CN114249675A - Preparation method of 2-nitro-4-methylsulfonylbenzoic acid - Google Patents
Preparation method of 2-nitro-4-methylsulfonylbenzoic acid Download PDFInfo
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- CN114249675A CN114249675A CN202011005177.2A CN202011005177A CN114249675A CN 114249675 A CN114249675 A CN 114249675A CN 202011005177 A CN202011005177 A CN 202011005177A CN 114249675 A CN114249675 A CN 114249675A
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- methylsulfonyltoluene
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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 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 29
- 150000001875 compounds 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 25
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 9
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052799 carbon Chemical group 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 150000007933 aliphatic carboxylic acids Chemical group 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical group [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical group [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000004304 potassium nitrite Substances 0.000 claims description 3
- 235000010289 potassium nitrite Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 235000010288 sodium nitrite Nutrition 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000001819 mass spectrum Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- KTWCUGUUDHJVIH-UHFFFAOYSA-N 2-hydroxybenzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(N(O)C2=O)=O)=C3C2=CC=CC3=C1 KTWCUGUUDHJVIH-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of synthesis, and discloses a preparation method of 2-nitro-4-methylsulfonylbenzoic acid. The method comprises the following steps: the method comprises the step of contacting a mixture containing an organic solvent, 2-nitro-4-methylsulfonyl toluene, a catalyst and a cocatalyst with oxygen-containing gas, wherein the catalyst is one or more of compounds with structures shown in formulas (I) to (III), the cocatalyst is one or more of nitric acid, nitrate and nitrite, and R in the formula1‑R12Each independently selected from hydrogen or alkyl with 1-3 carbon atoms, and X is nitrogen atom or carbon atom. The method has the advantages of low cost, high yield and less three wastes, and is particularly suitable for industrial production.
Description
Technical Field
The invention relates to the field of synthesis, and particularly relates to a preparation method of 2-nitro-4-methylsulfonylbenzoic acid.
Background
2-nitro-4-methylsulfonylbenzoic acid is widely used for synthesis of dyes, medicines and pesticides, and the preparation method thereof is receiving wide attention.
The reported synthesis methods mostly use 2-nitro-4-methylsulfonyl toluene as a raw material, and 2-nitro-4-methylsulfonyl benzoic acid is obtained by oxidation, wherein the oxidation method mainly comprises a chemical oxidation method and an air oxidation method.
At present, chemical oxidation is mainly used in industrial production, and BASF corporation (CN1038584C) discloses a method for oxidizing by nitric acid and air in the presence of vanadium or cobalt compounds with sulfuric acid as a solvent, wherein the method has low raw material cost and high yield, but uses high-concentration mixed acid and a highly toxic catalyst, and is safe and environmentally-friendly. The key point of the air oxidation method lies in the selection of a catalyst, and CN103787934A discloses a method which takes heteropoly acid-transition metal-halide as a catalytic system and takes low-grade saturated carboxylic acid as a solvent, and the yield is 90-92%; CN104844484A discloses a synthesis method using water, methanol, ethanol and sodium hydroxide solution with certain concentration as solvent and metal phthalocyanine or substituted metal phthalocyanine as catalyst, with yield of 12.9-94.1%. The air oxidation method is relatively clean and environment-friendly, but has the problems of high catalyst cost, low reaction yield and the like.
In a comprehensive view, the existing synthesis method for preparing 2-nitro-4-methylsulfonylbenzoic acid by a chemical oxidation method has the defects of large amount of three wastes and poor safety, and is not suitable for the current production environment. The research of the air oxidation method has been greatly advanced, but a cheaper, low-toxicity and high-efficiency catalyst is still to be searched.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide the preparation method of the 2-nitro-4-methylsulfonylbenzoic acid, which has the advantages of low cost, high yield and less three wastes and is particularly suitable for industrial production.
In order to achieve the above object, the present invention provides a method for preparing 2-nitro-4-methylsulfonylbenzoic acid, which comprises: a step of contacting a mixture containing an organic solvent, 2-nitro-4-methylsulfonyltoluene, a catalyst and a cocatalyst with an oxygen-containing gas,
wherein the catalyst is one or more of compounds with structures shown in formulas (I) to (III), the cocatalyst is one or more of nitric acid, nitrate and nitrite,
in the formula, R1-R12Each independently selected from hydrogen or alkyl with 1-3 carbon atoms, and X is nitrogen atom or carbon atom.
Preferably, R1-R12Each independently selected from hydrogen and X is a carbon atom.
Preferably, the organic solvent is an aliphatic carboxylic acid.
Preferably, the aliphatic carboxylic acid is formic acid and/or acetic acid.
Preferably, the nitrate is sodium nitrate and/or potassium nitrate.
Preferably, the nitrite is sodium nitrite and/or potassium nitrite.
Preferably, the catalyst is selected from one or more compounds with the structures shown in formula (I-1), formula (II-1) and formula (III-1),
preferably, the amount of the organic solvent is 1-10 times of the weight of the 2-nitro-4-methylsulfonyltoluene.
Preferably, the molar ratio of the 2-nitro-4-methylsulfonyltoluene to the catalyst is 1: 0.1-0.5.
Preferably, the molar ratio of the 2-nitro-4-methylsulfonyltoluene to the cocatalyst is 1: 0.1-0.2.
Preferably, the oxygen-containing gas is oxygen.
Preferably, the conditions of the contacting include: the contact temperature is 120-180 ℃, the contact time is actually 2-12 hours, and the oxygen pressure is 0.2-2 Mpa.
Preferably, the method further comprises the steps of cooling the reaction product and performing solid-liquid separation.
Through the technical scheme, the invention can provide the preparation method of the 2-nitro-4-methylsulfonylbenzoic acid, which has the advantages of low cost, high yield and less three wastes and is particularly suitable for industrial production.
Moreover, the method has extremely simple post-treatment, only needs to cool the reaction product and then carry out solid-liquid separation, greatly simplifies the operation, reduces the cost and is suitable for industrial production.
Drawings
FIG. 1 is a mass spectrum of a compound of the formula (I-1) prepared in preparation example 1.
FIG. 2 is a nuclear magnetic spectrum of the compound of the formula (I-1) prepared in preparation example 1.
FIG. 3 is a mass spectrum of the compound of the formula (II-1) prepared in preparation example 2.
FIG. 4 is a nuclear magnetic spectrum of the compound of the formula (II-1) prepared in preparation example 2.
FIG. 5 is a mass spectrum of the compound of the formula (III-1) prepared in preparation example 3.
FIG. 6 is a nuclear magnetic spectrum of the compound of the formula (III-1) prepared in preparation example 3.
FIG. 7 is a mass spectrum of 2-nitro-4-methylsulfonylbenzoic acid prepared in example 1.
FIG. 8 is a nuclear magnetic spectrum of 2-nitro-4-methylsulfonylbenzoic acid prepared in example 1.
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: a step of contacting a mixture containing an organic solvent, 2-nitro-4-methylsulfonyltoluene, a catalyst and a cocatalyst with oxygen-containing gas, wherein the catalyst is one or more of compounds with structures shown in formulas (I) to (III), and the cocatalyst is one or more of nitric acid, nitrate and nitrite,
in the formula, R1-R12Each independently selected from hydrogen or alkyl with 1-3 carbon atoms, and X is nitrogen atom or carbon atom.
In the present invention, examples of the alkyl group having 1 to 3 carbon atoms include: methyl, ethyl, n-propyl, isopropyl and the like.
Preferably, R is1-R12Each independently selected from hydrogen, X is a carbon atom; more preferably, the catalyst is selected from one or more compounds having the structure shown in formula (I-1), formula (II-1) and formula (III-1),
according to the invention, the method of the invention comprises: a step of contacting a mixture containing an organic solvent, 2-nitro-4-methylsulfonyltoluene, a catalyst and a cocatalyst with an oxygen-containing gas. The organic solvent is used for dissolving reactants, so that the reaction is rapidly carried out. The organic solvent is preferably an aliphatic carboxylic acid.
As the aliphatic carboxylic acid, only 2-nitro-4-methylsulfonyltoluene is preferably dissolved, and formic acid and/or acetic acid may be mentioned, for example. In addition, the amount of the organic solvent may be selected according to the amount of 2-nitro-4-methylsulfonyltoluene, preferably, the amount of the organic solvent is 1 to 10 times based on the weight of 2-nitro-4-methylsulfonyltoluene, and more preferably, the amount of the organic solvent is 5 to 10 times based on the weight of 2-nitro-4-methylsulfonyltoluene.
According to the present invention, the amount of the catalyst may be selected according to the amount of 2-nitro-4-methylsulfonyltoluene, for example, the molar ratio of 2-nitro-4-methylsulfonyltoluene to the catalyst is 1: 0.1-0.5; preferably, the molar ratio of the 2-nitro-4-methylsulfonyltoluene to the catalyst is 1: 0.1-0.2.
According to the invention, the amount of the cocatalyst can be selected according to the amount of the 2-nitro-4-methylsulfonyltoluene, for example, the molar ratio of the 2-nitro-4-methylsulfonyltoluene to the cocatalyst is 1: 0.1-0.5; preferably, the molar ratio of the 2-nitro-4-methylsulfonyltoluene to the cocatalyst is 1: 0.1-0.2.
In the present invention, the co-catalyst is one or more of nitric acid, nitrate and nitrite. Examples of the nitrate include: sodium nitrate and/or potassium nitrate, and the like. Examples of the nitrite include: sodium nitrite and/or potassium nitrite, and the like.
According to the present invention, the oxygen-containing gas is various gases generally used in the art for oxidation reactions, and may be, for example, oxygen or air, preferably oxygen.
According to the present invention, preferably, the conditions of the contacting include: the contact temperature is 120-180 ℃, the actual contact time is 2-12 hours, and the oxygen pressure is 0.2-2 Mpa; more preferably, the conditions of the contacting include: the contact temperature is 140 ℃ and 160 ℃, the contact time is actually 4-8 hours, and the oxygen pressure is 1-1.5 Mpa.
According to the invention, after the reaction is finished, the target compound (2-nitro-4-methylsulfonylbenzoic acid) can be obtained with high yield and high purity only by cooling the reaction product and then carrying out solid-liquid separation, and the method is extremely simple in post-treatment, greatly simplifies the operation, reduces the cost and is very suitable for industrial production.
The temperature after the temperature reduction is preferably room temperature, and may be, for example, 10 to 40 ℃ and preferably 15 to 30 ℃.
The present invention will be described in detail below by way of examples, but the present invention is not limited to the following examples.
Preparation example 1
Dissolving 16.3g (0.1mol) of N-hydroxyphthalimide in 30ml of acetic acid, heating to 40 ℃, dropwise adding 15.3g (0.15mol) of acetic anhydride, stirring for 2h, allowing the central control sampling raw material to disappear, cooling to 5 ℃, filtering, and drying a filter cake to obtain 17.5g of the compound with the structure shown in the formula (I-1), wherein the mass spectrum and nuclear magnetism data of the compound are shown in figures 1 and 2.
Preparation example 2
Dissolving 21.3g (0.1mol) of N-hydroxy-1, 8-naphthalimide in 30ml of acetic acid, heating to 40 ℃, dropwise adding 15.3g (0.15mol) of acetic anhydride, stirring for 2h, allowing the central control sampling raw material to disappear, cooling to 5 ℃, filtering, and drying a filter cake to obtain 24.6g of the compound with the structure shown in the formula (II-1), wherein the mass spectrum and nuclear magnetism data of the compound are shown in figures 3 and 4.
Preparation example 3
Dissolving 11.5g (0.1mol) of N-hydroxysuccinimide in 20ml of acetic acid, heating to 40 ℃, dropwise adding 15.3g (0.15mol) of acetic anhydride, stirring for 2h, allowing the central control sampling raw material to disappear, cooling to 5 ℃, filtering, and drying the filter cake to obtain 14.2g of the compound with the structure shown in the formula (III-1). The mass spectra and nuclear magnetic data are shown in FIGS. 5 and 6.
Example 1
40g of acetic acid, 4.3g of 2-nitro-4-methylsulfonyltoluene, 0.4g of a compound shown in the formula (I-1) and 0.4g of fuming nitric acid are added into a 100ml autoclave, the temperature is raised to 150 ℃, oxygen is introduced until the pressure in the autoclave is 1.0MPa, and the temperature is kept for 5 hours. After the reaction is finished, the temperature is reduced to 25 ℃, the mixture is filtered and dried for 3 hours at the temperature of 50 ℃, and the 2-nitro-4-methylsulfonylbenzoic acid is obtained, the content is 98.5 percent by weight, and the yield is 95.6 percent. The mass spectra and nuclear magnetic data are shown in FIGS. 7 and 8.
Example 2
40g of acetic acid, 4.3g of 2-nitro-4-methylsulfonyltoluene, 0.8g of the compound shown in the formula (I-1) and 0.4g of fuming nitric acid are added into a 100ml autoclave, the temperature is raised to 150 ℃, oxygen is introduced until the pressure in the autoclave is 1.5MPa, and the temperature is kept for 4 hours. After the reaction, the temperature is reduced to 25 ℃, the mixture is filtered and dried for 3 hours at 50 ℃ to obtain the 2-nitro-4-methylsulfonylbenzoic acid, the content is 98.6 percent by weight, and the yield is 95.8 percent.
Example 3
40g of acetic acid, 4.3g of 2-nitro-4-methylsulfonyltoluene, 0.6g of the compound shown in the formula (I-1) and 0.8g of fuming nitric acid are added into a 100ml autoclave, the temperature is raised to 150 ℃, oxygen is introduced until the pressure in the autoclave is 1.2MPa, and the temperature is kept for 6 hours. After the reaction is finished, the temperature is reduced to 25 ℃, the mixture is filtered and dried for 3 hours at the temperature of 50 ℃, and the 2-nitro-4-methylsulfonylbenzoic acid is obtained, the content is 98.5 percent by weight, and the yield is 95.6 percent.
Example 4
The procedure was carried out as in example 1, except that the compound having the structure represented by the formula (I-1) was replaced with the compound having the structure represented by the formula (II-1) in the same molar amount to obtain 2-nitro-4-methylsulfonylbenzoic acid in a content of 98.4% by weight in a yield of 94.4%.
Example 5
The procedure was carried out as in example 1, except that the compound having the structure represented by the formula (I-1) was replaced with the compound having the structure represented by the formula (III-1) in the same molar amount to obtain 2-nitro-4-methylsulfonylbenzoic acid in a content of 98.5% by weight in a yield of 94.3%.
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: a step of contacting a mixture containing an organic solvent, 2-nitro-4-methylsulfonyltoluene, a catalyst and a cocatalyst with an oxygen-containing gas,
wherein the catalyst is one or more of compounds with structures shown in formulas (I) to (III), the cocatalyst is one or more of nitric acid, nitrate and nitrite,
in the formula, R1-R12Each independently selected from hydrogen or alkyl with 1-3 carbon atoms, and X is nitrogen atom or carbon atom.
2. The method of claim 1, wherein R1-R12Each independently selected from hydrogen and X is a carbon atom.
3. The method of claim 1, wherein the organic solvent is an aliphatic carboxylic acid;
preferably, the aliphatic carboxylic acid is formic acid and/or acetic acid.
4. The method of claim 1, wherein the nitrate salt is sodium nitrate and/or potassium nitrate;
preferably, the nitrite is sodium nitrite and/or potassium nitrite.
5. The method according to any one of claims 1 to 4, wherein the catalyst is selected from one or more compounds having a structure represented by formula (I-1), formula (II-1) and formula (III-1),
6. the method according to any one of claims 1 to 4, wherein the organic solvent is used in an amount of 1 to 10 times based on the weight of 2-nitro-4-methylsulfonyltoluene.
7. The process according to any one of claims 1 to 4, wherein the molar ratio of 2-nitro-4-methylsulfonyltoluene to the catalyst is 1: 0.1-0.5.
8. The process according to any one of claims 1 to 4, wherein the molar ratio of 2-nitro-4-methylsulfonyltoluene to the cocatalyst is 1: 0.1-0.2.
9. The method of any of claims 1-4, wherein the oxygen-containing gas is oxygen;
preferably, the conditions of the contacting include: the contact temperature is 120-180 ℃, the contact time is actually 2-12 hours, and the oxygen pressure is 0.2-2 Mpa.
10. The process of claim 9, further comprising the step of cooling the reaction product and performing a solid-liquid separation.
Priority Applications (1)
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