CN108440352A - A kind of preparation method of mesotrione - Google Patents
A kind of preparation method of mesotrione Download PDFInfo
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- CN108440352A CN108440352A CN201810292770.6A CN201810292770A CN108440352A CN 108440352 A CN108440352 A CN 108440352A CN 201810292770 A CN201810292770 A CN 201810292770A CN 108440352 A CN108440352 A CN 108440352A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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Abstract
A kind of preparation method of mesotrione, using to methylsulfonyl o-nitrobenzoic acid as raw material, elder generation and 1 after chloride, 3 cyclohexanedione condensation reactions obtain 2 nitro of intermediate, 4 methyl sulfonylbenzoic acid [3 ' carbonyl, 1 ' cyclohexenol] ester, then under co-catalysis effect of the inorganic base with the stronger tertiary amines organic base of alkalinity, carry out the rearrangement of enol ester, obtain acylated ring-type 1, 3 dicarbonyl compound mesotriones, this method avoid the cyanide catalysts for using severe toxicity, reaction temperature is relatively low, reaction time is short, solvent is recyclable to be applied mechanically, the mesotrione product total moles yield of preparation can reach 95%, content is 98.5%, and this process safety environmental protection, quantity of three wastes is small, it is suitable for industrialized production.
Description
Technical field
The invention belongs to herbicide active compound preparation fields, and in particular to a kind of preparation method of mesotrione.
Background technology
P-hydroxybenzene pyruvic acid (HPP) ester dual oxide enzyme (HPPD) is plastoquinone and fertility necessary to plant normal growth
Key enzyme in phenol Biosynthetic pathway, can be catalyzed the biochemical process from tyrosine to plastoquinone in plant, and HPPD is current
One of most important herbicide action target.
Mesotrione can inhibit HPPD, and the final biosynthesis for influencing carotenoid is wide spectrum, interior suction, selection
Property, contact killing type herbicide.Mesotrione passes mainly by blade face and root absorption in xylem and bast Xiang Ding and to base
It leads, is distributed in entire plant.Weeds are after by medicine, blade face albefaction, then separate living tissue necrosis.The selectivity of mesotrione is derived from it
Metabolic different (4- hydroxy derivatives are metabolized as in crop) in crop and weeds, it is also possible to since crop is to it
Foliage Absorption will be slower than weeds.
Mesotrione is mainly used for corn, also can be used for lawn, sugarcane, rice, onion, sorghum and other small ancestor crops
Deng.Nitre sulphur grass copper be used for bud before or bud rear defence remove corn field annual broadleaf weed, as Siberian cocklebur, Ambrosia trifida, piemarker, lamb's-quarters,
Amaranth and knotweed etc., and corn field some grassy weeds can be prevented and kill off, especially effective to sulfonylurea resistant weed, mesotrione is not only
To corn safety, and to environment, succession crop safety.
In order to expand herbicidal spectrum, native list processing can be with Acetochlor, isopropyl methoxalamine, atrazine, piperazine grass before mesotrione bud
Ketone etc. is mixed, and spraying can be with methylated vegetable oil, Brominal, rimsulfuron, thifensulfuronmethyl, nicosulfuron, atrazine etc. after seedling
It is mixed.
Currently, the synthetic route of mesotrione mainly has three both at home and abroad：
Route one：Using dimethyl malenate as raw material, cyclization is 4- methoxies under conditions of sodium methoxide with 3- butene-2s -one
Base formoxyl -1, hydroresorcinol, then intermediate 1 is reacted to obtain with to methylsulfonyl ortho-nitrophenyl formyl chloride, intermediate 1 is in acetone cyanogen
Switch to obtain intermediate 2 under the catalytic action of alcohol, intermediate 2 obtains product mesotrione (specially with reference to China by hydrolysis, decarboxylic reaction
Sharp CN101671286A).
Reaction route is as follows：
The raw material 3- butene-2 -one that this route is used is not easy to obtain, and reaction needs hydrolysis, decarboxylation, and step is longer, is not suitable for work
Industry metaplasia is produced.
Route two：Using to methylsulfonyl o-nitrobenzaldehyde as raw material, and 1, hydroresorcinol occur addition reaction obtain it is intermediate
Body 3, intermediate 3 obtain product mesotrione (referring to Chinese patent CN103772243A) under hydrogen peroxide oxidation.
Reaction route is as follows：
The primary raw material of this route is not easy to obtain methylsulfonyl o-nitrobenzaldehyde, first carries out condensation reaction, then aoxidized
Reaction, yield is very low, and impurity is more to be difficult to purify, and production cost is higher, is unsuitable for industrializing.
Route three：To be raw material through thionyl chloride chlorination to methylsulfonyl o-nitrobenzoic acid, afterwards with 1, hydroresorcinol contracting
Intermediate 4 is reacted to obtain in conjunction, and intermediate 4 resets to obtain product nitre under the catalytic action of acetone cyanohydrin (or potassium cyanide, Cymag etc.)
Sulphur humulone (refers to United States Patent (USP) US4695673)
Reaction route is as follows：
In this route, can directly being purchased to methylsulfonyl o-nitrobenzoic acid raw material for use still, is reset by intermediate 4
During obtaining product mesotrione, need to use cyanide catalyst (acetone cyanohydrin, potassium cyanide or Cymag etc.), these
Catalyst belongs to extremely toxic substance, and there are huge security risks when production feeds intake, once leakage can cause environment very big dirt
Dye.
In addition, purine compound has been used to be prepared as rearrangement reagent in Chinese invention patent CN201510770055B
Nitre sulphur grass copper, but according to the condition, find that reactivity is very low by reaction verification, the conversion of only about 15% intermediate 4
For mesotrione product.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of nitre sulphur grass copper, optimize the rearrangement reaction item of enol ester
Part avoids the cyanide catalyst using severe toxicity, and rearrangement reaction temperature is relatively low, and the reaction time is short, and solvent is recyclable to be applied mechanically, nitre sulphur
Mesotrione product total moles yield can reach 95%, content 98.5%, and the environmental protection of this process safety, and quantity of three wastes is small, is suitable for industry
Metaplasia is produced.
In order to achieve the above object, the present invention provides the following technical solutions：
A kind of preparation method of nitre sulphur grass copper, includes the following steps：
1) acyl chloride reaction
Methylsulfonyl o-nitrobenzoic acid will be dissolved in aprotic solvent, and be warming up to 60-85 DEG C, chloride reagent is added dropwise,
Continue back flow reaction after dripping 0.5~2 hour, decompression steams solvent, obtains intermediate to methylsulfonyl ortho-nitrophenyl formyl chloride；
2) condensation reaction
Aprotic solvent is added into the product of step 1), 1 is added at 0~30 DEG C, acid binding agent is added dropwise in hydroresorcinol,
Insulation reaction is added dropwise 1~2 hour, obtains 2- nitro -4- methyl sulfonylbenzoic acids-[3 '-carbonyls -1 '-cyclohexenol] -ester
Reaction solution；
3) rearrangement reaction
Rearrangement catalyst is added into the reaction solution after condensation reaction, reaction temperature is 20-30 DEG C, insulation reaction 2-
6 hours, obtain mesotrione；
Wherein, the rearrangement catalyst is made of inorganic base and tertiary amines organic base, and the molar ratio of the two is nothing
Machine alkali：Tertiary amines organic base=3~100：1.
Preferably, step) in, the aprotic solvent is benzene, toluene, hexamethylene, dichloromethane, dichloroethanes, chlorine
At least one of imitate；In step 2), the aprotic solvent is benzene, toluene, hexamethylene, dichloromethane, dichloroethanes, chlorine
At least one of imitative, acetonitrile.
Also, the dosage of the aprotic solvent in step 1) and step 2) is respectively the 3~5 of corresponding starting reaction substrate weight
Times.
Preferably, in step 1), the chloride reagent is selected from thionyl chloride, phosphorus trichloride, phosphorus pentachloride, trichlorine oxygen
At least one of phosphorus, phosgene, surpalite, triphosgene；In step 2), acid binding agent in pyridine, trialkylamine at least one
Kind.
Preferably, in the rearrangement reagent of step 3), the inorganic base is selected from sodium carbonate, potassium carbonate, cesium carbonate, tertiary sodium phosphate
At least one of.
Also, in the rearrangement catalyst of step 3), the tertiary amines organic base is selected from 4-N, N '-dimethylamino naphthyridines
(DMAP), 11 carbon -7- alkene (DBU) of 1,8- diazabicylos or hexa.
Preferably, in step 3), the temperature of rearrangement reaction is 20-30 DEG C.
Further, in step 1), mole of the reaction substrate to methylsulfonyl o-nitrobenzoic acid, chloride reagent and acid binding agent
Than being 1：1~1.5：1~2.
Further, reaction substrate is to the molar ratio of the inorganic base in methylsulfonyl o-nitrobenzoic acid and rearrangement catalyst
1：0.3~1.
Further, mole of the reaction substrate to the tertiary amines organic base in methylsulfonyl o-nitrobenzoic acid and rearrangement reagent
Than being 1：0.01~0.15.
Present invention optimizes the rearrangement reaction conditions of enol ester, are reset using inorganic base+organic alkali composite catalyst
Reaction selects the stronger tertiary amines organic base of alkalinity, makes intermediate 2- nitro -4- methyl sulfonylbenzoic acids-[3 '-carbonyls -1 ' -
Cyclohexenol] -ester can be reset at 20-30 DEG C, and the reaction time is short, and solvent is recyclable to be applied mechanically, safety and environmental protection, the three wastes
It measures small, is suitable for industrialized production.
Compared with prior art, the present invention has the advantages that：
After the present invention obtains intermediate 2- nitro -4- methyl sulfonylbenzoic acids-[3 '-carbonyls -1 '-cyclohexenol] -ester, instead
Answer liquid that can directly carry out rearrangement reaction, under co-catalysis effect of the inorganic base with the stronger tertiary amines organic base of alkalinity, 2- nitre
Base -4- methyl sulfonylbenzoic acids-[3 '-carbonyls -1 '-cyclohexenol] -ester obtains acylated ring-type 1,3- dicarbapentaborane into rearrangement
Compound avoids the cyanide catalyst using the severe toxicity such as acetone cyanohydrin, potassium cyanide or Cymag.
Reaction temperature of the present invention is relatively low, and the reaction time is short, and solvent is recyclable to be applied mechanically, the mesotrione product total moles of preparation
Yield is 82% or more, and optimization process condition is even up to 95%, content 98.5%, and the environmental protection of this process safety, and three
Useless amount is small, reduces production cost, is suitable for industrialized production.
Specific implementation mode
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
Into dry reaction bulb, input stirs methylsulfonyl o-nitrobenzoic acid 25g (0.101mol) and dichloroethanes 75g
It mixes and is warming up to reflux, thionyl chloride 13g (0.108mol) is added dropwise, reacted 2 hours in reflux temperature after dripping off, decompression steams molten
Agent is obtained to methylsulfonyl ortho-nitrophenyl formyl chloride 26.6g.
Acetonitrile 80g is added into the ortho-nitrophenyl formyl chloride obtained above to methylsulfonyl, 1,3- hexamethylenes are added at 0-30 DEG C
Triethylamine 11g (0.108mol) is added dropwise at 0-30 DEG C for diketone 12g (0.106mol), temperature control, drips off within 1-2 hours, is protected at 20-30 DEG C
Temperature 2 hours, obtains intermediate 2- nitro -4- methyl sulfonylbenzoic acids-[3 '-carbonyls -1 '-cyclohexenol] -ester.
Cesium carbonate 9.8g (0.03mol), 4- dimethylamino pyridines 0.5g (0.004mol) are put into reaction system again,
20-30 DEG C keeps the temperature 3 hours, and decompression steams solvent, and 30g water is added, is acidified with hydrochloric acid, is extracted with dichloroethanes, dry, steams molten
Agent obtains product mesotrione 31.0g (0.090mol), content 98%, total recovery 88.65%.
Embodiment 2
It is put into dry reaction bulb to methylsulfonyl o-nitrobenzoic acid 25g (0.101mol) and dichloroethanes 125g,
Stirring is warming up to reflux, and thionyl chloride 17.85g (0.15mol) is added dropwise, and drips off reflux temperature and reacts 1 hour, decompression steams molten
Agent is obtained to methylsulfonyl ortho-nitrophenyl formyl chloride 26g.
Dichloroethanes 125g is added into the ortho-nitrophenyl formyl chloride obtained above to methylsulfonyl, 1 is added at 20-30 DEG C,
Triethylamine 22g (0.2mol) is added dropwise at 20-30 DEG C, drips off within 2 hours by hydroresorcinol 12g (0.106mol), is protected at 20-30 DEG C
Temperature 1 hour, obtains intermediate 2- nitro -4- methyl sulfonylbenzoic acids-[3 '-carbonyls -1 '-cyclohexenol] -ester.
Cesium carbonate 17g (0.05mol), DBU 0.5g (0.003mol) are put into reaction system again, is kept the temperature at 20-30 DEG C
Reaction 2 hours, decompression steam solvent, and 30g water is added, is acidified with hydrochloric acid, is extracted with dichloromethane, dry, steam solvent, obtain
Product mesotrione 33g (0.096mol), content 98.5%, yield 95.0%.
Embodiment 3
To according to the method in embodiment 1 obtain in methylsulfonyl ortho-nitrophenyl formyl chloride be added dichloroethanes 100g,
1, hydroresorcinol 12g (0.106mol) are added at 20-30 DEG C, the dropwise addition triethylamine 11g (0.108mol) at 30 DEG C, 1-2 hours
It drips off, 2 hours is kept the temperature at 20-30 DEG C, obtain intermediate 2- nitro -4- methyl sulfonylbenzoic acids-[3 '-carbonyls -1 '-cyclohexene
Alcohol] -ester.
Potassium carbonate 15g (0.1mol), hexa 0.15g (0.001mol), in 20- are put into reaction system again
30 DEG C keep the temperature 6 hours, and 30g water is added, is acidified with hydrochloric acid, extract, dry, and decompression steams solvent, obtains product mesotrione
29.7g (0.082mol), content 97%, yield 85%.
Embodiment 4
To according to the method in embodiment 1 obtain in methylsulfonyl ortho-nitrophenyl formyl chloride be added dichloroethanes 80g,
20-30 DEG C is added 1, hydroresorcinol 12g (0.106mol), and triethylamine 11g (0.108mol) is added dropwise at 20 DEG C, drips within 1-2 hours
It is complete, 2 hours are kept the temperature at 20-30 DEG C, obtains intermediate 2- nitro -4- methyl sulfonylbenzoic acids-[3 '-carbonyls -1 '-cyclohexene
Alcohol] -ester.
Potassium carbonate 7.4g (0.05mol), 4- dimethylamino pyridines 2g (0.015mol) are put into reaction system again,
20-30 DEG C keeps the temperature 6 hours, and 30g water is added, is acidified with hydrochloric acid, extracts, dry, and decompression steams solvent, obtains product mesotrione
30.5g (0.088mol), content 97.5%, yield 86.8%.
Embodiment 5
To according to the method in embodiment 1 obtain in methylsulfonyl ortho-nitrophenyl formyl chloride be added chloroform 80g, in 20-
30 DEG C are added 1, hydroresorcinol 12g (0.106mol), and triethylamine 11g (0.108mol) is added dropwise at 20-30 DEG C, drip within 1-2 hours
It is complete, 2 hours are kept the temperature at 20-30 DEG C, obtains intermediate 2- nitro -4- methyl sulfonylbenzoic acids-[3 '-carbonyls -1 '-cyclohexene
Alcohol] -ester.
Potassium carbonate 4.15g (0.03mol), 4- dimethylamino pyridines 0.5g (0.004mol) are put into reaction system again,
6 hours are kept the temperature at 20 DEG C, 30g water is added, is acidified with hydrochloric acid, is extracted, dry, decompression steams solvent, obtains product mesotrione
29.1g (0.084mol), content 97.5%, yield 82.8%.
Embodiment 6
To according to the method in embodiment 1 obtain in methylsulfonyl ortho-nitrophenyl formyl chloride be added chloroform 80g, in 20-
30 DEG C are added 1, hydroresorcinol 12g (0.106mol), and pyridine 11g (0.108mol) is added dropwise at 20-30 DEG C, drips off within 1-2 hours,
2 hours are kept the temperature at 20-30 DEG C, obtains intermediate 2- nitro -4- methyl sulfonylbenzoic acid-[3 '-carbonyls -1 '-cyclohexenol] -
Ester.
Potassium carbonate 7.4g (0.05mol), 4- dimethylamino pyridines 0.5g (0.004mol) are put into reaction system again,
20-30 DEG C keeps the temperature 4 hours, and 30g water is added, is acidified with hydrochloric acid, extracts, dry, and decompression steams solvent, obtains product mesotrione
31.1g (0.090mol), content 98%, yield 88.9%.
Comparative example 1
To according to the method in embodiment 1 obtain in methylsulfonyl ortho-nitrophenyl formyl chloride be added acetonitrile 80g, in 20-
30 DEG C are added 1, hydroresorcinol 12g (0.106mol), and triethylamine 11g (0.108mol) is added dropwise at 20-30 DEG C, drip within 1-2 hours
It is complete, 2 hours are kept the temperature at 20-30 DEG C, obtains intermediate 4.
Potassium carbonate 7.4g (0.0525mol), acetone cyanohydrin 0.5g (0.004mol) are put into again, and it is small that 16 are kept the temperature at 20-30 DEG C
When, decompression steams solvent, and 30g water is added, is acidified with hydrochloric acid, is extracted with dichloromethane, dry, steams solvent, obtains product nitre
Sulphur humulone 29g (0.096mol), content 97.5%, yield 83.4%.
Comparative example 2
Obtained in by embodiment 1 in methylsulfonyl ortho-nitrophenyl formyl chloride be added acetonitrile 80g, at 20-30 DEG C be added
Triethylamine 11g (0.108mol) is added dropwise at 20-30 DEG C, drips off within 1-2 hours, in 20- by 1, hydroresorcinol 12g (0.106mol)
30 DEG C keep the temperature 2 hours, obtain intermediate 4.Potassium carbonate 7.4g (0.0525mol), 1,2,4- triazole 0.5g are put into again
(0.004mol) keeps the temperature 16 hours at 20-30 DEG C, and decompression steams solvent, and 30g water is added, is acidified with hydrochloric acid, is extracted with dichloromethane
It takes, it is dry, solvent is steamed, product mesotrione 26.6g (0.080mol), content 95.5%, yield 75% are obtained.
Claims (10)
1. a kind of preparation method of mesotrione, includes the following steps：
1) acyl chloride reaction
Methylsulfonyl o-nitrobenzoic acid will be dissolved in aprotic solvent, and be warming up to 60-85 DEG C, chloride reagent is added dropwise, be added dropwise
Back flow reaction 0.5~2 hour after complete, decompression steam solvent, obtain to methylsulfonyl ortho-nitrophenyl formyl chloride；
2) condensation reaction
Aprotic solvent is added into the product of step 1), 1 is added at 0~30 DEG C, acid binding agent is added dropwise in hydroresorcinol, is added dropwise
It finishes insulation reaction 1~2 hour, obtains intermediate 2- nitro -4- methyl sulfonylbenzoic acid-[3 '-carbonyls -1 '-cyclohexenol] -
Ester；
3) rearrangement reaction
Rearrangement catalyst is added into the reaction solution after condensation reaction, reaction temperature is 20-30 DEG C, and insulation reaction 2-6 is small
When, obtain mesotrione；
Wherein, the rearrangement catalyst is made of inorganic base and tertiary amines organic base, and the molar ratio of the two is inorganic base：
Tertiary amines organic base=3~100：1.
2. the preparation method of mesotrione according to claim 1, which is characterized in that in step 1), described is non-proton molten
Agent is at least one of benzene, toluene, hexamethylene, dichloromethane, dichloroethanes, chloroform；In step 2), described is non-proton molten
Agent is at least one of benzene, toluene, hexamethylene, dichloromethane, dichloroethanes, chloroform, acetonitrile.
3. the preparation method of mesotrione according to claim 1, which is characterized in that in step 1), chloride examination
Agent is selected from least one of thionyl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, phosgene, surpalite, triphosgene；Step
2) in, acid binding agent is selected from least one of pyridine, trialkylamine.
4. the preparation method of mesotrione according to claim 1, which is characterized in that non-proton in step 1) and step 2)
The dosage of solvent is respectively 3~5 times of corresponding starting reaction substrate weight.
5. the preparation method of mesotrione according to claim 1, which is characterized in that described in the rearrangement reagent of step 3)
Inorganic base is selected from least one of sodium carbonate, potassium carbonate, cesium carbonate, tertiary sodium phosphate.
6. the preparation method of mesotrione according to claim 1, which is characterized in that in the rearrangement catalyst of step 3), institute
It states tertiary amines organic base and is selected from 4-N, N '-dimethylamino naphthyridines, 11 carbon -7- alkene of 1,8- diazabicylos or hexa-methylene four
Amine.
7. the preparation method of mesotrione according to claim 1, which is characterized in that in step 3), the temperature of rearrangement reaction
It is 20-30 DEG C.
8. according to the preparation method of any one of the claim 1-7 mesotriones, which is characterized in that in step 1), react bottom
Object is 1 to the molar ratio of methylsulfonyl o-nitrobenzoic acid, chloride reagent and acid binding agent：1~1.5：1~2,.
9. the preparation method of mesotrione according to claim 1, which is characterized in that methylsulfonyl o-nitrobenzoic acid and again
The molar ratio for arranging the inorganic base in catalyst is 1：0.3~1.
10. according to the preparation method of the mesotrione of claim 1 or 9, which is characterized in that methylsulfonyl o-nitrobenzoic acid
Molar ratio with the tertiary amines organic base in rearrangement catalyst is 1：0.01~0.15.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110256308A (en) * | 2019-07-09 | 2019-09-20 | 湖北广富林生物制剂有限公司 | A kind of synthesis technology of mesotrione |
| CN113845450A (en) * | 2020-06-28 | 2021-12-28 | 沈阳中化农药化工研发有限公司 | Synthesis method of mesotrione and homologs thereof |
| CN113943235A (en) * | 2020-07-17 | 2022-01-18 | 沈阳中化农药化工研发有限公司 | Method for preparing mesotrione herbicide |
| CN115784949A (en) * | 2022-12-08 | 2023-03-14 | 江苏扬农化工股份有限公司 | Preparation method of triketone compound |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256308A (en) * | 2019-07-09 | 2019-09-20 | 湖北广富林生物制剂有限公司 | A kind of synthesis technology of mesotrione |
| CN110256308B (en) * | 2019-07-09 | 2021-07-23 | 湖北广富林生物制剂有限公司 | Synthesis process of mesotrione |
| CN113845450A (en) * | 2020-06-28 | 2021-12-28 | 沈阳中化农药化工研发有限公司 | Synthesis method of mesotrione and homologs thereof |
| CN113943235A (en) * | 2020-07-17 | 2022-01-18 | 沈阳中化农药化工研发有限公司 | Method for preparing mesotrione herbicide |
| WO2022012482A1 (en) * | 2020-07-17 | 2022-01-20 | 沈阳中化农药化工研发有限公司 | Method for preparing mesotrione herbicide |
| CN113943235B (en) * | 2020-07-17 | 2022-06-14 | 沈阳中化农药化工研发有限公司 | Method for preparing mesotrione herbicide |
| CN115784949A (en) * | 2022-12-08 | 2023-03-14 | 江苏扬农化工股份有限公司 | Preparation method of triketone compound |
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