorantraniliprole is an insecticide with an o-formamido benzamide structure, and plays an important role in the pesticide industry due to the characteristics of high efficiency, broad spectrum, low toxicity, high selectivity and the like. In recent years, as the requirements of related industries are improved year by year, the production of chlorantraniliprole intermediates and phthalamidobenzamide series products is affected to different degrees. Therefore, the aim of seeking a clean and efficient production process to increase yield and reduce energy consumption is to produce 2-amino-5-chloro-N, 3-dimethylbenzamide.
The current technology of 2-amino-5-chloro-N, 3-dimethylbenzamide mainly comprises the processes of hydrogenation, cyclization, aminolysis, chlorination and the like. The synthesis of target compounds using 2-amino-3-methyl-5-chlorobenzoic acid and aqueous methylamine as reaction substrates is very challenging. The basic research reports: the carboxyl and amino compounds can directly obtain amide compounds under the action of the dehydrating agent, but the reaction is more severe, partial dehydrating agent cannot exert normal effects under the condition of water, and methylamine in the raw materials is a methylamine water solution, so the reaction is difficult to implement. Chinese patent CN201610265762.3 discloses a method for preparing 2-amino-5-chloro-N, 3-dimethylbenzamide by catalyzing the reaction of carboxyl and amino with carbodiimide and an auxiliary agent as additives, which has simple reaction operation, but complex synthesis steps, large amount of reaction additives and is not friendly to the environment. In addition, the carboxyl is activated in advance, the reaction activity of the carboxyl is enhanced, and the purpose of synthesizing the amide can be achieved, because the benzoic acid has lower reaction activity, generally, the benzoic acid is firstly activated to obtain acyl chloride and then reacts with aqueous solution of methylamine, phosphorus trichloride, phosphorus pentachloride, thionyl chloride and the like are inevitably used as chlorine sources in the step of acyl chlorination of the carboxyl, and the chloride can generate waste acid in the use process, so that the method is not friendly to the environment; or the benzoic acid is subjected to an esterification process to obtain an ester compound, and then is subjected to an ammonolysis process to prepare the amide compound in a high-efficiency synthesis manner. Chinese patent 2019110985279.3 discloses that benzoic acid is subjected to esterification reaction to obtain an amide compound, but the process has the advantages of complicated steps, inconvenient operation, low atomic economy and high energy consumption. Therefore, it is extremely important to research and develop a novel catalyst that can directly undergo an acylation process to obtain an amide compound.
In recent years, green catalysis is used as a new generation technology in the industrial production of organic synthesis, and researches show that amidation reaction of free radical process can also be used for efficiently synthesizing amide compounds. Based on this, the present invention proposes a new catalytic technology for the synthesis of 2-amino-5-chloro-N, 3-dimethylbenzamide. Compared with the prior art, the 2-amino-3-methyl-5-chlorobenzoic acid and aqueous solution of methylamine can be directly acylated to obtain the target product by the action of conventional free radical initiator dibenzoyl peroxide, and the method has the advantages of extremely high reaction efficiency, no byproduct generation, simple and convenient process operation, high atom economy, environmental friendliness and meeting the requirements of green chemistry.
Disclosure of Invention
Aiming at the current situation, the invention provides a method for synthesizing a key intermediate of chlorantraniliprole, which takes 2-amino-3-methyl-5-chlorobenzoic acid and aqueous solution of methylamine as raw materials, takes supported nano iron as a catalyst and takes TBHP (tertiary butyl hydroperoxide) as an additive, and reacts for 2 to 8 hours in a solvent at normal temperature and normal pressure; transferring the product into an alkalization kettle after recovering the supported nano iron, regulating the pH value to 6.0-6.5 by sodium bicarbonate solution, and performing filter pressing and drying to obtain the key intermediate 2-amino-5-chloro-N, 3-dimethylbenzamide of chlorantraniliprole; washing the recovered supported nano iron by anhydrous methanol, drying in vacuum, and reusing;
the preparation process of the supported nano iron comprises the following steps:
Taking 2-pyridylaldehyde, 1 mol/L sodium hydroxide and aluminum oxide as raw materials, carrying out microwave reflux reaction on the raw materials for 6 h, and then separating the raw materials to obtain 2- (2-hydroxymethyl) pyridine; and then taking 2- (2-hydroxymethyl) pyridine, ferric nitrate hexahydrate and dry methanol as raw materials, carrying out reflux reaction for 6 hours under the protection of N 2, carrying out suction filtration, washing and drying on a product by using anhydrous methanol, and uniformly loading the product on the surfaces of nickel oxide particles to obtain the supported nano iron catalyst, wherein the structural formula is as follows:
the dosage of the supported nano iron is 0.0025 times of the mass of the 2-amino-3-methyl-5-chlorobenzoic acid.
The dosage of TBHP is 0.01 times of the mass of the 2-amino-3-methyl-5-chlorobenzoic acid.
The solvent is used in an amount of 60L per thousand moles of 2-amino-3-methyl-5-chlorobenzoic acid.
The solvent is water or ethanol.
The reaction equation of the invention is:
the invention has the beneficial effects that: the invention adopts the supported nano iron as the catalyst, TBHP as the additive, and the 2-amino-5-chloro-N, 3-dimethylbenzamide is directly synthesized by acylation, and the activity of the recovered catalyst is not obviously reduced after the recovered catalyst is washed and dried by absolute methanol and is repeatedly used for 5 times. The synthesis process of the invention is green and environment-friendly, has high economy, no byproduct generation, good reaction selectivity, simple and convenient process operation, high atom economy, environment friendliness, meets the requirements of green chemistry and is suitable for industrial production.
Detailed Description
Example 1
Preparation of supported nano iron catalyst
2-Pyridinecarboxaldehyde (107 g,1 mol), 1mol/L sodium hydroxide 100g and aluminum oxide (51 g,0.5 mol) were weighed out, and 6: 6 h was refluxed in a microwave reactor, and after the reaction was completed, 2- (2-hydroxymethyl) pyridine (55 g, 0.5: 0.5 mol) was separated by filtration.
2- (2-Hydroxymethyl) pyridine (109 g,1 mol), ferric nitrate hexahydrate (420 g,1.2 mol) and dry methanol (1000 mL) are subjected to reflux reaction for 6 hours under the protection of N 2, after the solvent is recovered, ice water is added for washing and suction filtration, an intermediate (286.1 g, 0.96 mol) is obtained, then the intermediate is impregnated and uniformly loaded on the surface of nickel oxide, and the loaded nano-iron catalyst is obtained, wherein the effective catalytic amount of the catalyst is 97%.
Example 2
Sequentially adding solvent ethanol 60L, 2-amino-3-methyl-5-chlorobenzoic acid 186 kg, a supported nano iron catalyst 0.465 kg, TBHP of 1.86 kg and 40 wt% methylamine water solution 37.3 kg into a 300L reaction kettle, stirring and heating to 40 ℃ after nitrogen substitution for 3 times, reacting for 6 hours, filtering and recovering the catalyst, and sampling and detecting. Then transferring the reaction solution into an alkalization kettle, dropwise adding 10 wt% sodium bicarbonate aqueous solution 125: 125 kg to adjust the pH value to 6.0-6.5, stirring and cooling to room temperature, press-filtering to obtain a wet 2-amino-5-chloro-N, 3-dimethylbenzamide product, and vacuum drying at 95-100 ℃ for 10 hours to obtain 2-amino-5-chloro-N, 3-dimethylbenzamide 185-kg with the yield of 93% and the purity of 99.6% (HPLC detection).
Example 3
Sequentially adding solvent ethanol 60L, 2-amino-3-methyl-5-chlorobenzoic acid 186 kg, supported nano iron catalyst 0.562 kg, TBHP of 2.15 kg and 40 wt% methylamine water solution 39 kg into a 300L reaction kettle, stirring and heating to 40 ℃ after nitrogen substitution for 3 times, reacting for 12 hours, filtering and recovering the catalyst, sampling and detecting.
Then transferring the reaction liquid into an alkalization kettle, dropwise adding 10 wt% sodium bicarbonate aqueous solution 141 kg to adjust the pH value to 6.0-6.5, stirring and cooling to room temperature, and respectively carrying out filter pressing and vacuum drying on the products at 95-100 ℃ for 10 hours to obtain 2-amino-5-chloro-N, 3-dimethylbenzamide 189 kg, wherein the yield is 95%, and the purity is 99.2% (detected by HPLC).
Example 4
The influence of the solvent on the reaction yield was examined, and a comparative test was set by examining the influence of the solvent on the reaction by examining the kind of the solvent while controlling other process parameters with reference to example 1, as shown in table 1.
TABLE 1 influence of solvent on reaction yield
As can be seen from Table 1, the yield of 2-amino-5-chloro-N, 3-dimethylbenzamide was high when the solvent was water or ethanol.
Example 5
The influence of the concentration of the reaction system on the reaction yield was examined and verified, and the comparative test was set by changing the amount of the solvent and exploring the influence of the concentration of the reaction system on the reaction by controlling other process parameters with reference to example 1, as shown in table 2.
TABLE 2 influence of the concentration of the reaction System on the reaction yield
As can be seen from Table 2, when the solvent amount in the reaction system is 85-95L and the concentration of 2-amino-3-methyl-5-chlorobenzoic acid is 0.0105-0.0117 mol/L, the yield of 2-amino-5-chloro-N, 3-dimethylbenzamide is high; therefore, the concentration of the reaction system is preferably 0.0117 mol/L of 2-amino-3-methyl-5-chlorobenzoic acid solution.
Claims (5)
1. A method for synthesizing a key intermediate of chlorantraniliprole is characterized by comprising the following steps of: the synthesis method takes 2-amino-3-methyl-5-chlorobenzoic acid and methylamine water solution as raw materials, takes supported nano iron as a catalyst and TBHP as an additive, and reacts in a solvent at normal temperature and normal pressure for 2-8 hours; transferring the product into an alkalization kettle after recovering the supported nano iron, regulating the pH value to 6.0-6.5 by sodium bicarbonate solution, and performing filter pressing and drying to obtain the key intermediate 2-amino-5-chloro-N, 3-dimethylbenzamide of chlorantraniliprole; washing the recovered supported nano iron by anhydrous methanol, drying in vacuum, and reusing;
The preparation process of the supported nano iron comprises the following steps:
Taking 2-pyridylaldehyde, 1 mol/L sodium hydroxide and aluminum oxide as raw materials, carrying out microwave reflux reaction on the raw materials for 6 h, and then separating the raw materials to obtain 2- (2-hydroxymethyl) pyridine; and then taking 2- (2-hydroxymethyl) pyridine, ferric nitrate hexahydrate and dry methanol as raw materials, carrying out reflux reaction for 6 hours under the protection of N 2, carrying out suction filtration, washing and drying on a product by using anhydrous methanol, and uniformly loading the product on the surfaces of nickel oxide particles to obtain the supported nano iron catalyst, wherein the structural formula is as follows:
。
2. The method for synthesizing the key intermediate of chlorantraniliprole as claimed in claim 1, which is characterized by comprising the following steps: the dosage of the supported nano iron is 0.0025 times of the mass of the 2-amino-3-methyl-5-chlorobenzoic acid.
3. The method for synthesizing the key intermediate of chlorantraniliprole as claimed in claim 1, which is characterized by comprising the following steps: the dosage of TBHP is 0.01 times of the mass of the 2-amino-3-methyl-5-chlorobenzoic acid.
4. The method for synthesizing the key intermediate of chlorantraniliprole as claimed in claim 1, which is characterized by comprising the following steps: the solvent is used in an amount of 60L per thousand moles of 2-amino-3-methyl-5-chlorobenzoic acid.
5. The method for synthesizing the key intermediate of chlorantraniliprole as claimed in claim 1, which is characterized by comprising the following steps: the solvent is water or ethanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211629594.3A CN115772090B (en) | 2022-12-19 | Synthesis method of chlorantraniliprole key intermediate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211629594.3A CN115772090B (en) | 2022-12-19 | Synthesis method of chlorantraniliprole key intermediate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115772090A CN115772090A (en) | 2023-03-10 |
| CN115772090B true CN115772090B (en) | 2024-06-07 |
Family
ID=
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101072767A (en) * | 2004-12-07 | 2007-11-14 | 杜邦公司 | Method for preparing n-phenylpyrazole-1-carboxamides |
| CN102276580A (en) * | 2011-06-02 | 2011-12-14 | 南开大学 | Pyrazole formylthiourea derivative and preparation method and application |
| CN108191822A (en) * | 2017-12-06 | 2018-06-22 | 广东丸美生物技术股份有限公司 | A kind of synthetic method of Rynaxypyr |
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101072767A (en) * | 2004-12-07 | 2007-11-14 | 杜邦公司 | Method for preparing n-phenylpyrazole-1-carboxamides |
| CN102276580A (en) * | 2011-06-02 | 2011-12-14 | 南开大学 | Pyrazole formylthiourea derivative and preparation method and application |
| CN108191822A (en) * | 2017-12-06 | 2018-06-22 | 广东丸美生物技术股份有限公司 | A kind of synthetic method of Rynaxypyr |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107445830B (en) | Method for producing glyoxylic ester by oxidative dehydrogenation of glycolate | |
| CN110156620B (en) | Preparation method of tranexamic acid | |
| Mao et al. | Heterogeneous cobalt catalysts for selective oxygenation of alcohols to aldehydes, esters and nitriles | |
| CN109776337A (en) | The preparation method of 2- methoxyl group -4- nitroaniline | |
| CN107253912B (en) | Synthetic method of cyhalofop-butyl | |
| CN109575014B (en) | Benzimidazo [2,1-a ] isoquinolinone compound and preparation method thereof | |
| CN103922931B (en) | A kind of method of a step catalytically synthesizing glycol ether acetate | |
| Li et al. | Catalytic amidation of 5‐hydroxymethylfurfural to 2, 5‐furandicarboxamide over alkali manganese oxides | |
| EA036250B1 (en) | Method for preparing intermediates for preparing azoxystrobin | |
| KR20010053294A (en) | Method for producing ortho-alkylated benzoic acid derivatives | |
| CN115772090B (en) | Synthesis method of chlorantraniliprole key intermediate | |
| CN113214106A (en) | Method for efficiently synthesizing primary amide and N-methyl secondary amide compounds | |
| CN104860980B (en) | It is a kind of to be used to synthesize intermediate of Ezetimibe and its preparation method and application | |
| CN115772090A (en) | Method for synthesizing chlorantraniliprole key intermediate | |
| CN108623488B (en) | Synthetic method of aminomethylbenzoic acid | |
| CN107176906A (en) | A kind of synthetic method of substitution indone | |
| CN106588921B (en) | A kind of synthetic method of the methyl formate of 7 azaindole 3 | |
| CN102050721B (en) | Method for synthesizing phenylacetic acid from benzyl chloride carbonyl | |
| CN108069897B (en) | Method for synthesizing nicotinic acid by using carbon dioxide | |
| CN115286568B (en) | Preparation method of 2-hydroxy-4-trifluoromethyl pyridine | |
| CN112679527B (en) | Method for synthesizing 3-decarbamoyl-acetyl-cefuroxime acid compound | |
| CN105037192A (en) | One-step method for synthesizing p-formylamino benzene alkyl ether as octane booster | |
| CN106928083A (en) | The method that metallic sodium catalysis ester aminating reaction prepares acid amides | |
| CN108299236B (en) | Synthetic method of alpha-cyanoacrylate compound | |
| CN105801455A (en) | Method for oxidatively synthesizing p-carboxybenzene sulfonamide through oxygen |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |