CN108440352B - Preparation method of mesotrione - Google Patents
Preparation method of mesotrione Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- 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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- C07C2601/14—The ring being saturated
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Abstract
A process for preparing mesotrione includes such steps as using p-methylsulfonyl o-nitrobenzoic acid as raw material, acyl chlorination, condensation reaction with 1, 3-cyclohexanedione to obtain 2-nitro-4-methylsulfonylbenzoic acid- [3 '-carbonyl-1' -cyclohexenol ] -ester, and rearrangement reaction of enol ester under the action of inorganic alkali and tertiary amine organic alkali to obtain acylated cyclic 1, 3-dicarbonyl compound mesotrione, and features no use of virulent cyanide catalyst, low reaction temp, short reaction time, cyclic use of solvent, high total mole yield up to 95%, content up to 98.5%, high safety and environmental protection.
Description
Technical Field
The invention belongs to the field of herbicide technical preparation, and particularly relates to a preparation method of mesotrione.
Background
The p-hydroxyphenylpyruvate dioxygenase (HPPD) is a key enzyme in a plastoquinone and tocopherol biosynthesis pathway necessary for the normal growth of plants, can catalyze the biochemical process from tyrosine to plastoquinone in plants, and is one of the most important herbicide action targets at present.
Mesotrione can inhibit HPPD, ultimately affecting carotenoid biosynthesis, and is a broad-spectrum, systemic, selective, contact herbicide. Mesotrione is absorbed mainly through the leaf surface and root, and is conducted to the top and to the ground in the xylem and phloem, and is distributed throughout the plant. After the weeds are applied, the leaf surfaces whiten, and then meristem necrosis occurs. The selectivity of mesotrione arises from differences in its metabolism in crops and weeds (metabolism to the 4-hydroxy derivative in crops) and may also be due to crops absorbing foliar drag than weeds.
Mesotrione is mainly used for corn, and can also be used for lawn, sugarcane, rice, onion, sorghum, other small crops and the like. The copper mesotrione is used for preventing and removing annual broadleaf weeds in the corn field before or after germination, such as cocklebur, Ambrosia trifoliata, piemarker, quinoa, amaranth, polygonum and the like, and can prevent and remove some gramineous weeds in the corn field, especially the weeds with sulfonylurea resistance, and the mesotrione is safe to corn and is safe to environment and succeeding crops.
To expand the herbicidal spectrum, mesotrione pre-emergent soil surface treatment can be mixed with acetochlor, metolachlor, atrazine, metribuzin and the like, and post-emergent spray can be mixed with methyl esterified vegetable oil, bromoxynil, rimsulfuron, thifensulfuron methyl, nicosulfuron, atrazine and the like.
At present, the synthesis routes of mesotrione at home and abroad mainly comprise three routes:
route one: dimethyl malonate is taken as a raw material, is cyclized with 3-butene-2-ketone under the condition of sodium methoxide to form 4-methoxy formyl-1, 3-cyclohexanedione, then is reacted with p-methylsulfonyl o-nitrobenzoyl chloride to obtain an intermediate 1, the intermediate 1 is converted into an intermediate 2 under the catalytic action of acetone cyanohydrin, and the intermediate 2 is hydrolyzed and decarboxylated to obtain a product mesotrione (refer to Chinese patent CN 101671286A).
The reaction route is as follows:
the raw material 3-butene-2-ketone used in the route is not easy to obtain, hydrolysis and decarboxylation are needed in the reaction, and the method is long in step and not suitable for industrial production.
And a second route: p-methylsulfonyl o-nitrobenzaldehyde is taken as a raw material and undergoes an addition reaction with 1, 3-cyclohexanedione to obtain an intermediate 3, and the intermediate 3 is oxidized by hydrogen peroxide to obtain the product mesotrione (refer to Chinese patent CN 103772243A).
The reaction route is as follows:
the main raw material of the route is not easy to obtain the methylsulfonyl o-nitrobenzaldehyde, the condensation reaction is firstly carried out, then the oxidation reaction is carried out, the yield is very low, more impurities are difficult to purify, the production cost is higher, and the method is not suitable for industrialization.
And a third route: p-methylsulfonyl o-nitrobenzoic acid is taken as a raw material, chlorinated by thionyl chloride, and then condensed with 1, 3-cyclohexanedione to obtain an intermediate 4, and the intermediate 4 is rearranged under the catalysis of acetone cyanohydrin (or potassium cyanide, sodium cyanide and the like) to obtain the product mesotrione (refer to US4695673)
The reaction route is as follows:
in the route, the adopted p-methylsulfonyl-o-nitrobenzoic acid raw material can be directly purchased, but in the process of obtaining the product mesotrione by rearranging the intermediate 4, cyanide catalysts (acetone cyanohydrin, potassium cyanide or sodium cyanide and the like) are needed, and all the catalysts belong to highly toxic substances, so that great potential safety hazards exist during production and feeding, and once leakage happens, the environment is greatly polluted.
In addition, in the chinese invention patent CN201510770055B, purine compounds are used as rearrangement reagents to prepare copper mesotrione, but according to the above conditions, reaction verification shows that the reaction activity is very low, and only about 15% of intermediate 4 is converted into mesotrione product.
Disclosure of Invention
The invention aims to provide a preparation method of mesotrione copper, which optimizes rearrangement reaction conditions of enol ester, avoids using a virulent cyanide catalyst, has lower rearrangement reaction temperature, short reaction time, recyclable solvent, high total molar yield of mesotrione product up to 95 percent and high content of mesotrione up to 98.5 percent, is safe and environment-friendly, has small amount of three wastes and is suitable for industrial production.
In order to achieve the purpose, the invention provides the following technical scheme:
the preparation method of the pyroxsulam copper comprises the following steps:
1) acyl chlorination reaction
Dissolving p-methylsulfonyl o-nitrobenzoic acid in an aprotic solvent, heating to 60-85 ℃, dropwise adding an acyl chlorination reagent, continuing to perform reflux reaction for 0.5-2 hours after dropwise adding is finished, and evaporating the solvent under reduced pressure to obtain an intermediate p-methylsulfonyl o-nitrobenzoyl chloride;
2) condensation reaction
Adding an aprotic solvent into the product obtained in the step 1), adding 1, 3-cyclohexanedione at 0-30 ℃, dropwise adding an acid binding agent, and reacting for 1-2 hours while keeping the temperature after dropwise adding to obtain a reaction solution of 2-nitro-4-methylsulfonylbenzoic acid- [3 '-carbonyl-1' -cyclohexenol ] -ester;
3) rearrangement reaction
Adding a rearrangement catalyst into the reaction liquid after the condensation reaction is finished, keeping the temperature at 20-30 ℃ and reacting for 2-6 hours to obtain mesotrione;
wherein, the rearrangement catalyst is composed of inorganic base and tertiary amine organic base, the molar ratio of the inorganic base to the tertiary amine organic base is as follows: tertiary amine organic bases 3 to 100: 1.
preferably, in step (b), the aprotic solvent is at least one of benzene, toluene, cyclohexane, dichloromethane, dichloroethane, chloroform; in the step 2), the aprotic solvent is at least one of benzene, toluene, cyclohexane, dichloromethane, dichloroethane, chloroform and acetonitrile.
And the dosage of the aprotic solvent in the step 1) and the step 2) is 3-5 times of the weight of the corresponding initial reaction substrate.
Preferably, in step 1), the acyl chlorination reagent is at least one selected from thionyl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, phosgene, diphosgene and triphosgene; in the step 2), the acid binding agent is selected from at least one of pyridine and trialkylamine.
Preferably, in the rearrangement reagent of step 3), the inorganic base is selected from at least one of sodium carbonate, potassium carbonate, cesium carbonate, trisodium phosphate.
In the rearrangement catalyst of the step 3), the tertiary amine organic base is selected from 4-N, N' -Dimethylaminopyridine (DMAP), 1, 8-diazabicycloundec-7-ene (DBU) or hexamethylenetetramine.
Preferably, in step 3), the temperature of the rearrangement reaction is 20 to 30 ℃.
Further, in the step 1), the molar ratio of the reaction substrate to the methylsulfonyl o-nitrobenzoic acid, the acyl chlorination reagent and the acid-binding agent is 1: 1-1.5: 1 to 2.
Still further, the molar ratio of the reaction substrate to the methylsulfonyl o-nitrobenzoic acid to the inorganic base in the rearrangement catalyst is 1: 0.3 to 1.
Still further, the molar ratio of the reaction substrate to the methylsulfonyl o-nitrobenzoic acid to the tertiary amine organic base in the rearrangement reagent is 1: 0.01 to 0.15.
The invention optimizes the rearrangement reaction condition of enol ester, adopts inorganic base and organic base composite catalyst to carry out rearrangement reaction, selects tertiary amine organic base with stronger alkalinity to ensure that the intermediate 2-nitro-4-methylsulfonyl benzoic acid- [3 '-carbonyl-1' -cyclohexenol ] -ester can be rearranged at the temperature of 20-30 ℃, has short reaction time, can recycle solvent, is safe and environment-friendly, has small amount of three wastes, and is suitable for industrial production.
Compared with the prior art, the invention has the following beneficial effects:
after the intermediate 2-nitro-4-methylsulfonylbenzoic acid- [3 '-carbonyl-1' -cyclohexenol ] -ester is obtained, the reaction liquid can be directly subjected to rearrangement reaction, and the 2-nitro-4-methylsulfonylbenzoic acid- [3 '-carbonyl-1' -cyclohexenol ] -ester is subjected to rearrangement under the co-catalysis of inorganic base and tertiary amine organic base with strong alkalinity to obtain an acylated annular 1, 3-dicarbonyl compound, so that the use of virulent cyanide catalysts such as acetone cyanohydrin, potassium cyanide or sodium cyanide is avoided.
The method has the advantages of low reaction temperature, short reaction time, recyclable solvent, total molar yield of the prepared mesotrione product of more than 82%, optimized process conditions of even 95% and 98.5% content, safety, environmental protection, small amount of three wastes, reduction of production cost and suitability for industrial production.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
Adding 25g (0.101mol) of p-methylsulfonyl-o-nitrobenzoic acid and 75g of dichloroethane into a dry reaction bottle, stirring and heating to reflux, dropwise adding 13g (0.108mol) of thionyl chloride, reacting at the reflux temperature for 2 hours after the dropwise adding is finished, and evaporating the solvent under reduced pressure to obtain 26.6g of p-methylsulfonyl-o-nitrobenzoyl chloride.
Adding 80g of acetonitrile into the obtained p-methylsulfonyl o-nitrobenzoyl chloride, adding 12g (0.106mol) of 1, 3-cyclohexanedione at 0-30 ℃, dropwise adding 11g (0.108mol) of triethylamine at 0-30 ℃ under controlled temperature, finishing dropwise within 1-2 hours, and preserving heat at 20-30 ℃ for 2 hours to obtain an intermediate 2-nitro-4-methylsulfonylbenzoic acid- [3 '-carbonyl-1' -cyclohexenol ] -ester.
And then adding 9.8g (0.03mol) of cesium carbonate and 0.5g (0.004mol) of 4-dimethylaminopyridine into the reaction system, preserving the temperature at 20-30 ℃ for 3 hours, distilling off the solvent under reduced pressure, adding 30g of water, acidifying with hydrochloric acid, extracting with dichloroethane, drying, and distilling off the solvent to obtain 31.0g (0.090mol) of the mesotrione product, wherein the content is 98%, and the total yield is 88.65%.
Example 2
Adding 25g (0.101mol) of p-methylsulfonyl-o-nitrobenzoic acid and 125g of dichloroethane into a dry reaction bottle, stirring and heating to reflux, dropwise adding 17.85g (0.15mol) of thionyl chloride, reacting for 1 hour at the reflux temperature, and evaporating the solvent under reduced pressure to obtain 26g of p-methylsulfonyl-o-nitrobenzoyl chloride.
Adding 125g of dichloroethane to the obtained p-methylsulfonyl-o-nitrobenzoyl chloride, adding 12g (0.106mol) of 1, 3-cyclohexanedione at 20-30 ℃, dropwise adding 22g (0.2mol) of triethylamine at 20-30 ℃, finishing dropwise adding within 2 hours, and preserving heat at 20-30 ℃ for 1 hour to obtain an intermediate 2-nitro-4-methylsulfonylbenzoic acid- [3 '-carbonyl-1' -cyclohexenol ] -ester.
And then 17g (0.05mol) of cesium carbonate and 0.5g (0.003mol) of DBU are added into the reaction system, the mixture is subjected to heat preservation reaction at the temperature of 20-30 ℃ for 2 hours, the solvent is evaporated under reduced pressure, 30g of water is added, hydrochloric acid is used for acidification, dichloromethane is used for extraction, drying is carried out, and the solvent is evaporated to obtain 33g (0.096mol) of the product mesotrione, wherein the content is 98.5 percent, and the yield is 95.0 percent.
Example 3
100g of dichloroethane was added to p-methylsulfonyl-o-nitrobenzoyl chloride obtained in the same manner as in example 1, 12g (0.106mol) of 1, 3-cyclohexanedione was added at 20 to 30 ℃, 11g (0.108mol) of triethylamine was added dropwise at 30 ℃ over 1 to 2 hours, and the mixture was incubated at 20 to 30 ℃ for 2 hours to obtain 2-nitro-4-methylsulfonylbenzoic acid- [3 '-carbonyl-1' -cyclohexenol ] -ester as an intermediate.
Then adding 15g (0.1mol) of potassium carbonate and 0.15g (0.001mol) of hexamethylenetetramine into the reaction system, preserving the temperature for 6 hours at 20-30 ℃, adding 30g of water, acidifying with hydrochloric acid, extracting, drying, and evaporating the solvent under reduced pressure to obtain 29.7g (0.082mol) of mesotrione with the content of 97 percent and the yield of 85 percent.
Example 4
80g of dichloroethane was added to p-methylsulfonyl-o-nitrobenzoyl chloride obtained in the same manner as in example 1, 12g (0.106mol) of 1, 3-cyclohexanedione was added thereto at 20 to 30 ℃, 11g (0.108mol) of triethylamine was added dropwise thereto at 20 ℃ over 1 to 2 hours, and the mixture was incubated at 20 to 30 ℃ for 2 hours to obtain 2-nitro-4-methylsulfonylbenzoic acid- [3 '-carbonyl-1' -cyclohexenol ] -ester as an intermediate.
And adding 7.4g (0.05mol) of potassium carbonate and 2g (0.015mol) of 4-dimethylaminopyridine into the reaction system, preserving the temperature at 20-30 ℃ for 6 hours, adding 30g of water, acidifying with hydrochloric acid, extracting, drying, and evaporating the solvent under reduced pressure to obtain 30.5g (0.088mol) of the product mesotrione with the content of 97.5 percent and the yield of 86.8 percent.
Example 5
80g of chloroform was added to p-methylsulfonyl-o-nitrobenzoyl chloride obtained in the same manner as in example 1, 12g (0.106mol) of 1, 3-cyclohexanedione was added thereto at 20 to 30 ℃, 11g (0.108mol) of triethylamine was added dropwise thereto at 20 to 30 ℃ over 1 to 2 hours, and the mixture was incubated at 20 to 30 ℃ for 2 hours to obtain 2-nitro-4-methylsulfonylbenzoic acid- [3 '-carbonyl-1' -cyclohexenol ] -ester as an intermediate.
4.15g (0.03mol) of potassium carbonate and 0.5g (0.004mol) of 4-dimethylaminopyridine are added into the reaction system, the temperature is kept at 20 ℃ for 6 hours, 30g of water is added, acidification is carried out by hydrochloric acid, extraction and drying are carried out, and the solvent is evaporated under reduced pressure, so that 29.1g (0.084mol) of the product mesotrione with the content of 97.5 percent and the yield of 82.8 percent is obtained.
Example 6
80g of chloroform was added to p-methylsulfonyl-o-nitrobenzoyl chloride obtained in the same manner as in example 1, 12g (0.106mol) of 1, 3-cyclohexanedione was added thereto at 20 to 30 ℃, 11g (0.108mol) of pyridine was added dropwise thereto at 20 to 30 ℃ over 1 to 2 hours, and the mixture was incubated at 20 to 30 ℃ for 2 hours to obtain 2-nitro-4-methylsulfonylbenzoic acid- [3 '-carbonyl-1' -cyclohexenol ] -ester as an intermediate.
Then adding 7.4g (0.05mol) of potassium carbonate and 0.5g (0.004mol) of 4-dimethylaminopyridine into the reaction system, preserving the temperature for 4 hours at 20-30 ℃, adding 30g of water, acidifying with hydrochloric acid, extracting, drying, and evaporating the solvent under reduced pressure to obtain 31.1g (0.090mol) of the product mesotrione with the content of 98 percent and the yield of 88.9 percent.
Comparative example 1
To p-methylsulfonyl-o-nitrobenzoyl chloride obtained in the manner described in example 1 was added acetonitrile 80g, 1, 3-cyclohexanedione 12g (0.106mol) at 20-30 deg.C, triethylamine 11g (0.108mol) was added dropwise at 20-30 deg.C for 1-2 hours, and the mixture was incubated at 20-30 deg.C for 2 hours to give intermediate 4.
Then adding 7.4g (0.0525mol) of potassium carbonate and 0.5g (0.004mol) of acetone cyanohydrin, preserving the temperature at 20-30 ℃ for 16 hours, distilling off the solvent under reduced pressure, adding 30g of water, acidifying with hydrochloric acid, extracting with dichloromethane, drying, and distilling off the solvent to obtain 29g (0.096mol) of mesotrione, the content of which is 97.5 percent, and the yield of which is 83.4 percent.
Comparative example 2
To the p-methylsulfonyl-o-nitrobenzoyl chloride obtained in example 1 was added acetonitrile 80g, 1, 3-cyclohexanedione 12g (0.106mol) was added at 20 to 30 ℃, triethylamine 11g (0.108mol) was added dropwise at 20 to 30 ℃ for 1 to 2 hours, and the mixture was allowed to stand at 20 to 30 ℃ for 2 hours to obtain intermediate 4. Then adding 7.4g (0.0525mol) of potassium carbonate and 0.5g (0.004mol) of 1,2, 4-triazole, preserving the temperature at 20-30 ℃ for 16 hours, distilling off the solvent under reduced pressure, adding 30g of water, acidifying with hydrochloric acid, extracting with dichloromethane, drying, distilling off the solvent to obtain 26.6g (0.080mol) of the product mesotrione with the content of 95.5 percent and the yield of 75 percent.
Claims (6)
1. A process for the preparation of mesotrione, comprising the steps of:
1) acyl chlorination reaction
Dissolving p-methylsulfonyl o-nitrobenzoic acid in an aprotic solvent, heating to 60-85 ℃, dropwise adding an acyl chlorination reagent, carrying out reflux reaction for 0.5-2 hours after dropwise adding is finished, and reducing pressure to evaporate the solvent to obtain p-methylsulfonyl o-nitrobenzoyl chloride;
2) condensation reaction
Adding an aprotic solvent into the product obtained in the step 1), adding 1, 3-cyclohexanedione at 0-30 ℃, dropwise adding an acid-binding agent, and reacting for 1-2 hours while keeping the temperature after dropwise adding to obtain an intermediate 2-nitro-4-methylsulfonylbenzoic acid- [3 '-carbonyl-1' -cyclohexenol ] -ester;
3) rearrangement reaction
Adding a rearrangement catalyst into the reaction liquid after the condensation reaction is finished, keeping the temperature at 20-30 ℃ and reacting for 2-6 hours to obtain mesotrione;
wherein, the rearrangement catalyst is composed of inorganic base and tertiary amine organic base, the molar ratio of the inorganic base to the tertiary amine organic base is as follows: tertiary amine organic bases 3 to 100: 1, the molar ratio of p-methylsulfonyl o-nitrobenzoic acid to tertiary amine organic alkali in the rearrangement catalyst is 1: 0.01 to 0.15; the tertiary amine organic base is selected from 4-N, N' -dimethylamino pyridine, 1, 8-diazabicycloundec-7-ene or hexamethylenetetramine; the inorganic base is at least one of sodium carbonate, potassium carbonate, cesium carbonate and trisodium phosphate.
2. The process for preparing mesotrione according to claim 1, wherein in step 1) the aprotic solvent is at least one of benzene, toluene, cyclohexane, dichloromethane, dichloroethane or chloroform; in the step 2), the aprotic solvent is at least one of benzene, toluene, cyclohexane, dichloromethane, dichloroethane, chloroform and acetonitrile.
3. The method for preparing mesotrione according to claim 1, wherein in step 1), the acyl chlorination reagent is at least one selected from thionyl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, phosgene, diphosgene and triphosgene; in the step 2), the acid binding agent is selected from at least one of pyridine and trialkylamine.
4. The process for the preparation of mesotrione according to claim 1, wherein the amount of aprotic solvent used in step 1) and step 2) is 3 to 5 times the weight of the corresponding starting reaction substrate.
5. The process for the preparation of mesotrione as claimed in any one of claims 1 to 4, wherein in step 1) the molar ratio of reaction substrate to methylsulfonyl ortho-nitrobenzoic acid, acid chloride reagent and acid binding agent is in the range of 1: 1-1.5: 1 to 2.
6. The process for preparing mesotrione according to claim 1, wherein the molar ratio of p-methylsulfonyl o-nitrobenzoic acid to inorganic base in the rearrangement catalyst is 1: 0.3 to 1.
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| 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 |
| 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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| CN1272837A (en) * | 1997-11-27 | 2000-11-08 | 曾尼卡有限公司 | Process for preparation of acylated cyclic 1,3-dicarbonyl compounds |
| CN105712912A (en) * | 2014-12-02 | 2016-06-29 | 浙江省诸暨合力化学对外贸易有限公司 | Preparation method of triketone compound and triketone compound intermediate |
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