CN113735746B - Preparation method of 2-nitro-4-methylsulfonyl benzoic acid - Google Patents
Preparation method of 2-nitro-4-methylsulfonyl benzoic acid Download PDFInfo
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a novel method for preparing 2-nitro-4-methylsulfonyl benzoic acid by catalysis, belonging to the technical field of fine chemical engineering. 2-nitro-4-methylsulfonyl toluene is used as a raw material, 30% hydrogen peroxide is used as an oxidant, MOFs is used as a main catalyst, pyridine ionic liquid is used as a cocatalyst and a reaction medium, and the selective oxidation reaction is carried out under stirring to prepare the 2-nitro-4-methylsulfonyl benzoic acid. After the reaction is finished, the ionic liquid/MOFs catalyst phase is precipitated at the bottom of the flask, separation of the catalyst phase and a product phase can be realized through extraction and liquid separation of dichloromethane, a target product can be obtained through recovery of a solvent, and the separated ionic liquid/MOFs catalyst phase can be well recycled for catalytic oxidation reaction without treatment. The method for preparing the 2-nitro-4-methylsulfonyl benzoic acid by one step is simple in technological process operation, high in efficiency, high in selectivity and environment-friendly, is a potential alternative method for the traditional production process, and has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering. Relates to an intermediate, in particular to a catalytic preparation method of 2-nitro-4-methylsulfonyl benzoic acid.
Technical Field
2-nitro-4-methylsulfonyl benzoic acid is an important organic synthesis intermediate, is widely applied to the fields of dyes, medicines, pesticides and the like, and is a key intermediate for synthesizing herbicide mesotrione especially in the pesticide field. The mesotrione has the characteristics of wide weed control spectrum, high activity, strong miscibility, flexible use, safety to aftercrop and the like, is environment-friendly, and has excellent market prospect in China. At present, the domestic process for producing 2-nitro-4-methylsulfonyl benzoic acid is not perfect, and the popularization and the use of mesotrione in China are greatly limited, so that the development of a novel synthesis process of 2-nitro-4-methylsulfonyl benzoic acid is very important (CN 107056662A; CN111254456A; CN106432006A; pesticide, 2013,52 (3): 174-177). The production process of 2-nitro-4-methylsulfonyl benzoic acid adopts an oxidation method, which is currently commonly adopted at home and abroad, and uses 2-nitro-4-methylsulfonyl toluene as a raw material to oxidize methyl on benzene rings to prepare corresponding acid. The preparation method is simple and easy to operate, but because two electron withdrawing groups are connected to the benzene ring of the 2-nitro-4-methylsulfonyl toluene, the oxidation difficulty is high, the oxidation degree is difficult to control, and therefore, strong oxidants such as a potassium permanganate oxidation method, a dichromate oxidation method, a nitric acid oxidation method, a ferrate oxidation method and the like (CN 101921215; US5424481; WO9427959; CN108715581A; CN 108752247A) are generally needed in the oxidation process, and the oxidation methods have different problems of high production cost, corrosion equipment, low product yield, environmental pollution, large three waste treatment capacity and the like in spite of relatively mild reaction conditions, simple and convenient operation and low equipment requirements. Molecular oxygen or hydrogen peroxide is used as an oxidant, has little harm to the environment and has the characteristics of cleanness and environmental friendliness, so the method is always considered as a clean production path for preparing the 2-nitro-4-methylsulfonyl benzoic acid, and is also always the focus of research in various countries. The air (oxygen) liquid phase oxidation method (CN 102329256a, CN 103787934B) uses lower fatty acid as solvent, transition metal compound as catalyst, and uses air or oxygen to oxidize methyl on benzene ring to obtain carboxylic acid. Its advantages are high selectivity, no waste gas and waste liquid, high oxidizing power, low conversion rate, high catalyst cost, complex post-treatment and low productivity. The oxydol has higher oxidability than molecular oxygen, the only byproduct in the reaction process is water, and the oxydol has the advantages of higher selectivity and conversion rate, simple operation, high atomic economy and the like, and is widely applied to green oxidation reaction. The existing oxidation preparation method of 2-nitro-4-methylsulfonylbenzoic acid hydrogen peroxide (CN 104262215A; CN102584650A; CN 101503383A) still has the problems of low reaction selectivity and product yield, large hydrogen peroxide consumption, three-waste treatment and the like. Therefore, how to design a novel catalyst with high conversion rate and high selectivity to promote the high-selectivity oxidation reaction of 2-nitro-4-methylsulfonyl toluene to prepare 2-nitro-4-methylsulfonyl benzoic acid is a challenging research subject.
Disclosure of Invention
The invention aims to develop an environment-friendly method for preparing 2-nitro-4-methylsulfonyl benzoic acid by one-step oxidation of 2-nitro-4-methylsulfonyl toluene with high conversion rate and high selectivity.
The technical solution for achieving the purpose of the invention is as follows: the new method for preparing 2-nitro-4-methylsulfonyl benzoic acid by catalyzing 2-nitro-4-methylsulfonyl toluene hydrogen peroxide with pyridine ionic liquid/metal-organic framework Materials (MOFs) is characterized in that 2-nitro-4-methylsulfonyl toluene is taken as a raw material, 30% hydrogen peroxide is taken as an oxidant, MOFs is taken as a main catalyst, pyridine ionic liquid is taken as a cocatalyst and a reaction medium, and the selective control synthesis reaction of 2-nitro-4-methylsulfonyl benzoic acid is realized under a mild condition without adding other organic solvents.
The commercial pyridine ionic liquid reaction medium used in the invention is derived from Shanghai magnesium strontium barium real company and Shanghai Chemie Co, and has the following structure:
the main catalysts used in the invention are commercial metal-organic framework materials MOF-5, PCN-222 and UiO-66, and are derived from Siam Azimuth biotechnology Co and Siam Raschi biotechnology Co.
The invention is characterized in that 2-nitro-4-methylsulfonyl toluene is used as a raw material, 30% hydrogen peroxide is used as an oxidant, MOFs is used as a main catalyst, pyridine ionic liquid is used as a cocatalyst and a reaction medium, and the material, MOFs and pyridine ionic liquid are mixed according to a proportion, stirred and reacted.
The molar ratio of the materials used in the invention is 2-nitro-4-methylsulfonyl toluene: 30% hydrogen peroxide=1:1 to 6, more preferably 1:2 to 4.
The MOFs main catalyst used in the invention is 1-30% of the mass of the 2-nitro-4-methylsulfonyl toluene, and more preferably 5-20%.
The amount of the ionic liquid used in the invention is 20-200% of the mass of the 2-nitro-4-methylsulfonyl toluene, and more preferably 50-150%.
The reaction temperature of the present invention is 20℃to 60℃and more preferably 25℃to 50 ℃.
The reaction time of the present invention is 0.5 to 5 hours, more preferably 0.5 to 3 hours.
The catalyst is one of MOF-5, PCN-222 and UiO-66, and PCN-222 is preferred.
The invention relates to pyridine ionThe liquid is [ BSO ] 3 Py]HSO 4 、[BSO 3 Py]ClO 4 、[BSO 3 Py]BF 4 、[EAPy]MnO 4 、[EAPy]PF 6 、[EAPy]HSeO 4 One of them, preferably [ BSO ] 3 Py]ClO 4 Or [ EAPy ]]HSeO 4 。
According to the method for preparing 2-nitro-4-methylsulfonyl benzoic acid based on pyridine ionic liquid/MOFs catalytic 2-nitro-4-methylsulfonyl toluene hydrogen peroxide selective oxidation, in the reaction process, pyridine ionic liquid is used as a cocatalyst and a reaction medium, so that the selective oxidation reaction can be catalyzed on one hand, and MOFs main catalyst can be well dispersed in an ionic liquid environment on the other hand, so that a novel catalytic system, namely a pyridine ionic liquid/MOFs catalytic oxidation reaction system, is formed. After the reaction is finished, cooling and standing, precipitating an ionic liquid/catalyst phase at the bottom of a flask, and extracting an oxidation product phase by methylene dichloride to recover a solvent to obtain an oxidation product 2-nitro-4-methylsulfonyl benzoic acid. The ionic liquid/MOFs catalyst phase can be recycled without treatment for the next batch of catalytic oxidation reaction.
According to the method for preparing 2-nitro-4-methylsulfonyl benzoic acid, the key technology is that pyridine ionic liquid/MOFs is adopted to catalyze the selective oxidation reaction of 2-nitro-4-methylsulfonyl toluene hydrogen peroxide to prepare 2-nitro-4-methylsulfonyl benzoic acid.
Compared with the prior art, the invention has the advantages that: (1) The novel catalytic oxidation reaction system of the pyridine ionic liquid cocatalyst/MOFs main catalyst is constructed, and the catalytic system has good stability and can be recycled. (2) The catalytic reaction system has high catalytic activity, high reaction selectivity, good product quality and high yield. (3) The traditional reaction process has the environmental problems of three-waste treatment and the like, the catalytic reaction system is simple to operate, only products and water are generated in the reaction process, and the system is environment-friendly.
Drawings
FIG. 1 is an HPLC chart of example 7.
Detailed Description
The following embodiments are merely descriptions of the best embodiments of the present invention, and do not limit the scope of the present invention in any way, the essence of the present invention is further explained by the following examples.
Example 1
Into a reaction flask, 2-nitro-4-methylsulfonylbenzoic acid (0.1 mol), [ BSO 3 Py]HSO 4 (30g) MOF-5 (3 g), 30% hydrogen peroxide (0.4 mol) was slowly added with stirring, and the reaction was continued with stirring at 45℃for 3 hours. Cooling and standing, extracting the oxidation product phase by methylene dichloride (30 mL), and separating liquid to recover the ionic liquid/MOFs catalyst phase. The methylene dichloride product phase is distilled to recover the solvent and dried to obtain the oxidized product 2-nitro-4-methylsulfonyl benzoic acid with the yield of 69 percent and the purity of 93.5 percent by HPLC analysis as in example 7.
Example 2
Into a reaction flask, 2-nitro-4-methylsulfonylbenzoic acid (0.1 mol), [ BSO 3 Py]HSO 4 (25g) PCN-222 (2.5 g) was slowly added with 30% hydrogen peroxide (0.3 mol) under stirring, and the reaction was continued with stirring at 40℃for 2 hours. Cooling and standing, extracting the oxidation product phase by methylene dichloride (30 mL), and separating liquid to recover the ionic liquid/MOFs catalyst phase. The methylene chloride product phase was distilled to recover the solvent and dried to give 2-nitro-4-methylsulfonylbenzoic acid in 83% yield and 94.6% purity by HPLC analysis as in example 7.
Example 3
Into a reaction flask, 2-nitro-4-methylsulfonylbenzoic acid (0.1 mol), [ BSO 3 Py]HSO 4 (30g) UiO-66 (4 g), 30% hydrogen peroxide (0.4 mol) was slowly added with stirring, and the reaction was continued with stirring at 50℃for 3 hours. Cooling and standing, extracting the oxidation product phase by methylene dichloride (30 mL), and separating liquid to recover the ionic liquid/MOFs catalyst phase. The methylene chloride product phase was distilled to recover the solvent and dried to give 2-nitro-4-methylsulfonylbenzoic acid in 57% yield and 92.3% purity by HPLC analysis as in example 7.
Example 4
Into a reaction flask, 2-nitro-4-methylsulfonylbenzoic acid (0.1 mol), [ BSO 3 Py]ClO 4 (25g) PCN-222 (3 g), 30% hydrogen peroxide (0.3 mol) was slowly added with stirring, and stirring was continued at 40 ℃The mixture was stirred and reacted for 2 hours. Cooling and standing, extracting the oxidation product phase by methylene dichloride (30 mL), and separating liquid to recover the ionic liquid/MOFs catalyst phase. The methylene dichloride product phase is distilled to recover the solvent and dried to obtain the 2-nitro-4-methylsulfonyl benzoic acid, the yield is 92%, and the purity is 96.8% by HPLC analysis of the same as in example 7.
Example 5
Into a reaction flask, 2-nitro-4-methylsulfonylbenzoic acid (0.1 mol), [ BSO 3 Py]BF 4 (30g) PCN-222 (4 g), 30% hydrogen peroxide (0.4 mol) was slowly added with stirring, and the reaction was continued with stirring at 45℃for 2.5 hours. Cooling and standing, extracting the oxidation product phase by methylene dichloride (30 mL), and separating liquid to recover the ionic liquid/MOFs catalyst phase. The methylene dichloride product phase is distilled to recover the solvent and dried to obtain the 2-nitro-4-methylsulfonyl benzoic acid with the yield of 78 percent and the purity of 95.2 percent by HPLC analysis as in example 7.
Example 6
In a reaction flask, 2-nitro-4-methylsulfonylbenzoic acid (0.1 mol) [ EAPy ]]MnO 4 (30g) PCN-222 (3 g), 30% hydrogen peroxide (0.3 mol) was slowly added with stirring, and the reaction was continued with stirring at 45℃for 3 hours. Cooling and standing, extracting the oxidation product phase by methylene dichloride (30 mL), and separating liquid to recover the ionic liquid/MOFs catalyst phase. The methylene chloride product phase was distilled to recover the solvent and dried to give 2-nitro-4-methylsulfonylbenzoic acid in a yield of 81% and purity of 94.5% by HPLC analysis as in example 7.
Example 7
In a reaction flask, 2-nitro-4-methylsulfonylbenzoic acid (0.1 mol) [ EAPy ]]HSeO 4 (25g) PCN-222 (2.5 g) was slowly added with 30% hydrogen peroxide (0.3 mol) under stirring, and the reaction was continued with stirring at 40℃for 2 hours. Cooling and standing, extracting the oxidation product phase by methylene dichloride (30 mL), and separating liquid to recover the ionic liquid/MOFs catalyst phase. The methylene dichloride product phase is distilled to recover the solvent and dried to obtain the 2-nitro-4-methylsulfonyl benzoic acid with the yield of 96 percent and the purity of 97.5 percent (HPLC is shown in figure 1).
Example 8
In a reaction flask, 2-nitro-4-methylsulfonylbenzoic acid (0.1 mol) [ EAPy ]]PF 6 (30g)PCN-222 (3.5 g) was slowly added with stirring with 30% hydrogen peroxide (0.4 mol), and the reaction was continued with stirring at 50℃for 2.5 hours. Cooling and standing, extracting the oxidation product phase by methylene dichloride (30 mL), and separating liquid to recover the ionic liquid/MOFs catalyst phase. The methylene chloride product phase was distilled to recover the solvent and dried to give 2-nitro-4-methylsulfonylbenzoic acid in 62% yield and 92.8% purity by HPLC analysis as in example 7.
Example 9
The catalyst in example 7 was recovered, and the catalytic reaction was carried out under the conditions in example 7, and the recovered catalyst was reused 4 times, and the experimental results showed that the catalyst activity was not decreased, the product yield was 92 to 95%, and the content was 96% or more.
Claims (9)
1. The preparation method of the 2-nitro-4-methylsulfonyl benzoic acid is characterized in that 2-nitro-4-methylsulfonyl toluene is used as a raw material, 30% hydrogen peroxide is used as an oxidant, MOFs is used as a main catalyst, pyridine ionic liquid is used as a cocatalyst and a reaction medium, oxidation reaction is carried out under stirring, cooling and standing are carried out after the reaction is finished, the ionic liquid/MOFs catalyst is precipitated at the bottom of a flask, and an oxidation product 2-nitro-4-methylsulfonyl benzoic acid can be obtained after the oxidation product phase is subjected to dichloromethane extraction treatment and solvent recovery; MOFs of the main catalyst are one of MOF-5, PCN-222 and UiO-66; the pyridine ionic liquid as cocatalyst is [ BSO ] 3 Py]HSO 4 、[BSO 3 Py]ClO 4 、[BSO 3 Py]BF 4 、[EAPy]MnO 4 、[EAPy]PF 6 、[EAPy]HSeO 4 One of them.
2. The method for preparing 2-nitro-4-methylsulfonyl benzoic acid according to claim 1 wherein the MOFs of the main catalyst are PCN-222 and the pyridine-type ionic liquid as a cocatalyst is [ BSO ] 3 Py]ClO 4 Or [ EAPy ]]HSeO 4 。
3. The method for preparing 2-nitro-4-methylsulfonyl benzoic acid according to claim 1, wherein the molar ratio of the materials used is 2-nitro-4-methylsulfonyl toluene: 30% hydrogen peroxide=1:1-6, and the consumption of MOFs catalyst is 1-30% of the mass of 2-nitro-4-methylsulfonyl toluene.
4. The method for preparing 2-nitro-4-methylsulfonyl benzoic acid according to claim 3, wherein the molar ratio of the used materials is 1:2-4, and the amount of MOFs catalyst is 5-20%.
5. The preparation method of 2-nitro-4-methylsulfonyl benzoic acid according to claim 1, wherein the amount of the ionic liquid is 20-200% of the mass of 2-nitro-4-methylsulfonyl toluene.
6. The method for preparing 2-nitro-4-methylsulfonyl benzoic acid according to claim 4, wherein the amount of ionic liquid is 50-150%.
7. The method for preparing 2-nitro-4-methylsulfonyl benzoic acid according to claim 1, wherein the reaction temperature is 20-60 ℃ and the reaction time is 0.5-5 hours.
8. The method for preparing 2-nitro-4-methylsulfonyl benzoic acid according to claim 7, wherein the reaction temperature is 25-50 ℃ and the reaction time is 0.5-3 hours.
9. The method for preparing 2-nitro-4-methylsulfonyl benzoic acid according to claim 1 wherein the recovered ionic liquid/MOFs catalyst phase can be recycled for subsequent catalytic oxidation without treatment.
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