CN115672395A - Catalyst system and method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation - Google Patents
Catalyst system and method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation Download PDFInfo
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- QNOUABMNRMROSL-UHFFFAOYSA-N 110964-79-9 Chemical compound CS(=O)(=O)C1=CC=C(C(O)=O)C([N+]([O-])=O)=C1 QNOUABMNRMROSL-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 66
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 230000003647 oxidation Effects 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 58
- 150000002466 imines Chemical class 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 229910052802 copper Inorganic materials 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 150000002739 metals Chemical class 0.000 claims abstract description 26
- OXBDLEXAVKAJFD-UHFFFAOYSA-N 1-methyl-4-methylsulfonyl-2-nitrobenzene Chemical compound CC1=CC=C(S(C)(=O)=O)C=C1[N+]([O-])=O OXBDLEXAVKAJFD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 16
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- VTULOVFSIMMKKO-UHFFFAOYSA-N 2-methoxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(OC)C(=O)C2=C1 VTULOVFSIMMKKO-UHFFFAOYSA-N 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 102
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 66
- 239000000243 solution Substances 0.000 claims description 20
- 239000012295 chemical reaction liquid Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000003916 acid precipitation Methods 0.000 claims description 3
- 235000021317 phosphate Nutrition 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims description 2
- 150000003840 hydrochlorides Chemical class 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 7
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 7
- 230000002378 acidificating effect Effects 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 150000002736 metal compounds Chemical class 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010505 homolytic fission reaction Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- NZSLSTXKPQAVHL-UHFFFAOYSA-N 2-$l^{1}-oxidanylisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N([O])C(=O)C2=C1 NZSLSTXKPQAVHL-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000005578 Mesotrione Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- KPUREKXXPHOJQT-UHFFFAOYSA-N mesotrione Chemical compound [O-][N+](=O)C1=CC(S(=O)(=O)C)=CC=C1C(=O)C1C(=O)CCCC1=O KPUREKXXPHOJQT-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation with catalyst system, wherein the catalyst system comprisesThe composite material comprises a compound containing two metals and an imine compound, wherein the two metals are Cu and Mn or Cu and Co respectively; the imine-containing compound is one or more of N-hydroxyphthalimide, N' -dihydroxypyromellitic imine and N-methoxyphthalimide. The invention takes 2-nitro-4-methylsulfonyl toluene as a raw material, utilizes a catalytic system constructed by two metal compounds and imine-containing compounds to catalyze and oxidize to prepare the 2-nitro-4-methylsulfonylbenzoic acid, and solves the problems of more potential safety hazards and NO existing in the traditional nitric acid oxidation process X And the problems of serious pollution of the acidic wastewater, high treatment cost of the acidic wastewater, serious corrosion of equipment and the like. Meanwhile, the oxidation process of the 2-nitro-4-methylsulfonylbenzoic acid is oxidized and generated at the next step under mild conditions under the catalytic action of a catalyst, so that the reaction efficiency and selectivity in the oxidation process are improved, the conversion rate is improved, and the production cost is reduced.
Description
Technical Field
The invention relates to the technical field of chemical catalytic preparation, in particular to a catalyst system and a method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation.
Background
2-nitro-4-methylsulfonylbenzoic acid is white or light yellow crystalline powder at normal temperature, is widely applied to the industries such as dye, medicine and the like, is also an important intermediate for synthesizing mesotrione (herbicide), is widely applied in the world at present, and is widely concerned in synthesis.
At present, the traditional preparation method of 2-nitro-4-methylsulfonylbenzoic acid is prepared by using 2-nitro-4-methylsulfonyltoluene as a raw material and oxidizing the raw material by using nitric acid. This method is reported in various documents, such as US5424481a; hebei chemical industry, 2005, 5; hubei agricultural science, 2012,51 (5): 924-926; chemical industry, 2012,43 (1): 12-14; university of Zhejiang university, 2009,37 (3): 267-271 and patent CN103073461a.
The traditional method has the advantages of low price, good selectivity for certain oxidation reactions, high yield and simple process. The disadvantages are that the whole reaction process is violent, the danger of the reaction system is large, the using amount of nitric acid is large, and a large amount of NO is generated along with the reaction X The method has the advantages of acid wastewater pollution, environmental friendliness, serious equipment corrosion and high production cost.
Therefore, a new preparation process is needed to solve the problems of more potential safety hazards, serious environmental pollution, serious equipment corrosion, high production cost and the like in the preparation process of the 2-nitro-4-methylsulfonylbenzoic acid.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a catalyst system and a method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation, to eliminate the traditional technology of using nitric acid as an oxidant, to prepare 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation of a catalyst system constructed by using two metal compounds and imine-containing compounds and using 2-nitro-4-methylsulfonyltoluene as a raw material, and to solve the problems of more potential safety hazards and NO existing in the traditional nitric acid oxidation process X And the problems of serious pollution of the acidic wastewater, high treatment cost of the acidic wastewater, serious corrosion of equipment and the like. Meanwhile, the oxidation process of the 2-nitro-4-methylsulfonylbenzoic acid is oxidized and generated at the next step under mild conditions under the catalytic action of the catalyst, so that the reaction efficiency and selectivity in the oxidation process are improved, the conversion rate is improved, and the production cost is reduced.
The invention provides a catalyst system, which comprises a compound containing two metals and an imine compound, wherein the two metals are Cu and Mn or Cu and Co respectively; the imine compound is one or more of N-hydroxyphthalimide, N' -dihydroxypyromellitic imine and N-methoxyphthalimide.
Preferably, the compound of the two metals is one or more of oxides, hydrochlorides, sulfates, phosphates, acetates, carbonates of Cu and Mn or Cu and Co, or hydrates of the above salts.
Preferably, the ratio of Cu: mn: the molar ratio of the imine compound is 1: (0.1-15): (1-100).
Preferably, the ratio of Cu: co: the molar ratio of the imine compound is 1: (0.1-20): (1-100).
The invention also provides a method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation, which comprises the following steps:
(1) Weighing two compounds of Cu and Mn or Cu and Co and an imine-containing compound, and uniformly mixing to prepare a catalyst;
(2) Dissolving 2-nitro-4-methylsulfonyl toluene in acetic acid to prepare a solution, adding a catalyst, stirring and heating;
(3) Slowly dripping peroxyacetic acid when the acetic acid solution of the 2-nitro-4-methylsulfonylbenzoic acid is raised to the required reaction temperature;
(4) After the dropwise addition is finished, preserving the temperature at the reaction temperature for oxidation reaction for a certain time;
(5) And after the reaction is finished, obtaining an oxidation reaction liquid, and carrying out post-treatment on the oxidation reaction liquid to obtain a finished product of the 2-nitro-4-methylsulfonylbenzoic acid.
Preferably, the volume concentration of the acetic acid used in the step (2) is 50-100%, and the dosage of the acetic acid is 2-nitro-4-methylsulfonyltoluene by weight: acetic acid =1: (2-10).
Preferably, the catalyst used in step (2) is 2-nitro-4-methylsulfonylbenzoic acid by weight: catalyst =1: (0.08-0.3).
Preferably, the volume concentration of the peroxyacetic acid used in the step (3) is 30-40%, and the amount of the peroxyacetic acid is 2-nitro-4-methylsulfonylbenzoic acid by weight: peroxyacetic acid =1: (1.4-4).
Preferably, the dropping time of the peracetic acid in the step (3) is 3 to 11 hours.
Preferably, the reaction temperature in the step (3) and the step (4) is 80-118 ℃, and the heat preservation oxidation reaction time in the step (4) is 1-3 h.
Preferably, the post-treatment in the step (5) comprises crude crystallization, alkali dissolution and acid precipitation treatment, wherein the crude crystallization comprises dilution crystallization and filtration washing; the alkali dissolution comprises alkali adjustment and filtration; the acid precipitation comprises acid adjustment and filtration washing.
The working principle of the invention is as follows: the catalyst system and the method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation use 2-nitro-4-methylsulfonyltoluene as a raw material, and utilize a catalytic system constructed by two metal compounds and an imine-containing compound to catalyze and oxidize, so that methyl in the 2-nitro-4-methylsulfonyltoluene is substituted by carboxyl to prepare the 2-nitro-4-methylsulfonylbenzoic acid. NHPI is amine-containing compound, wherein O-H bond is easy to generate homolytic cleavage to generate free radical-N-oxyphthalimide free radical (PINO), the free radical is easy to deprive H from C-H bond in organic reaction substrate to enable the substrate to generate homolytic cleavage to generate carbon free radical, thereby initiating free radical chain reaction; the transition metals such as Co, mn, cu and the like have empty d orbitals, can supply electrons and can accept the electrons, so that the oxidation state and the coordination number of the transition metals can be reversibly changed, and when the transition metals are coordinated with an organic compound, a special electronic effect and a special space effect can be generated, thereby being beneficial to improving the selectivity of the oxidation reaction. In the catalytic oxidation reaction process, under the synergistic action of the metal ions and the amine-containing compound, the oxidation reaction can occur at a lower temperature, and the reaction is more complete, so that the product conversion rate and the reaction rate are improved.
The invention has the beneficial effects that: the catalyst system and the method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation of the catalyst system provided by the invention abandon the traditional technology of using nitric acid as an oxidant, use 2-nitro-4-methylsulfonyltoluene as a raw material, and utilize the catalytic system constructed by two metal compounds and imine-containing compounds to prepare 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation, thereby solving the problems of more potential safety hazards and NO (nitric oxide) in the traditional nitric acid oxidation process X And the problems of serious pollution of the acidic wastewater, high treatment cost of the acidic wastewater, serious corrosion of equipment and the like. Meanwhile, the oxidation process of the 2-nitro-4-methylsulfonylbenzoic acid is oxidized and generated at the next step under mild conditions under the catalytic action of the catalyst, so that the reaction efficiency and selectivity in the oxidation process are improved, the conversion rate is improved, and the production cost is reduced.
The invention can lead the oxidation process of the 2-nitro-4-methylsulfonylbenzoic acid to be oxidized and generated in one step under mild conditions, has the characteristics of high conversion rate, high selectivity and environmental friendliness, and can be suitable for large-scale industrial production process.
Detailed Description
In order to make the technical solution of the present invention easier to understand, the technical solution of the present invention is now clearly and completely described by way of specific embodiments.
Example 1:
the catalyst system of the embodiment comprises a compound of two metals and an imine-containing compound, wherein the two metals are respectively Cu and Mn, and the compound of the two metals is an oxide of Cu and Mn; the imine-containing compound is N-hydroxyphthalimide; the Cu: mn: the molar ratio of the imine-containing compounds is 1:0.1:1.
the method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation of the embodiment comprises the following steps: (1) according to a molar ratio of Cu: mn: imine-containing compound =1:0.1: weighing two compounds of Cu and Mn and imine-containing compounds, and uniformly mixing to prepare a catalyst; (2) Dissolving 2-nitro-4-methylsulfonyl toluene in acetic acid with volume concentration of 50% to prepare a solution, adding a catalyst, stirring and heating; the dosage of the acetic acid is 2-nitro-4-methylsulfonyltoluene by weight: acetic acid =1:2; the dosage of the catalyst is 2-nitro-4-methylsulfonylbenzoic acid by weight: catalyst =1:0.08; (3) Slowly dripping peroxyacetic acid with volume concentration of 30 percent when the acetic acid solution of the 2-nitro-4-methylsulfonylbenzoic acid is heated to the required reaction temperature of 80 ℃; the amount of the peroxyacetic acid is 2-nitro-4-methylsulfonylbenzoic acid by weight: peroxyacetic acid =1:1.4; the dripping time of the peroxyacetic acid is 3 hours; (4) After the dropwise addition is finished, carrying out heat preservation and oxidation reaction for 3 hours at the reaction temperature of 80 ℃; (5) And after the reaction is finished, obtaining an oxidation reaction liquid, and carrying out post-treatment on the oxidation reaction liquid to obtain a finished product of the 2-nitro-4-methylsulfonylbenzoic acid.
Example 2:
the catalyst system of the embodiment comprises a compound of two metals and an imine-containing compound, wherein the two metals are respectively Cu and Mn, and the compound of the two metals is hydrochloride of Cu and Mn; the imine compound is N, N' -dihydroxy pyromellitic imine; the Cu: mn: the molar ratio of the imine compound is 1:1:10.
the method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation of the embodiment comprises the following steps: (1) according to a molar ratio of Cu: mn: imine-containing compound =1:1: weighing two compounds of Cu and Mn and an imine-containing compound, and uniformly mixing to prepare a catalyst; (2) Dissolving 2-nitro-4-methylsulfonyl toluene in acetic acid with volume concentration of 60% to prepare a solution, adding a catalyst, stirring and heating; the dosage of the acetic acid is 2-nitro-4-methylsulfonyltoluene by weight: acetic acid =1:4; the dosage of the catalyst is 2-nitro-4-methylsulfonylbenzoic acid by weight: catalyst =1:0.1; (3) Slowly dripping peroxyacetic acid with the volume concentration of 30 percent when the acetic acid solution of the 2-nitro-4-methylsulfonylbenzoic acid is heated to the required reaction temperature of 90 ℃; the amount of peroxyacetic acid used is 2-nitro-4-methylsulfonylbenzoic acid by weight: peroxyacetic acid =1:2; the dripping time of the peroxyacetic acid is 5 hours; (4) After the dropwise addition is finished, the temperature is kept at 90 ℃ for oxidation reaction for 2.5h; (5) And after the reaction is finished, obtaining an oxidation reaction liquid, and carrying out post-treatment on the oxidation reaction liquid to obtain a finished product of the 2-nitro-4-methylsulfonylbenzoic acid.
Example 3:
the catalyst system of the embodiment comprises a compound of two metals and an imine-containing compound, wherein the two metals are Cu and Mn respectively, and the compound of the two metals is a sulfate of Cu and Mn; the imine-containing compound is N-methoxy phthalimide; the Cu: mn: the molar ratio of the imine compound is 1:3:30.
the method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation of the embodiment comprises the following steps: (1) according to a molar ratio of Cu: mn: imine-containing compound =1:3:30, weighing two compounds of Cu and Mn and imine-containing compounds, and uniformly mixing to prepare a catalyst; (2) Dissolving 2-nitro-4-methylsulfonyl toluene in acetic acid with volume concentration of 70% to prepare a solution, adding a catalyst, stirring and heating; the dosage of the acetic acid is 2-nitro-4-methylsulfonyltoluene by weight: acetic acid =1:5; the dosage of the catalyst is 2-nitro-4-methylsulfonylbenzoic acid by weight: catalyst =1:0.15; (3) Slowly dripping peroxyacetic acid with volume concentration of 30 percent when the acetic acid solution of the 2-nitro-4-methylsulfonylbenzoic acid is heated to the required reaction temperature of 95 ℃; the amount of the peroxyacetic acid is 2-nitro-4-methylsulfonylbenzoic acid by weight: peroxyacetic acid =1:2.5; the dripping time of the peroxyacetic acid is 7 hours; (4) After the dropwise addition is finished, carrying out heat preservation and oxidation reaction for 2 hours at the reaction temperature of 95 ℃; (5) And after the reaction is finished, obtaining an oxidation reaction liquid, and carrying out post-treatment on the oxidation reaction liquid to obtain a finished product of the 2-nitro-4-methylsulfonylbenzoic acid.
Example 4:
the catalyst system of the embodiment comprises a compound of two metals and an imine-containing compound, wherein the two metals are Cu and Co respectively, and the compound of the two metals is a phosphate of Cu and Co; the imine-containing compound is N-hydroxyphthalimide; the Cu: co: the molar ratio of the imine compound is 1:5:50.
the method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation of the embodiment comprises the following steps: (1) according to a molar ratio of Cu: co: imine-containing compound =1:5:50, weighing two compounds of Cu and Co and imine-containing compounds, and uniformly mixing to prepare a catalyst; (2) Dissolving 2-nitro-4-methylsulfonyl toluene in acetic acid with volume concentration of 80% to prepare a solution, adding a catalyst, stirring and heating; the dosage of the acetic acid is 2-nitro-4-methylsulfonyltoluene by weight: acetic acid =1:6; the dosage of the catalyst is 2-nitro-4-methylsulfonylbenzoic acid by weight: catalyst =1:0.2; (3) Slowly dripping peroxyacetic acid with the volume concentration of 40 percent when the acetic acid solution of the 2-nitro-4-methylsulfonylbenzoic acid is heated to the required reaction temperature of 100 ℃; the amount of the peroxyacetic acid is 2-nitro-4-methylsulfonylbenzoic acid by weight: peroxyacetic acid =1:3; the dripping time of the peroxyacetic acid is 9 hours; (4) After the dropwise addition is finished, the temperature is kept at 100 ℃ for oxidation reaction for 1.8h; (5) And after the reaction is finished, obtaining an oxidation reaction liquid, and carrying out post-treatment on the oxidation reaction liquid to obtain a finished product of the 2-nitro-4-methylsulfonylbenzoic acid.
Example 5:
the catalyst system of the embodiment comprises compounds of two metals and imine-containing compounds, wherein the two metals are Cu and Co respectively, and the compounds of the two metals are acetates of Cu and Co; the imine compound is N, N' -dihydroxy pyromellitic imine; the Cu: co: the molar ratio of the imine compound is 1:10:80.
the method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation of the embodiment comprises the following steps: (1) according to a molar ratio of Cu: co: imine-containing compound =1:10:80, weighing two compounds of Cu and Co and an imine-containing compound, and uniformly mixing to prepare a catalyst; (2) Dissolving 2-nitro-4-methylsulfonyl toluene in acetic acid with volume concentration of 90% to prepare a solution, adding a catalyst, stirring and heating; the dosage of the acetic acid is 2-nitro-4-methylsulfonyltoluene by weight: acetic acid =1:8; the dosage of the catalyst is 2-nitro-4-methylsulfonylbenzoic acid by weight: catalyst =1:0.25; (3) Slowly dripping peracetic acid with volume concentration of 40% when the acetic acid solution of the 2-nitro-4-methylsulfonylbenzoic acid is heated to the required reaction temperature of 110 ℃; the amount of the peroxyacetic acid is 2-nitro-4-methylsulfonylbenzoic acid by weight: peroxyacetic acid =1:3.5; the dripping time of the peroxyacetic acid is 10 hours; (4) After the dropwise addition is finished, the temperature is kept at 110 ℃ for oxidation reaction for 1.5h; (5) And after the reaction is finished, obtaining an oxidation reaction liquid, and carrying out post-treatment on the oxidation reaction liquid to obtain a finished product of the 2-nitro-4-methylsulfonylbenzoic acid.
Example 6:
the catalyst system of the embodiment comprises a compound of two metals and an imine-containing compound, wherein the two metals are Cu and Co respectively, and the compound of the two metals is a carbonate of Cu and Co; the imine-containing compound is N-methoxy phthalimide; the Cu: co: the molar ratio of the imine compound is 1:15:100.
the method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation of the embodiment comprises the following steps: (1) according to a molar ratio of Cu: co: imine-containing compound =1:15:100, weighing two compounds of Cu and Co and imine-containing compounds, and uniformly mixing to prepare a catalyst; (2) Dissolving 2-nitro-4-methylsulfonyl toluene in acetic acid with volume concentration of 100% to prepare a solution, adding a catalyst, stirring and heating; the dosage of the acetic acid is 2-nitro-4-methylsulfonyl toluene by weight: acetic acid =1: 10; the dosage of the catalyst is 2-nitro-4-methylsulfonylbenzoic acid by weight: catalyst =1:0.3; (3) Slowly dripping peroxyacetic acid with the volume concentration of 40 percent when the acetic acid solution of the 2-nitro-4-methylsulfonylbenzoic acid is heated to the required reaction temperature of 118 ℃; the amount of the peroxyacetic acid is 2-nitro-4-methylsulfonylbenzoic acid by weight: peroxyacetic acid =1:4; the dripping time of the peracetic acid is 11 hours; (4) After the dropwise addition is finished, carrying out heat preservation and oxidation reaction for 3 hours at the reaction temperature of 118 ℃; (5) And after the reaction is finished, obtaining an oxidation reaction liquid, and carrying out post-treatment on the oxidation reaction liquid to obtain a finished product of the 2-nitro-4-methylsulfonylbenzoic acid.
The 2-nitro-4-methylsulfonyl toluene is used as a raw material, a catalytic system constructed by two metal compounds and an imine-containing compound is used for catalytic oxidation to prepare the 2-nitro-4-methylsulfonyl benzoic acid, and the yield is over 90 percent.
Table 1: the product index of the invention for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation
| Yield (%) | Purity (%) | |
| Example 1 | 90.1 | 99.2 |
| Example 2 | 90.5 | 99.0 |
| Example 3 | 91.0 | 99.3 |
| Example 4 | 90.0 | 99.0 |
| Example 5 | 91.3 | 99.1 |
| Example 6 | 90.6 | 99.2 |
It should be noted that the embodiments described herein are only some embodiments of the present invention, and not all implementations of the present invention, and the embodiments are only examples, which are only used to provide a more intuitive and clear understanding of the present invention, and are not intended to limit the technical solutions of the present invention. All other embodiments, as well as other simple substitutions and various changes to the technical solutions of the present invention, which can be made by those skilled in the art without inventive work, are within the scope of the present invention without departing from the spirit of the present invention.
Claims (10)
1. A catalyst system is characterized by comprising a compound containing two metals and an imine compound, wherein the two metals are Cu and Mn or Cu and Co respectively; the imine compound is one or more of N-hydroxyphthalimide, N' -dihydroxypyromellitic imine and N-methoxyphthalimide.
2. The catalyst system of claim 1, wherein the compound of the two metals is one or more of oxides, hydrochlorides, sulfates, phosphates, acetates, carbonates of Cu and Mn or Cu and Co or hydrates of the above salts.
3. The catalyst system of claim 1, wherein the Cu: mn: the molar ratio of the imine compound is 1: (0.1-15): (1-100); the Cu: co: the molar ratio of the imine compound is 1: (0.1-20): (1-100).
4. A method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation is characterized by comprising the following steps:
(1) Weighing two compounds of Cu and Mn or Cu and Co and an imine-containing compound, and uniformly mixing to prepare a catalyst;
(2) Dissolving 2-nitro-4-methylsulfonyl toluene in acetic acid to prepare a solution, adding a catalyst, stirring and heating;
(3) Slowly dripping peroxyacetic acid when the acetic acid solution of the 2-nitro-4-methylsulfonylbenzoic acid is raised to the required reaction temperature;
(4) After the dropwise addition is finished, preserving the temperature at the reaction temperature for oxidation reaction for a certain time;
(5) And after the reaction is finished, obtaining an oxidation reaction liquid, and carrying out post-treatment on the oxidation reaction liquid to obtain a finished product of the 2-nitro-4-methylsulfonylbenzoic acid.
5. The method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation with the catalyst system as claimed in claim 4, wherein the volume concentration of acetic acid used in step (2) is 50-100%, and the amount of acetic acid used is, by weight, 2-nitro-4-methylsulfonyltoluene: acetic acid =1: (2-10).
6. The method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation of the catalyst system according to claim 4, wherein the catalyst is used in the step (2) in an amount of 2-nitro-4-methylsulfonylbenzoic acid by weight: catalyst =1: (0.08-0.3).
7. The process for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation with a catalyst system according to claim 4, wherein the peroxyacetic acid used in step (3) has a volume concentration of 30 to 40%, and is used in an amount of 2-nitro-4-methylsulfonylbenzoic acid by weight: peroxyacetic acid =1: (1.4-4).
8. The method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation with the catalyst system as claimed in claim 4, wherein the peracetic acid is added in step (3) for 3 to 11 hours.
9. The method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation with the catalyst system as claimed in claim 4, wherein the reaction temperature in the step (3) and the step (4) is 80-118 ℃, and the temperature-maintaining oxidation reaction time in the step (4) is 1-3 h.
10. The method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation of the catalyst system as claimed in claim 4, wherein the post-treatment in step (5) comprises crude crystallization, alkali dissolution and acid precipitation, wherein the crude crystallization comprises dilution crystallization and filtration washing; the alkali dissolution comprises alkali adjustment and filtration; the acidification comprises acid adjustment and filtration washing.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6355842B1 (en) * | 1998-11-25 | 2002-03-12 | Dsm Fine Chemicals Austria Nfg Gmbh & Cokg | Process for the oxidation of substrates containing methyl, methylene or methine groups |
| CN1935376A (en) * | 2006-10-17 | 2007-03-28 | 郑州大学 | Catalyst and its use for synthesizing 4-nitro-3-methyl benzoic acid |
| CN104059001A (en) * | 2013-03-18 | 2014-09-24 | 华中师范大学 | Preparation method of o-nitro sulfuryl benzoic acid |
| CN104557640A (en) * | 2015-01-22 | 2015-04-29 | 武汉凯马仕精细化工有限公司 | Method for preparing 2-nitro-4-methylsulfuryl benzoic acid by molecular oxygen catalytic oxidation |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6355842B1 (en) * | 1998-11-25 | 2002-03-12 | Dsm Fine Chemicals Austria Nfg Gmbh & Cokg | Process for the oxidation of substrates containing methyl, methylene or methine groups |
| CN1935376A (en) * | 2006-10-17 | 2007-03-28 | 郑州大学 | Catalyst and its use for synthesizing 4-nitro-3-methyl benzoic acid |
| CN104059001A (en) * | 2013-03-18 | 2014-09-24 | 华中师范大学 | Preparation method of o-nitro sulfuryl benzoic acid |
| CN104557640A (en) * | 2015-01-22 | 2015-04-29 | 武汉凯马仕精细化工有限公司 | Method for preparing 2-nitro-4-methylsulfuryl benzoic acid by molecular oxygen catalytic oxidation |
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