CN113801045A - Preparation method of 2-nitro-4-methylsulfonylbenzoic acid - Google Patents
Preparation method of 2-nitro-4-methylsulfonylbenzoic acid Download PDFInfo
- Publication number
- CN113801045A CN113801045A CN202010549219.2A CN202010549219A CN113801045A CN 113801045 A CN113801045 A CN 113801045A CN 202010549219 A CN202010549219 A CN 202010549219A CN 113801045 A CN113801045 A CN 113801045A
- Authority
- CN
- China
- Prior art keywords
- nitro
- catalyst
- reaction
- bis
- methylsulfonyl
- 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.)
- Granted
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/24—Phosphines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of herbicides, and discloses a preparation method of 2-nitro-4-methylsulfonylbenzoic acid. The preparation method of the 2-nitro-4-methylsulfonylbenzoic acid comprises the following steps: 1) in the presence of alkali and a catalyst ligand, 2-nitro-4-methylsulfonyl chlorobenzene is subjected to coupling reaction with carbon monoxide and alcohol with the carbon atom number of 1-3 to obtain 2-nitro-4-methylsulfonyl alkyl benzoate; 2) and (2) carrying out hydrolysis reaction on the 2-nitro-4-methylsulfonylbenzoic acid alkyl ester obtained in the step 1), wherein the catalyst is one or more of palladium acetate, palladium chloride, palladium nitrate and copper acetate, and the catalyst ligand is one or more of triphenylphosphine, bis-diphenylphosphinoethane, bis-diphenylphosphinopropane, bis (diphenylphosphino) benzene and bis (diphenylphosphino) dimethyl xanthene. The preparation method is simple and convenient to operate, and safe and environment-friendly because nitric acid and sulfuric acid mixed acid is not used as an oxidant, a heavy metal oxidant, a toxic raw material and the like.
Description
Technical Field
The invention relates to the field of herbicides, and in particular relates to a preparation method of 2-nitro-4-methylsulfonylbenzoic acid.
Background
Mesotrione (Mesotrione), also known as Mesotrione and Mesotrione, is chemically 2- (2-nitro-4-methylsulfonylbenzoyl) cyclohexane-1, 3-dione, a triketone herbicide developed by the firm of prenatal. As a novel systemic herbicide specially used for corn fields, mesotrione has the characteristics of wide weed control spectrum, high activity, strong miscibility, safety to crops, strong environmental compatibility and the like, and has a wide development and application prospect in China.
2-nitro-4-methylsulfonylbenzoic acid (NMSBA) is an important intermediate for the synthesis of mesotrione, has a molecular weight of 245.21, a melting point of 211-212 ℃, and is a white or light yellow solid at normal temperature. It can be prepared by oxidation of 2-nitro-4-methylsulfonyltoluene (NMST):
the nitro and the methylsulfonyl in the molecule of the 2-nitro-4-methylsulfonyl toluene are strong electron-withdrawing groups, so that the oxidation of methyl is very difficult, and harsh reaction conditions are required. In addition, heavy metal oxidants such as dichromate, permanganate and the like are used in the process, so that the environment is easily polluted. If oxygen is used as the oxidizing agent, the reaction conditions are generally harsh due to the poor reactivity of oxygen itself.
Disclosure of Invention
The invention aims to provide a novel preparation method of 2-nitro-4-methylsulfonylbenzoic acid, which is simple and convenient to operate, and is safe and environment-friendly because nitric acid and sulfuric acid mixed acid is not used as an oxidant, a heavy metal oxidant, a toxic raw material and the like.
In order to achieve the above objects, the present invention provides a method for preparing 2-nitro-4-methylsulfonylbenzoic acid, which comprises the steps of,
1) in the presence of alkali and a catalyst ligand, 2-nitro-4-methylsulfonyl chlorobenzene is subjected to coupling reaction with carbon monoxide and alcohol with the carbon atom number of 1-3 to obtain 2-nitro-4-methylsulfonyl alkyl benzoate;
2) carrying out hydrolysis reaction on the 2-nitro-4-methylsulfonylbenzoic acid alkyl ester obtained in the step (1),
the catalyst is one or more of palladium acetate, palladium chloride, palladium nitrate and copper acetate, and the catalyst ligand is one or more of triphenylphosphine, bis (diphenylphosphinoethane), bis (diphenylphosphinopropane), bis (diphenylphosphino) benzene and bis (diphenylphosphino) dimethylxanthene.
Preferably, the molar ratio of the 2-nitro-4-methylsulfonyl chlorobenzene to the catalyst is 1: 0.01 to 0.2, preferably 1: 0.05-0.1.
Preferably, the molar ratio of the catalyst to the catalyst ligand is 1: 1-1.5, preferably 1: 1.2-1.3.
Preferably, the catalyst is palladium acetate and/or palladium chloride, and the catalyst ligand is bis-diphenylphosphinopropane.
Preferably, the base is one or more of triethylamine and a pyridine compound.
Preferably, the molar ratio of the 2-nitro-4-methylsulfonyl chlorobenzene to the base is 1: 1-10.
Preferably, the alcohol having 1 to 3 carbon atoms is one or more of methanol, ethanol and isopropanol, and preferably methanol.
Preferably, the amount of the alcohol having 1 to 3 carbon atoms is 120ml or more, more preferably 120-.
Preferably, the conditions of the coupling reaction include: the reaction temperature is 120-; more preferably, the conditions of the coupling reaction include: the reaction temperature is 150 ℃ and 180 ℃, the reaction time is 1-3h, and the carbon monoxide pressure is 2-3 Mpa.
Preferably, the hydrolysis reaction is carried out by removing the solvent from the product obtained in step 1).
Preferably, the hydrolysis is carried out at a pH below 7; more preferably, the hydrolysis reaction is carried out at a pH of 1 to 3 or less.
Preferably, the temperature of the hydrolysis reaction is 40-80 ℃, and the time of the hydrolysis reaction is 0.5-10 h.
Through the technical scheme, the invention can provide a novel preparation method of 2-nitro-4-methylsulfonylbenzoic acid, and the method is simple and convenient to operate, safe and environment-friendly, and can obtain the 2-nitro-4-methylsulfonylbenzoic acid with high yield and high purity.
Furthermore, the post-treatment steps of the invention are extremely simple, and the invention is particularly suitable for industrial production.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of 2-nitro-4-methylsulfonylbenzoic acid, which comprises the following steps,
1) in the presence of alkali and a catalyst ligand, 2-nitro-4-methylsulfonyl chlorobenzene is subjected to coupling reaction with carbon monoxide and alcohol with the carbon atom number of 1-3 to obtain 2-nitro-4-methylsulfonyl alkyl benzoate;
2) carrying out hydrolysis reaction on the 2-nitro-4-methylsulfonylbenzoic acid alkyl ester obtained in the step 1),
the catalyst is one or more of palladium acetate, palladium chloride, palladium nitrate and copper acetate, and the catalyst ligand is one or more of triphenylphosphine, bis (diphenylphosphinoethane), bis (diphenylphosphinopropane), bis (diphenylphosphino) benzene and bis (diphenylphosphino) dimethylxanthene.
In the invention, 2-nitro-4-methylsulfonyl chlorobenzene is reacted with carbon monoxide and alcohol with 1-3 carbon atoms in the presence of alkali and a catalyst ligand, so as to obtain 2-nitro-4-methylsulfonyl alkyl benzoate, and then the 2-nitro-4-methylsulfonyl alkyl benzoate obtained in the step 1) is subjected to hydrolysis reaction to obtain a target product, namely 2-nitro-4-methylsulfonyl benzoic acid, wherein the reaction route is shown as follows.
In the above synthetic route, R represents an alkyl group having 1 to 3 carbon atoms.
In the invention, gas carbon monoxide and alcohol with 1-3 carbon atoms and 2-nitro-4-methylsulfonyl chlorobenzene are used for coupling reaction, wherein the alcohol with 1-3 carbon atoms is used as a reaction raw material and a solvent, so that the three wastes are small, the solvent is easy to use, and a nitric acid and sulfuric acid mixed acid is not used as an oxidant, an oxidant and a toxic raw material, so that a reaction container is difficult to corrode, and the method is safe and environment-friendly.
According to the invention, the molar ratio of the 2-nitro-4-methylsulfonyl chlorobenzene to the catalyst is preferably 1: 0.01-0.2; more preferably, the molar ratio of the 2-nitro-4-methylsulfonyl chlorobenzene to the catalyst is 1: 0.03-0.1; further preferably, the molar ratio of the 2-nitro-4-methylsulfonyl chlorobenzene to the catalyst is 1: 0.04-0.1; still more preferably, the molar ratio of the 2-nitro-4-methylsulfonyl chlorobenzene to the catalyst is 1: 0.04-0.05.
In the present invention, the catalyst ligand is used to coordinate with the catalyst, and the amount thereof may be selected according to the amount of the catalyst. Preferably, the molar ratio of the catalyst to the catalyst ligand is 1: 1-1.5; more preferably, the molar ratio of the catalyst to the catalyst ligand is 1: 1.2-1.3.
According to the invention, the catalyst is one or more of palladium acetate, palladium chloride, palladium nitrate and copper acetate; preferably, the catalyst is palladium acetate and/or palladium chloride.
According to the present invention, preferably, the catalyst ligand is triphenylphosphine (PPh)3) One or more of bis (diphenylphosphinoethane) (DPPE), bis (diphenylphosphinopropane) (DPPP), bis (diphenylphosphino) benzene (DPPBE), bis (diphenylphosphino) yl dimethylxanthene (xanthphos); more preferably, the catalyst ligand is bis diphenylphosphinopropane.
According to the present invention, 2-nitro-4-methylsulfonylbenzoic acid can be obtained with high purity by using the above ligand in a simple operation.
The present inventors have also found that when the catalyst ligand is bis diphenylphosphinopropane, the yield can be extremely remarkably improved.
In a preferred embodiment of the present invention, the catalyst is palladium acetate and/or palladium chloride and the catalyst ligand is bis diphenylphosphinopropane.
According to the invention, the base is preferably an organic base. Specifically, for example, the base may be one or more of triethylamine and a pyridine compound; preferably, the base is triethylamine and/or pyridine.
In addition, the amount of the base used may be selected according to the amount of the 2-nitro-4-methylsulfonylchlorobenzene, for example, the molar ratio of the 2-nitro-4-methylsulfonylchlorobenzene to the base is 1: 1-10; preferably, the molar ratio of the 2-nitro-4-methylsulfonyl chlorobenzene to the base is 1: 3-5; particularly preferably, the molar ratio of the 2-nitro-4-methylsulfonyl chlorobenzene to the base is 1: 4.
according to the present invention, preferably, the alcohol having 1 to 3 carbon atoms is one or more of methanol, ethanol and isopropanol, and preferably methanol.
In the present invention, the alcohol having 1 to 3 carbon atoms is used as both a reaction raw material and a reaction solvent, and therefore, the alcohol having 1 to 3 carbon atoms is usually used in an excess amount, for example, the alcohol having 1 to 3 carbon atoms is used in an amount of 120ml or more based on 1mol of the 2-nitro-4-methylsulfonylchlorobenzene; preferably, the amount of the alcohol with 1-3 carbon atoms is 120-5000ml relative to 1mol of the 2-nitro-4-methylsulfonyl chlorobenzene; more preferably, the alcohol having 1 to 3 carbon atoms is used in an amount of 500-3500ml with respect to 1mol of the 2-nitro-4-methylsulfonylchlorobenzene.
According to the present invention, preferably, the conditions of the coupling reaction include: the reaction temperature is 120-; more preferably, the conditions of the coupling reaction include: the reaction temperature is 150 ℃ and 180 ℃, the reaction time is 1-3h, and the carbon monoxide pressure is 2-3 MPa. The pressure is a gauge pressure.
According to the invention, the hydrolysis reaction is preferably carried out by removing the solvent from the product obtained in step 1). Therefore, the treatment of the step 1) is extremely simple, the loss of intermediate products is avoided, and the solvent can be recycled for reuse, so that the purposes of simple operation and no waste generation can be realized.
According to the present invention, preferably, the hydrolysis reaction is carried out at a pH of 7 or less; more preferably, the hydrolysis reaction is carried out at a pH of 1 to 3 or less. By performing the hydrolysis reaction at the above pH value, the hydrolysis efficiency can be improved.
According to the invention, preferably, the temperature of the hydrolysis reaction is 40-80 ℃, and the time of the hydrolysis reaction is 0.5-10 h; more preferably, the temperature of the hydrolysis reaction is 50-60 ℃, and the time of the hydrolysis reaction is 0.5-2 h.
According to the present invention, the target product can be obtained in high yield and high purity by a simple treatment after the completion of the hydrolysis reaction. Specifically, the target product can be obtained by performing solid-liquid separation, washing and drying on the hydrolysate.
According to the invention, the method of the invention is particularly suitable for industrial production, since the work-up in steps 1) and 2) is extremely simple.
According to the present invention, the 2-nitro-4-methylsulfonylchlorobenzene can be prepared according to methods and conditions known to those skilled in the art, and preferably, the present invention adopts the following reaction scheme to prepare 2-nitro-4-methylsulfonylchlorobenzene:
(a) reacting o-chloronitrobenzene with chlorosulfonic acid in an organic solvent to obtain 3-nitro-4-chlorobenzenesulfonyl chloride;
(b) reacting the 3-nitro-4-chlorobenzenesulfonyl chloride obtained in the step (a) with a reducing agent sulfite in water in the presence of bicarbonate, reacting at 60-70 ℃ for 1-5 hours, then mixing with chloroacetic acid at 20-30 ℃ in the presence of a catalyst p-toluenesulfonic acid, and heating and refluxing the obtained mixture until the reaction liquid does not generate bubbles any more to obtain the 2-nitro-4-methylsulfonyl chlorobenzene.
In step (a), the molar ratio of o-chloronitrobenzene to chlorosulfonic acid may be 1: 1-5; the method also comprises the step of carrying out the reaction of the o-chloronitrobenzene and the chlorosulfonic acid in the step (a) in the presence of sodium chloride, wherein the molar ratio of the sodium chloride to the o-chloronitrobenzene can be 0.1-0.5: 1; the dosage of the organic solvent can be 100-500ml relative to 1mol of o-chloronitrobenzene; the organic solvent may be selected from one or more of 1, 2-dichloroethane, dichloromethane and chloroform.
The reaction conditions of o-chloronitrobenzene and chlorosulfonic acid in said step (a) may be the conditions conventional for this reaction, for example, the reaction temperature may be 50 to 60 ℃ and the reaction time may be 1 to 10 hours.
In the step (a), 3-nitro-4-chlorobenzenesulfonyl chloride can be separated from the reaction product mixture by various methods conventional in the art, for example, mixing the reaction product with an ice-water mixture, stirring, standing, separating an organic layer, and then desolventizing to obtain 3-nitro-4-chlorobenzenesulfonyl chloride.
In the step (b), the molar equivalent ratio of the sulfite to the 3-nitro-4-chlorobenzenesulfonyl chloride may be 1 to 1.2: the molar equivalent ratio of bicarbonate to 3-nitro-4-chlorobenzenesulfonyl chloride may be 1-2: 1. the bicarbonate may be sodium bicarbonate and the sulfite may be sodium sulfite; the amount of water may be 800-.
The chloroacetic acid may be used in an amount of 1.0 to 1.5 moles with respect to 1 mole of 3-nitro-4-chlorobenzenesulfonyl chloride, and the molar ratio of the chloroacetic acid to p-toluenesulfonic acid may be 1: 0.1-0.5.
The resulting mixture is heated under reflux for at least such a time as to prevent the reaction solution from generating bubbles, and the heating under reflux may be carried out for 4 to 10 hours in general.
In the step (b), the 2-nitro-4-methylsulfonylchlorobenzene is separated from the reaction product mixture by various conventional solid-liquid separation methods and conditions, such as suction filtration, and then washing and drying steps are included.
The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples. In the following examples, the product purity test method used therein was Agilent HPLC1200, and quantitative analysis was performed using an external standard method.
Preparation of example 1
This example illustrates the preparation of 2-nitro-4-methylsulfonylchlorobenzene
(1) 174.8 g (1.5 mol) of chlorosulfonic acid, 8.8 g (0.15 mol) of sodium chloride and 150ml of 1, 2-dichloroethane are added into a reaction bottle in sequence; starting stirring, heating, and heating to 55-60 deg.C; then, a 1, 2-dichloroethane solution (1, 2-dichloroethane 250ml) containing 79.8 g of o-chloronitrobenzene (0.5 mol, 99%) was added dropwise to the above mixed solution over 20 minutes; after the dropwise addition, the reaction is carried out for 5 hours under the condition of heat preservation, the mixture is poured into 500ml of ice-water mixture, stirred and kept stand, and an organic layer is separated; and drying the organic layer, and desolventizing to obtain light yellow solid 3-nitro-4-chlorobenzenesulfonyl chloride.
(2) 75.6 g (0.6 mol) of anhydrous sodium sulfite, 400ml of water and 84 g (1.0 mol) of anhydrous sodium bicarbonate are added into a reaction flask in sequence; starting stirring, heating to 70 ℃, adding all the 3-nitro-4-chlorobenzene sulfonyl chloride prepared in the step (1), continuing to react for 3 hours at 70 ℃, and then cooling to room temperature. 70.5 g (0.75 mol) of chloroacetic acid and 10 g (0.065 mol) of p-toluenesulfonic acid were added, and the mixture was heated under reflux for 8 hours until no more bubbles were formed in the reaction solution. After the reaction is finished, cooling by using an ice water bath, carrying out suction filtration, washing for three times, and drying; recrystallization from ethanol gave 113.5g of 2-nitro-4-methylsulfonylchlorobenzene as a pale yellow solid in 87.5% overall yield and 98.7% purity by weight.
Example 1
This example illustrates the preparation of 2-nitro-4-methylsulfonylbenzoic acid
Putting 20.0g of 2-nitro-4-methylsulfonyl chlorobenzene, 250ml of methanol and 34.1g of triethylamine into a 1L stainless steel autoclave, adding 0.9g of palladium acetate and 2.1g of DPPP, filling CO gas for three times for replacement, introducing CO to 2MPa, heating to 170 ℃, preserving heat and maintaining pressure for reaction for 2h, cooling, filtering, desolventizing filtrate under negative pressure, adding 500ml of water and adding 30 wt% hydrochloric acid to adjust the pH to 2, heating to 50 ℃, preserving heat for reaction for 1h, cooling to 20 ℃, filtering, washing filter cakes with 25ml of water, drying the filter cakes at 90 ℃ to obtain 17.8g of products (identified as 2-nitro-4-methylsulfonylbenzoic acid by nuclear magnetic and mass spectrometry), wherein the yield is 85.2% and the purity is 98.5 wt%.
Example 2
This example illustrates the preparation of 2-nitro-4-methylsulfonylbenzoic acid
Putting 20.0g of 2-nitro-4-methylsulfonyl chlorobenzene, 250ml of ethanol and 34.1g of triethylamine into a 1L stainless steel autoclave, adding 0.9g of palladium acetate and 2.1g of DPPP, filling CO gas for three times for replacement, introducing CO to 3MPa, heating to 180 ℃, preserving heat and maintaining pressure for reaction for 2 hours, cooling, filtering, desolventizing filtrate under negative pressure, adding 500ml of water and adding 30 wt% hydrochloric acid to adjust the pH to 2, heating to 60 ℃, preserving heat for reaction for 1 hour, cooling to 20 ℃, filtering, washing filter cakes with 25ml of water, drying the filter cakes at 90 ℃ to obtain 17.4g of products (identified as 2-nitro-4-methylsulfonylbenzoic acid by nuclear magnetic and mass spectrometry), wherein the yield is 83.5% and the purity is 98.5 wt%.
Example 3
This example illustrates the preparation of 2-nitro-4-methylsulfonylbenzoic acid
Putting 20.0g of 2-nitro-4-methylsulfonyl chlorobenzene, 250ml of methanol and 34.1g of triethylamine into a 1L stainless steel autoclave, adding 0.7g of palladium chloride and 2.1g of DPPP, filling CO gas for three times for replacement, introducing CO to 2MPa, heating to 170 ℃, preserving heat and maintaining pressure for reaction for 2h, cooling, filtering, desolventizing filtrate under negative pressure, adding 500ml of water and adding 30 wt% hydrochloric acid to adjust the pH to 2, heating to 55 ℃, preserving heat for reaction for 1h, cooling to 20 ℃, filtering, washing filter cakes with 25ml of water, drying the filter cakes at 90 ℃ to obtain a product (identified as 2-nitro-4-methylsulfonylbenzoic acid by nuclear magnetic and mass spectrometry), wherein the yield is 82.6%, and the purity is 98.4 wt%.
Example 4
This example illustrates the preparation of 2-nitro-4-methylsulfonylbenzoic acid
Putting 20.0g of 2-nitro-4-methylsulfonyl chlorobenzene, 250ml of ethanol and 34.1g of triethylamine into a 1L stainless steel autoclave, adding 0.7g of palladium chloride and 2.1g of DPPP, filling CO gas for three times for replacement, introducing CO to 2MPa, heating to 160 ℃, preserving heat and maintaining pressure for reaction for 2 hours, cooling, filtering, desolventizing filtrate under negative pressure, adding 500ml of water and adding 30 wt% hydrochloric acid to adjust the pH to 2, heating to 55 ℃, preserving heat for reaction for 1 hour, cooling to 20 ℃, filtering, washing filter cakes with 25ml of water, drying the filter cakes at 90 ℃ to obtain 16.8g of products (identified as 2-nitro-4-methylsulfonylbenzoic acid by nuclear magnetic and mass spectrometry), wherein the yield is 80.4% and the purity is 98.4 wt%.
Example 5
The procedure was followed as in example 1, except that copper acetate was used in place of palladium acetate in the same molar amount, to give 15.5g of 2-nitro-4-methylsulfonylbenzoic acid in 74.2% yield and 97.7% purity by weight.
Examples 6 to 9
The procedure of example 1 was followed, except that the same molar amounts of the ligands shown in Table 1 were used instead of DPPP, respectively, and the results are shown in Table 1.
TABLE 1
| Ligands | Product weight (g) | Purity of the product (% by weight) | Yield (%) |
| DPPE | 5.2 | 93.3 | 23.3 |
| DPPBE | 5.8 | 93.8 | 26.2 |
| Xantphos | 8.9 | 94.1 | 40.3 |
| PPh3 | 2.3 | 85.2 | 9.4 |
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A preparation method of 2-nitro-4-methylsulfonylbenzoic acid is characterized by comprising the following steps,
1) in the presence of alkali and a catalyst ligand, 2-nitro-4-methylsulfonyl chlorobenzene is subjected to coupling reaction with carbon monoxide and alcohol with the carbon atom number of 1-3 to obtain 2-nitro-4-methylsulfonyl alkyl benzoate;
2) carrying out hydrolysis reaction on the 2-nitro-4-methylsulfonylbenzoic acid alkyl ester obtained in the step 1),
the catalyst is one or more of palladium acetate, palladium chloride, palladium nitrate and copper acetate, and the catalyst ligand is one or more of triphenylphosphine, bis (diphenylphosphinoethane), bis (diphenylphosphinopropane), bis (diphenylphosphino) benzene and bis (diphenylphosphino) dimethylxanthene.
2. The method of claim 1, wherein the molar ratio of the 2-nitro-4-methylsulfonylchlorobenzene to the catalyst is 1: 0.01 to 0.2, preferably 1: 0.04-0.1.
3. The process according to claim 1 or 2, wherein the catalyst is used in a molar ratio of the catalyst to the catalyst ligand of 1: 1-1.5, preferably 1: 1.2-1.3.
4. A process according to any one of claims 1 to 3, wherein the catalyst is palladium acetate and/or palladium chloride and the catalyst ligand is bis diphenylphosphinopropane.
5. The method according to any one of claims 1 to 4, wherein the base is one or more of triethylamine and a pyridine compound;
preferably, the molar ratio of the 2-nitro-4-methylsulfonyl chlorobenzene to the base is 1: 1-10.
6. The method according to any one of claims 1 to 5, wherein the alcohol having 1 to 3 carbon atoms is one or more of methanol, ethanol and isopropanol, preferably methanol;
preferably, the alcohol having 1 to 3 carbon atoms is used in an amount of 120ml or more, preferably 120-5000ml, more preferably 500-3500ml, based on 1mol of the 2-nitro-4-methylsulfonylchlorobenzene.
7. The method of any one of claims 1-6, wherein the conditions of the coupling reaction comprise: the reaction temperature is 120-;
preferably, the conditions of the coupling reaction include: the reaction temperature is 150 ℃ and 180 ℃, the reaction time is 1-3h, and the carbon monoxide pressure is 2-3 MPa.
8. The process according to any one of claims 1 to 7, wherein the hydrolysis reaction is carried out by removing the solvent from the product obtained in step 1).
9. The process of any one of claims 1 to 7, wherein the hydrolysis reaction is carried out at a pH of 7 or less.
10. The process according to any one of claims 1 to 7, wherein the temperature of the hydrolysis reaction is 40 to 80 ℃ and the time of the hydrolysis reaction is 0.5 to 10 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010549219.2A CN113801045B (en) | 2020-06-16 | 2020-06-16 | Preparation method of 2-nitro-4-methylsulfonyl benzoic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010549219.2A CN113801045B (en) | 2020-06-16 | 2020-06-16 | Preparation method of 2-nitro-4-methylsulfonyl benzoic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113801045A true CN113801045A (en) | 2021-12-17 |
| CN113801045B CN113801045B (en) | 2023-09-15 |
Family
ID=78944468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010549219.2A Active CN113801045B (en) | 2020-06-16 | 2020-06-16 | Preparation method of 2-nitro-4-methylsulfonyl benzoic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113801045B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116102473A (en) * | 2023-01-10 | 2023-05-12 | 启农生物科技(北京)有限公司 | Preparation process of 2-nitro-4-methylsulfonyl-benzoic acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1224420A (en) * | 1997-03-24 | 1999-07-28 | 道农业科学公司 | 1-alkyl-4-benzoyl-5-hydroxypyrazole compounds and their use as herbicides |
| CN101628885A (en) * | 2009-08-21 | 2010-01-20 | 北京颖泰嘉和科技股份有限公司 | Preparation method of 2-nitryl-4-thiamphenicol benzoic acid |
| CN111254457A (en) * | 2020-03-31 | 2020-06-09 | 四川大学 | Electrochemical synthesis method of aromatic carboxylic acid and alkyl carboxylic acid |
-
2020
- 2020-06-16 CN CN202010549219.2A patent/CN113801045B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1224420A (en) * | 1997-03-24 | 1999-07-28 | 道农业科学公司 | 1-alkyl-4-benzoyl-5-hydroxypyrazole compounds and their use as herbicides |
| CN101628885A (en) * | 2009-08-21 | 2010-01-20 | 北京颖泰嘉和科技股份有限公司 | Preparation method of 2-nitryl-4-thiamphenicol benzoic acid |
| CN111254457A (en) * | 2020-03-31 | 2020-06-09 | 四川大学 | Electrochemical synthesis method of aromatic carboxylic acid and alkyl carboxylic acid |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116102473A (en) * | 2023-01-10 | 2023-05-12 | 启农生物科技(北京)有限公司 | Preparation process of 2-nitro-4-methylsulfonyl-benzoic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113801045B (en) | 2023-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105218378A (en) | Prepare the method for substituted biphenyl | |
| CN114409515B (en) | Preparation method of gem-difluoroolefin compound | |
| Li et al. | Nickel-catalyzed C–H direct amination of benzoxazoles with secondary Amines | |
| CN108690007B (en) | C-H coupling reaction catalyzed by transition metal for efficiently preparing o-cyanoated aromatic ring or unsaturated aliphatic ring compound | |
| CN105348038A (en) | Synthetic method for 4,4'-dihalogenated-3,3'-dialkyl(alkoxyl) biphenyl compounds | |
| CN113801045A (en) | Preparation method of 2-nitro-4-methylsulfonylbenzoic acid | |
| CN103965242A (en) | Synthesis method of novel difluoromethylene phosphate salt, and application of novel difluoromethylene phosphate salt | |
| EP1951677B1 (en) | Process for the production of carboxanilides | |
| US3968124A (en) | Process for preparing phenyl-acetic acid esters | |
| US6206819B1 (en) | Halogenation catalyst | |
| CN105294415A (en) | Preparation method of 3-halogenated fluorenone compound | |
| JPH0430387B2 (en) | ||
| CN106458820A (en) | Process for the production of 2,6-dimethylbenzoquinone | |
| US2562151A (en) | Halogenated nitro ethers | |
| CN108101729A (en) | A kind of synthetic method of seven fluoronaphthalene of compound 2- bromines | |
| US4057585A (en) | Method of preparing 2,3-dichloroanisole | |
| CN109503532A (en) | A kind of 3- phenyl -3- Benzylbenzofuran ketone compounds and its high-efficiency synthesis method | |
| CN115385781B (en) | Method for preparing 1, 4-tetraalkoxy-2-butene compound | |
| CN113372200B (en) | Preparation method of 2-bromo-6-fluoroanisole | |
| CN108503583B (en) | Alkylation method of nitrogen-hydrogen-containing compound and application thereof | |
| CN117105977A (en) | Convenient synthesis method of o-carbonyl phosphate compound | |
| US20220064184A1 (en) | Method for preparing 2-arylmalonic acid derivative and intermediate, and use thereof | |
| CN116444452A (en) | Preparation process of intermediate I for synthesizing topramezone | |
| CN118047707A (en) | Direct cross coupling method of sulfoxide ylide and aryl fluorosulfonate | |
| CN116425671A (en) | Synthesis method of 2-chloro-4- (trifluoromethyl) pyridine |
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 |