CN115850235B - Preparation method of chlorantraniliprole intermediate - Google Patents
Preparation method of chlorantraniliprole intermediate Download PDFInfo
- Publication number
- CN115850235B CN115850235B CN202211682156.3A CN202211682156A CN115850235B CN 115850235 B CN115850235 B CN 115850235B CN 202211682156 A CN202211682156 A CN 202211682156A CN 115850235 B CN115850235 B CN 115850235B
- Authority
- CN
- China
- Prior art keywords
- formula
- chlorantraniliprole
- compound
- preparation
- reaction
- 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 27
- 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 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 63
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- LGZDNJBUAAXEMN-UHFFFAOYSA-N 1,2,2,3-tetramethyl-1-oxidopiperidin-1-ium Chemical compound CC1CCC[N+](C)([O-])C1(C)C LGZDNJBUAAXEMN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims abstract description 14
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 22
- 239000000413 hydrolysate Substances 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 230000020477 pH reduction Effects 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 12
- -1 3-chloro-2-pyridyl Chemical group 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 26
- 239000000543 intermediate Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 9
- FORBXGROTPOMEH-UHFFFAOYSA-N 5-bromo-2-(3-chloropyridin-2-yl)pyrazole-3-carboxylic acid Chemical compound OC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl FORBXGROTPOMEH-UHFFFAOYSA-N 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000006356 dehydrogenation reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 1
- 229910014265 BrCl Inorganic materials 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 241000258937 Hemiptera Species 0.000 description 1
- 241000256602 Isoptera Species 0.000 description 1
- 241000255777 Lepidoptera Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Abstract
The invention relates to the technical field of organic synthesis, and provides a preparation method of a chlorantraniliprole intermediate. According to the invention, 3-bromo-1- (3-chloro-2-pyridyl) -4, 5-dihydro-1H-pyrazole-5-ethyl formate is taken as a raw material, water is taken as a solvent, hydrolysis is carried out under the condition of sodium hydroxide, and oxidative dehydrogenation is carried out by taking hydrogen peroxide as an oxidant under the catalysis of tetramethylpiperidine oxide, so that a target product is obtained. The preparation method avoids the use of reagents such as persulfate, concentrated sulfuric acid, acetonitrile and the like, does not generate high-salt high-COD wastewater in the reaction process, has the advantages of simple and easily obtained raw materials and small pollution, adopts a one-pot method for hydrolysis and oxidative dehydrogenation reaction, is simple to operate, is easy for industrial production, and has high product yield. The results of the examples show that the yield of the chlorantraniliprole intermediate prepared by the method can reach 91.7%.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of a chlorantraniliprole intermediate.
Background
Novel efficient and low-toxicity o-formamido benzamide pesticide with chemical name of 3-bromo-N- [ 4-chloro-2-methyl-6- [ (methylcarbamoyl) benzene]-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide having the formula C 18 H 14 BrCl 2 N 5 O 2 The structural formula is shown as the following formula A. The pesticide has the characteristics of broad spectrum, high efficiency and environmental friendliness, has good control effect on lepidoptera, coleoptera, diptera, hemiptera and termite insects, and has good safety and wide application prospect.
3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxylic acid is a key intermediate in the preparation of chlorantraniliprole. At present, the general synthetic route for this key intermediate is as follows:
in the synthetic route, the compound I is taken as a raw material, dehydrogenation is carried out under the action of persulfate and concentrated sulfuric acid to obtain a compound II, and then the chlorantraniliprole intermediate is obtained through hydrolysis. In the synthesis process, a large amount of sulfate such as potassium persulfate and the like are needed in the dehydrogenation step, concentrated sulfuric acid with stronger corrosiveness is needed, the solvent is acetonitrile and the like with higher toxicity, a large amount of high-salt high-COD wastewater can be generated in the reaction process and is difficult to treat, and the hydrous acetonitrile after the reaction needs to be dehydrated and recovered, so that the operation method is complex and the cost is higher; in addition, after the compound IV is obtained in the synthetic route, the compound IV needs to be separated by means of filtration, rotary evaporation, drying and the like, and then subsequent reactions are carried out, which also results in complicated operation steps, and the total yield of the two-step reactions in the synthetic route is about 70%, so that the yield needs to be further improved.
Therefore, a preparation method of chlorantraniliprole intermediate with simple operation, little pollution and high yield is needed to be provided at present.
Disclosure of Invention
In view of this, the present invention provides a process for the preparation of chlorantraniliprole intermediates. The preparation method provided by the invention is simple to operate, small in pollution and high in yield.
In order to achieve the above object, the present invention provides the following technical solutions:
a method for preparing chlorantraniliprole intermediate, comprising the following steps:
mixing a compound with a structure shown in a formula I, water and sodium hydroxide for hydrolysis reaction to obtain hydrolysate feed liquid, wherein the hydrolysate has a structure shown in a formula II;
mixing the hydrolysate feed liquid, tetramethyl piperidine oxide and hydrogen peroxide for oxidative dehydrogenation reaction, and acidizing after the reaction is finished to obtain chlorantraniliprole intermediate; the structure of the chlorantraniliprole intermediate is shown as a formula III;
preferably, the ratio of the mass of the compound with the structure shown in the formula I to the volume of water is 100 g/0.1-5000 mL.
Preferably, the molar ratio of the compound with the structure shown in the formula I to the sodium hydroxide is 1:1-2.
Preferably, the temperature of the hydrolysis reaction is 80 ℃ or higher, and the time of the hydrolysis reaction is 0.5-64 h.
Preferably, the mass of the tetramethylpiperidine oxide is 0.5 to 1% of the mass of the compound having the structure shown in the formula I.
Preferably, the hydrogen peroxide is added in the form of hydrogen peroxide; the mol ratio of the compound with the structure shown in the formula I to the hydrogen peroxide is 1 (1-5).
Preferably, before the hydrolysate feed liquid is mixed with the tetramethylpiperidine oxide and the hydrogen peroxide, the method further comprises the step of adjusting the pH value of the hydrolysate feed liquid to 6-7.
Preferably, the temperature of the oxidative dehydrogenation reaction is 60-80 ℃, and the time of the oxidative dehydrogenation reaction is 0.5-24 h.
Preferably, after acidification, the method further comprises the steps of sequentially filtering, washing and drying the solid product separated out after acidification to obtain the chlorantraniliprole intermediate.
The invention provides a preparation method of chlorantraniliprole intermediate, which comprises the following steps: mixing a compound with a structure shown in a formula I, water and sodium hydroxide for hydrolysis reaction to obtain hydrolysate feed liquid, wherein the hydrolysate has a structure shown in a formula II; mixing the hydrolysate feed liquid, tetramethyl piperidine oxide and hydrogen peroxide for oxidative dehydrogenation reaction, and acidizing after the reaction is finished to obtain the chlorantraniliprole intermediate with the structure shown in the formula III. The method takes a compound with a structure shown in a formula I as a raw material, takes water as a solvent, carries out hydrolysis under the condition of sodium hydroxide, and then carries out oxidative dehydrogenation under the catalysis of tetramethylpiperidine oxide by taking hydrogen peroxide as an oxidant to obtain a target product; the preparation method avoids the use of reagents such as persulfate, concentrated sulfuric acid, acetonitrile and the like, does not generate high-salt high-COD wastewater in the reaction process, has simple and easily obtained raw materials and small pollution, adopts a one-pot method for hydrolysis and dehydrogenation reaction, does not need to separate products after the hydrolysis reaction, can directly perform the next reaction, and has simple operation, easy industrial production and high product yield. The results of the examples show that the yield of the chlorantraniliprole intermediate prepared by the method can reach 91.7%.
Drawings
FIG. 1 is a mass spectrum of 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxylic acid prepared in example 1.
Detailed Description
The invention provides a preparation method of chlorantraniliprole intermediate, which comprises the following steps:
mixing a compound with a structure shown in a formula I, water and sodium hydroxide for hydrolysis reaction to obtain hydrolysate feed liquid, wherein the hydrolysate has a structure shown in a formula II;
mixing the hydrolysate feed liquid, tetramethyl piperidine oxide and hydrogen peroxide to perform oxidative dehydrogenation reaction, and acidizing by hydrochloric acid after the reaction is finished to obtain chlorantraniliprole intermediate; the structure of the chlorantraniliprole intermediate is shown as a formula III;
in the invention, the synthetic route of the chlorantraniliprole intermediate is as follows:
the preparation method of the present invention will be described in detail.
The invention mixes the compound with the structure shown in the formula I, water and sodium hydroxide for hydrolysis reaction to obtain hydrolysate feed liquid, wherein the hydrolysate has the structure shown in the formula II. In the invention, the chemical name of the compound with the structure shown in the formula I is 3-bromo-1- (3-chloro-2-pyridyl) -4, 5-dihydro-1H-pyrazole-5-ethyl formate; the ratio of the mass of the compound having the structure of formula I to the volume of water is preferably 100g:0.5 to 5000mL, more preferably 100g:100 to 1000mL, more preferably 1 g/2 mL; the sodium hydroxide is preferably used in the form of sodium hydroxide solid or sodium hydroxide aqueous solution, the concentration of the sodium hydroxide aqueous solution is not particularly required, any mass fraction of sodium hydroxide solution can be adopted, in the specific embodiment of the invention, the mass fraction of the sodium hydroxide aqueous solution is preferably 30%, and when the mass and water volume ratio of the compound with the structure shown in the formula I is calculated when the sodium hydroxide aqueous solution is adopted, the water introduced into the sodium hydroxide aqueous solution is not counted; the molar ratio of the compound having the structure shown in the formula I to the sodium hydroxide is preferably 1:1-2, more preferably 1:1-1.5, and even more preferably 1:1.2.
In the present invention, the temperature of the hydrolysis reaction is 80℃or higher, more preferably 80 to 95℃and the time of the hydrolysis reaction is preferably 0.5 to 64 hours, more preferably 2 to 48 hours, still more preferably 4 to 12 hours. In the specific embodiment of the invention, HPLC is preferably used for detecting the reaction feed liquid, and the reaction is considered to be finished when the content of the compound with the structure shown in the formula I in the feed liquid is lower than 0.5 weight percent.
After the hydrolysis reaction is finished, the hydrolysate feed liquid, the tetramethylpiperidine oxide and the hydrogen peroxide are mixed for oxidative dehydrogenation reaction, and hydrochloric acid is adopted for acidification after the reaction is finished to obtain chlorantraniliprole intermediate; the chemical name of the chlorantraniliprole intermediate is 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxylic acid. In the invention, after the hydrolysis reaction is finished, the temperature is directly reduced to the temperature of oxidative dehydrogenation reaction without post-treatment; after cooling, the invention preferably adjusts the pH value of the hydrolysate feed liquid to 6-7, and then mixes the hydrolysate feed liquid with tetramethyl piperidine oxide and hydrogen peroxide, wherein the reagent for adjusting the pH value of the hydrolysate feed liquid is preferably hydrochloric acid solution, and the concentration of the hydrochloric acid solution is preferably 30wt%.
In the present invention, the mass of the tetramethylpiperidine oxide is preferably 0.5 to 1% of the mass of the compound having the structure shown in formula I, more preferably 0.6 to 0.8%; the hydrogen peroxide is preferably added in the form of hydrogen peroxide, the concentration of the hydrogen peroxide is not particularly required, any concentration of hydrogen peroxide is adopted, and in the specific embodiment of the invention, the mass fraction of the hydrogen peroxide is preferably 30%; the molar ratio of the compound having the structure shown in formula I to hydrogen peroxide is preferably 1 (1-5), more preferably 1:1.5. In the specific embodiment of the invention, the hydrolysate feed liquid is preferably cooled, then hydrochloric acid is adopted to adjust the pH value to 6-7, then tetramethyl piperidine oxide is added, hydrogen peroxide is dropwise added into the feed liquid, the dropwise adding time of the hydrogen peroxide is preferably 3h, and the reaction is continuously carried out by heat preservation after the dropwise adding is finished.
In the present invention, the temperature of the oxidative dehydrogenation is preferably 60 to 80 ℃, more preferably 65 to 75 ℃, and the time of the oxidative dehydrogenation is preferably 0.5 to 24 hours, more preferably 0.8 to 12 hours, still more preferably 1 to 5 hours.
After the dehydrogenation oxidation reaction is finished, the product feed liquid is acidified, the acid for acidification is preferably hydrochloric acid solution, the mass fraction of the hydrochloric acid solution is preferably 30%, and the pH value of the product feed liquid is preferably adjusted to 3-4; a large amount of white solid products are separated out after acidification, and the solid products separated out after acidification are filtered, washed and dried in sequence to obtain chlorantraniliprole intermediates; the washing detergent is preferably water.
The following describes the aspects of the invention in detail in connection with examples, but they should not be construed as limiting the scope of the invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
In a reaction bottle, a compound (3-bromo-1- (3-chloro-2-pyridyl) -4, 5-dihydro-1H-pyrazole-5-ethyl formate) (100 g,99%,0.3 mol) with a structure shown in a formula I, 200mL of water and 30% aqueous sodium hydroxide solution (48 g,0.36 mol) are added, stirring and heating are carried out to 85 ℃, after reaction is carried out for 4 hours, the system is dissolved, and the content of the compound with the structure shown in the formula I detected by HPLC is lower than 0.5%.
Cooling the reaction liquid to 70 ℃, dropwise adding 30% hydrochloric acid, regulating the pH value to 6.5, then adding a catalyst tetramethylpiperidine oxide (1 g), dropwise adding 30% hydrogen peroxide (51 g,30% and 0.45 mol), after 3 hours, preserving heat for 1 hour, and detecting that the content of the compound with the structure shown in the formula II is lower than 0.5% by HPLC.
Continuously dropwise adding 30% hydrochloric acid, regulating the pH of the system to 3.5, precipitating a large amount of white solid, filtering, washing with a proper amount of water, and drying a filter cake to obtain the product 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxylic acid (83.3 g,98%,0.275mol, yield 91.7%).
FIG. 1 is a mass spectrum of 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxylic acid prepared in this example, and it can be seen from FIG. 1 that the product obtained in the present invention has a target structure.
Example 2
In a reaction bottle, a compound (3-bromo-1- (3-chloro-2-pyridyl) -4, 5-dihydro-1H-pyrazole-5-ethyl formate) (100 g,99%,0.3 mol) with a structure shown in a formula I, 200mL of water and 30% aqueous sodium hydroxide solution (48 g,0.36 mol) are added, stirring and heating are carried out to 95 ℃, after 2 hours of reaction, the system is dissolved, and the content of the compound with the structure shown in the formula I detected by HPLC is lower than 0.5%.
Cooling the reaction liquid to 70 ℃, dropwise adding 30% hydrochloric acid, regulating the pH value to 6.5, then adding a catalyst tetramethylpiperidine oxide (1 g), dropwise adding 30% hydrogen peroxide (51 g,30% and 0.45 mol), after 3 hours, preserving heat for 1 hour, and detecting that the content of the compound with the structure shown in the formula II is lower than 0.5% by HPLC.
Continuously dropwise adding 30% hydrochloric acid, regulating the pH of the system to 3.5, precipitating a large amount of white solid, filtering, washing with a proper amount of water, and drying a filter cake to obtain the product 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxylic acid (79.6 g,97% by mol, 0.263% by mol, yield 87.6%).
Example 3
In a reaction bottle, a compound (3-bromo-1- (3-chloro-2-pyridyl) -4, 5-dihydro-1H-pyrazole-5-ethyl formate) (100 g,99%,0.3 mol) with a structure shown in a formula I, 200mL of water and 30% aqueous sodium hydroxide solution (48 g,0.36 mol) are added, stirring and heating are carried out to 80 ℃, after reaction is carried out for 6 hours, the system is dissolved, and the content ratio of the compound with the structure shown in the formula I detected by HPLC is lower than 0.5%.
Cooling the reaction liquid to 70 ℃, dropwise adding 30% hydrochloric acid, regulating the pH value to 6.5, then adding a catalyst tetramethylpiperidine oxide (1 g), dropwise adding 30% hydrogen peroxide (51 g,30% and 0.45 mol), after 3 hours, preserving heat for 1 hour, and detecting that the content of the compound with the structure shown in the formula II is lower than 0.5% by HPLC.
Continuously dropwise adding 30% hydrochloric acid, regulating the pH of the system to 3.5, precipitating a large amount of white solid, filtering, washing with a proper amount of water, and drying a filter cake to obtain the product 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxylic acid (80.6 g,97.5%,0.266mol, yield 88.7%).
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The preparation method of the chlorantraniliprole intermediate is characterized by comprising the following steps of:
mixing a compound with a structure shown in a formula I, water and sodium hydroxide for hydrolysis reaction to obtain hydrolysate feed liquid, wherein the hydrolysate has a structure shown in a formula II;
mixing the hydrolysate feed liquid, tetramethyl piperidine oxide and hydrogen peroxide for oxidative dehydrogenation reaction, and acidizing after the reaction is finished to obtain chlorantraniliprole intermediate; the structure of the chlorantraniliprole intermediate is shown as a formula III;
2. the preparation method according to claim 1, wherein the ratio of the mass of the compound having the structure represented by formula I to the volume of water is 100 g:0.1-5000 mL.
3. The preparation method according to claim 1, wherein the molar ratio of the compound having the structure shown in formula I to sodium hydroxide is 1:1-2.
4. The method according to claim 1, 2 or 3, wherein the hydrolysis reaction is carried out at a temperature of 80 ℃ or higher, and the hydrolysis reaction is carried out for a period of 0.5 to 64 hours.
5. The preparation method according to claim 1, wherein the mass of the tetramethylpiperidine oxide is 0.5 to 1% of the mass of the compound having the structure shown in formula I.
6. The method of claim 1, wherein the hydrogen peroxide is added in the form of hydrogen peroxide; the mol ratio of the compound with the structure shown in the formula I to the hydrogen peroxide is 1 (1-5).
7. The method according to claim 1, wherein the hydrolysis product liquid is further adjusted to a pH of 6 to 7 before mixing with tetramethylpiperidine oxide and hydrogen peroxide.
8. The method according to claim 1, wherein the oxidative dehydrogenation is carried out at a temperature of 60 to 80 ℃ for a time of 0.5 to 24 hours.
9. The preparation method according to claim 1, wherein the process further comprises the steps of sequentially filtering, washing and drying the solid product precipitated after acidification to obtain the chlorantraniliprole intermediate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211682156.3A CN115850235B (en) | 2022-12-27 | 2022-12-27 | Preparation method of chlorantraniliprole intermediate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211682156.3A CN115850235B (en) | 2022-12-27 | 2022-12-27 | Preparation method of chlorantraniliprole intermediate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115850235A CN115850235A (en) | 2023-03-28 |
| CN115850235B true CN115850235B (en) | 2024-01-09 |
Family
ID=85655011
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211682156.3A Active CN115850235B (en) | 2022-12-27 | 2022-12-27 | Preparation method of chlorantraniliprole intermediate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115850235B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104557860A (en) * | 2015-02-05 | 2015-04-29 | 浙江新安化工集团股份有限公司 | Formamido-benzamide derivative and preparation method thereof and insecticide |
| CN105085477A (en) * | 2015-09-10 | 2015-11-25 | 南京广方生物科技有限公司 | Dihalopyridylpyrazolyl amide compounds and application thereof |
| CN106187998A (en) * | 2016-07-20 | 2016-12-07 | 南通雅本化学有限公司 | A kind of preparation technology of 1 (3 chloropyridine 2 base) 3 bromine 1H pyrazoles 5 formic acid |
| CN109320498A (en) * | 2018-11-27 | 2019-02-12 | 利尔化学股份有限公司 | The bromo- 1-(3- chloro-2-pyridyl of 3-) -1H- pyrazoles -5- formic acid alkyl ester preparation method |
| CN112552284A (en) * | 2020-12-18 | 2021-03-26 | 重庆华歌生物化学有限公司 | Preparation method of chlorantraniliprole |
| CN115304581A (en) * | 2022-02-16 | 2022-11-08 | 山东省农药科学研究院 | Preparation method of intermediate pyrazole acid and application of intermediate pyrazole acid in preparation of bisamide insecticide |
| WO2022263498A1 (en) * | 2021-06-15 | 2022-12-22 | Grünenthal GmbH | Substituted pyrazole amides |
-
2022
- 2022-12-27 CN CN202211682156.3A patent/CN115850235B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104557860A (en) * | 2015-02-05 | 2015-04-29 | 浙江新安化工集团股份有限公司 | Formamido-benzamide derivative and preparation method thereof and insecticide |
| CN105085477A (en) * | 2015-09-10 | 2015-11-25 | 南京广方生物科技有限公司 | Dihalopyridylpyrazolyl amide compounds and application thereof |
| CN106187998A (en) * | 2016-07-20 | 2016-12-07 | 南通雅本化学有限公司 | A kind of preparation technology of 1 (3 chloropyridine 2 base) 3 bromine 1H pyrazoles 5 formic acid |
| CN109320498A (en) * | 2018-11-27 | 2019-02-12 | 利尔化学股份有限公司 | The bromo- 1-(3- chloro-2-pyridyl of 3-) -1H- pyrazoles -5- formic acid alkyl ester preparation method |
| CN112552284A (en) * | 2020-12-18 | 2021-03-26 | 重庆华歌生物化学有限公司 | Preparation method of chlorantraniliprole |
| WO2022263498A1 (en) * | 2021-06-15 | 2022-12-22 | Grünenthal GmbH | Substituted pyrazole amides |
| CN115304581A (en) * | 2022-02-16 | 2022-11-08 | 山东省农药科学研究院 | Preparation method of intermediate pyrazole acid and application of intermediate pyrazole acid in preparation of bisamide insecticide |
Non-Patent Citations (1)
| Title |
|---|
| "Synthesis, nematicidal activity and docking study of novel chromone derivatives containing substituted pyrazole";Li, Wei, et al.;《Chinese Chemical Letters》;第29卷(第6期);第911-914页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115850235A (en) | 2023-03-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101941947B (en) | Synthesis method of 2-chloro-6-chloroquinoxaline | |
| CN108440301A (en) | A kind of preparation method preparing adjacent nitro benzyl bromine | |
| CN116178338A (en) | Preparation method of chlorantraniliprole compound | |
| CN104557597A (en) | Clean production method of 3-(N,N-di-substituted)aminoacetanilide compounds | |
| CN109369610A (en) | A kind of synthetic method of cyclobutanol and nitro substituted naphthol class compound | |
| CN115850235B (en) | Preparation method of chlorantraniliprole intermediate | |
| CN113999171A (en) | Synthesis method of high-content dipyrithione | |
| CN113845417A (en) | Method for synthesizing (+/-) -naproxen by oxidation through continuous flow microchannel reactor | |
| CN110337434A (en) | The method for preparing 2- cyanoimidazole compound | |
| CN113943218B (en) | Preparation method and application of p-phenyl acetophenone | |
| CN107674037A (en) | The method of one kind 5 methyl 2 (triazoles of 2H 1,2,3) benzoic acid of synthesis | |
| CN103613518B (en) | The preparation method of a kind of α-benzene ethyl sulfonic acid | |
| CN108047033B (en) | Reaction device and method for preparing mandelic acid compound | |
| CN113234030A (en) | Preparation method of 6-bromo-3-hydroxy-2-pyrazinecarboxamide | |
| CN104592101A (en) | New synthesis method of sodium 3,5,6-trichloropyridyl-2-alkoxide | |
| CN113979944B (en) | Synthesis method of high-selectivity 1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-ol | |
| CN105949108B (en) | A kind of 3- (4- Methoxv-phenylsulfanvls) -1- methyl -- the preparation method of 1H- pyrrole-2,5-diones compounds | |
| CN115304541B (en) | Preparation method of 3-chloro-4- (2-pyridylmethoxy) aniline | |
| CN117843596A (en) | Preparation method of 5-chlorofuroic acid | |
| CN103772200A (en) | Preparation method for isooctyl (2,4-dichlorophenoxy) acetate | |
| CN113248402B (en) | Method for preparing salicylonitrile by adopting micro-flow field technology | |
| CN107417622B (en) | A refining method of 4(5) -chloro-2-cyano-5 (4) - (4' -methylphenyl) imidazole | |
| RU2702653C1 (en) | Method of producing triethylammonium salt of tosyl methacrylic acid | |
| CN117777021A (en) | Preparation method of 1-ethyl-3-methyl-pyrazole-5-carboxylic acid ethyl ester | |
| CN114790133A (en) | Method for synthesizing 2-chloro-4-fluorobenzoic acid by taking 2-chloro-4-aminobenzonitrile as raw material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |