A kind of preparation method of 2-nitro-4-methylsulfonyl benzoic acid

A technology of thiamphenicol benzoic acid and thiamphenicol toluene, which is applied in the field of preparation of 2-nitro-4-thiamphenicol benzoic acid, which can solve the problems of heavy metal pollution, difficulty in methyl oxidation, and difficult availability of raw materials, etc. problem, to achieve the effect of stable and efficient catalytic oxidation process, easy to realize industrial production, and green and environmental protection in the production process

Active Publication Date: 2020-07-31
ZHEJIANG UNIV OF TECH
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Problems solved by technology

[0003] The synthesis of 2-nitro-4-thiamphenicol benzoic acid has multiple methods, which are divided into according to different starting materials: (1) hydrolysis method: CN200910091467 discloses a hydrolysis of 2-nitro-4-thiamphenicol benzene Nitrile prepares 2-nitro-4-thiamphenicol benzoic acid, but the raw material is not easy to obtain and the price is relatively expensive, and is not suitable for industrialized production; (2) oxidation method: due to the aromatic ring of 2-nitro-4-thiamphenicol toluene There are two strong electron-withdrawing groups attached to it, which makes it difficult to oxidize the methyl group on the aromatic ring, so the oxidation requires the use of stronger oxidants and catalysts to accelerate the reaction.
This method has mild oxidation conditions and high yield, but it will produce heavy metal pollution and is not environmentally friendly; (ii). Nitric acid oxidation: CN201510133705 and others disclose that nitric acid is used as an oxidant, and vanadium pentoxide is commonly used as a catalyst to realize oxidation.
This method is also the main method used in industrial production at present. The advantage of this method is that nitric acid is cheap and easy to get but can produce a large amount of waste acid, and the catalyst is highly toxic, and the pressure on environmental protection is large; (iii). Peroxide oxidation: CN201110001352 reported the use of Hydrogen peroxide is used as oxidant, and hydrogen peroxide is more green and environment-friendly as oxidant, but its consumption is large, and yield is lower; (iv). Oxygen / air oxidation: for example, patent US5591890 has reported that cobalt acetate is used as catalyst, and air is oxidant; CN201110288563 uses metalloporphyrin Prepare 2-nitro-4-thiamphenicol benzoic acid for catalyst, but these methods have low oxidation ability, problems such as poor oxidation effect
[0004] On the whole, in the synthetic method of existing 2-nitro-4-thiamphenicol benzoic acid, prepare 2-nitro-4-thiamphenicol benzoic acid with oxidation 2-nitro-4-thiamphenicol toluene The process generally has defects such as large amount of three wastes, poor selectivity, and high production cost.

Method used

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  • A kind of preparation method of 2-nitro-4-methylsulfonyl benzoic acid

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] In a 500mL autoclave, add 21.5g 2-nitro-4-thiamphenicol toluene, add 200g glacial acetic acid, add 1.5g N-hydroxyphthalimide, 0.5g fuming nitric acid, and feed air into the kettle The internal pressure was 1.0 MPa, stirring and heating were started, the reaction temperature was controlled at 110°C, and the reaction was carried out for 8 hours. After the reaction was completed, it was cooled to room temperature, the solution was filtered, and the filter cake was washed with 150 mL of water. Then the filter cake was dissolved with 0.1M sodium hydroxide, the insoluble matter was filtered off, the obtained filtrate was acidified with hydrochloric acid, and after drying, 11.9 g of light yellow solid was obtained. The melting point is 213.3-214.7°C. After HPLC analysis, the purity of 2-nitro-4-thiamphenicol benzoic acid is 98.8%, and the yield is 48%.

Embodiment 2

[0024] Add 21.5g of 2-nitro-4-thiamphenicol toluene to a 500mL autoclave, add 200g of glacial acetic acid, add 3g of N,N'-dihydroxypyromellitic imide, 0.5g of fuming nitric acid, and let air in When the pressure in the kettle is 4.0MPa, start stirring and heating, and control the reaction temperature at 110°C. Reaction 10h. Cool to room temperature after the reaction, filter the solution, and wash the filter cake with 150 mL of water. Then the filter cake was dissolved with 0.1M sodium hydroxide, the insoluble matter was filtered off, the obtained filtrate was acidified with hydrochloric acid, and after drying, 17.1 g of light yellow solid was obtained. The melting point is 212.7-214.1°C. After HPLC analysis, the purity of 2-nitro-4-thiamphenicol benzoic acid is 98.3%, and the yield is 68.6%.

Embodiment 3

[0026] Add 21.5g of 2-nitro-4-thiamphenicol toluene to a 500mL autoclave, add 200g of glacial acetic acid, add 1.5g of N,N'-dihydroxypyromellitic imide, 0.2g of fuming nitric acid, and Oxygen until the pressure inside the kettle is 1.5MPa, start stirring and heating, and control the reaction temperature at 140°C. Reaction 3h. Cool to room temperature after the reaction, filter the solution, and wash the filter cake with 150 mL of water. Then the filter cake was dissolved with 0.1M sodium hydroxide, the insoluble matter was filtered off, the obtained filtrate was acidified with hydrochloric acid, and after drying, 19.5 g of light yellow solid was obtained. The melting point is 212.5-213.8°C. After HPLC analysis, the purity of 2-nitro-4-thiamphenicol benzoic acid is 98.6%, and the yield is 78.3%.

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Abstract

The invention provides a preparation method of 2-nitryl-4-methanesulfonyl-benzoic acid. The preparation method takes 2-nitryl-4-methylsulfonyl toluene as a starting raw material, aliphatic carboxylicacid as a solvent, one or more N-hydroxylamine compounds as a catalyst, one or more of nitric acid, nitrate or nitrite as a co-catalyst, and molecular oxygen as a catalyst to react for 0.5 to 15h under the conditions that the pressure is 0.1 to 5MPa and the temperature is 60 to 180 DEG C, so as to obtain 2-nitryl-4-methanesulfonyl-benzoic acid. According to the method provided by the invention, the defects of an existing industrial production method of 2-nitryl-4-methanesulfonyl-benzoic acid that the amount of three wastes is great, equipment is seriously corroded and the like are overcome andclean production of 2-nitryl-4-methanesulfonyl-benzoic acid is easy to realize.

Description

technical field [0001] The invention relates to a preparation method of 2-nitro-4-thiamphenicol benzoic acid. Background technique [0002] 2-nitro-4-thiamphenicol benzoic acid is an important intermediate in the synthesis of mesotrione, which is an excellent herbicide and has been widely used worldwide. In addition, 2-nitro-4-thiamphenicol benzoic acid is also widely used in dyestuffs, medicine and other industries, and its synthesis has received extensive attention. [0003] The synthesis of 2-nitro-4-thiamphenicol benzoic acid has multiple methods, which are divided into according to different starting materials: (1) hydrolysis method: CN200910091467 discloses a hydrolysis of 2-nitro-4-thiamphenicol benzene Nitrile prepares 2-nitro-4-thiamphenicol benzoic acid, but the raw material is not easy to obtain and the price is relatively expensive, and is not suitable for industrialized production; (2) oxidation method: due to the aromatic ring of 2-nitro-4-thiamphenicol toluen...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C315/04C07C317/44
CPCC07C315/04C07C317/44
Inventor 余志群刘继明苏为科
Owner ZHEJIANG UNIV OF TECH
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