CN104557640A - Method for preparing 2-nitro-4-methylsulfuryl benzoic acid by molecular oxygen catalytic oxidation - Google Patents
Method for preparing 2-nitro-4-methylsulfuryl benzoic acid by molecular oxygen catalytic oxidation Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 49
- 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 32
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 31
- 230000003647 oxidation Effects 0.000 title claims abstract description 28
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910001882 dioxygen Inorganic materials 0.000 title claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 17
- 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 26
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 150000001868 cobalt Chemical class 0.000 claims abstract description 11
- 150000002696 manganese Chemical class 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000002798 polar solvent Substances 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 24
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical group C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 claims description 11
- 229940011182 cobalt acetate Drugs 0.000 claims description 9
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 9
- 229940071125 manganese acetate Drugs 0.000 claims description 8
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- -1 nitroxide free radical Chemical class 0.000 claims description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 claims description 3
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical group CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 3
- 235000010288 sodium nitrite Nutrition 0.000 claims description 3
- VTURQLGQZRYNSS-UHFFFAOYSA-N 2-hydroxy-4-(pyridin-3-ylmethyl)isoindole-1,3-dione Chemical compound ON1C(C=2C(C1=O)=C(C=CC=2)CC=1C=NC=CC=1)=O VTURQLGQZRYNSS-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical group [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- KDMCQAXHWIEEDE-UHFFFAOYSA-L cobalt(2+);7,7-dimethyloctanoate Chemical compound [Co+2].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O KDMCQAXHWIEEDE-UHFFFAOYSA-L 0.000 claims description 2
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 24
- 239000002904 solvent Substances 0.000 abstract description 11
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- 238000005260 corrosion Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000007800 oxidant agent Substances 0.000 abstract description 7
- 230000009471 action Effects 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 239000012043 crude product Substances 0.000 description 11
- 238000001514 detection method Methods 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000007865 diluting Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
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- 238000007670 refining Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- INZUQGFQRYAKQQ-UHFFFAOYSA-N 2-acetylisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(C(=O)C)C(=O)C2=C1 INZUQGFQRYAKQQ-UHFFFAOYSA-N 0.000 description 3
- 239000005578 Mesotrione Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 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 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 229940016409 methylsulfonylmethane Drugs 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater 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
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- 108091006149 Electron carriers Proteins 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- TYGDMAQFSSHPRP-UHFFFAOYSA-N acetaldehyde;acetic acid Chemical compound CC=O.CC(O)=O TYGDMAQFSSHPRP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 235000005822 corn Nutrition 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a new process for preparing 2-nitro-4-methylsulfuryl benzoic acid from o-nitro-p-methylsulfuryl toluene by molecular oxygen catalytic oxidation. By using an organic polar solvent as a solvent, cobalt salt and manganese salt as a metal catalyst and molecular oxygen as an oxidizer, o-nitro-p-methylsulfuryl toluene is catalytically oxidized into the 2-nitro-4-methylsulfuryl benzoic acid under the actions of a nitrogen-oxygen free-radical initiator and an accelerator. The process has the advantages of low relative environmental pollution, low equipment corrosion and high controllability, and has industrial application value.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation of molecular oxygen.
Background
2-Nitro-4-Methylsulfonylbenzoic Acid, also known as O-Nitro-P-Methylsulfonylbenzoic Acid, having the name of 2-Nitro-4-merhylulfonylbenzoic Acid or O-Nitro-P-Methylsulfobenzic Acid (NMSBA for short), and having the molecular formula of C8H7NO6S, molecular weight of 245.21, white or light yellow crystal powder at normal temperature.
2-nitro-4-methylsulfonylbenzoic acid is an important chemical raw material, is widely applied to the production of pesticides, medicines and dyes, and is an important intermediate for synthesizing mesotrione particularly in the aspect of pesticides. The mesotrione is a triketone herbicide developed by Zeneca agricultural chemical company, is a special herbicide for corn fields, and has been quite successful at home and abroad due to the characteristics of wide weed control spectrum, high activity, strong mixability, low toxicity, environmental friendliness, flexible use and the like. The existing synthesis process of 2-nitro-4-methylsulfonylbenzoic acid is incomplete, so that the development of the mesotrione in China is greatly limited, and the research on the synthesis process has wide application prospect.
The preparation of 2-nitro-4-methylsulfonylbenzoic acid can be prepared by oxidation of o-nitro-p-methylsulfonyl toluene:
at present, a plurality of reports on the preparation technology of synthesizing the 2-nitro-4-methylsulfonylbenzoic acid from o-nitro-p-methylsulfonyltoluene include acidic oxidation processes of sodium dichromate, potassium permanganate, nitric acid, persulfuric acid or ozone, and catalytic oxidation alkaline oxidation processes of sodium hypochlorite, hydrogen peroxide and metalloporphyrin. However, the mainstream process of the current domestic and foreign industrial devices is a sulfuric acid solvent and a nitric acid oxidation process under the condition of a vanadium catalyst, and other processes are reported a lot, so that most of the processes lack industrial application value, and the development of the industry is seriously influenced by the heavy pollution, heavy corrosivity and high risk of the nitric acid oxidation process.
U.S. Pat. No. 5,5424,481 (CN1090843) reports a method for preparing 2-nitro-4-methylsulfonylbenzoic acid by nitric acid oxidation, wherein 70% sulfuric acid solvent is used, vanadium pentoxide catalyst and o-nitro-p-methylsulfonylbenzoic acid are added, 65% nitric acid is dropwise added at 145 ℃, air is used as an auxiliary oxidant to carry out oxidation reaction, and the reaction yield is 83%. The method has the problems that the corrosion to synthesis equipment is very strong at the temperature of 145 ℃, 70% sulfuric acid and nitric acid, sulfuric acid tail acid is discharged in the process, and nitric oxide yellow smoke is recycled and absorbed, which brings a plurality of problems to the production environment, the three-waste treatment and the equipment corrosion prevention.
US patent US5591890 reports a molecular oxygen oxidation process under acetic acid solvent conditions, which uses acetic acid as solvent, cobalt acetate as catalyst, reaction temperature 100 ℃, oxygen introduction to 62bar, slow pressing of acetaldehyde-acetic acid mixture as initiator for oxidation reaction, and which has problems of corrosion to equipment under acetic acid solvent conditions at 62bar pressure and corresponding safety problems, requiring high equipment investment and safety investment, and high process safety risk.
The Chinese patent CN101177369A reports an ozone-nitric acid combined oxidation process, and the method is promoted in the patent CN1090843, does not effectively solve the problems of waste acid, yellow smoke of oxynitride and equipment corrosion, and also has the problem of ozone utilization rate under the high-temperature condition.
Chinese patent CN102329256A discloses a catalytic oxidation technique using metalloporphyrin and molecular oxygen in methanol solvent under alkaline condition, which has the characteristics of cleanness, no pollution, mild reaction and high safety, but is easy to couple under alkaline condition, has many impurities, poor selectivity, low process yield, high production cost of product, has no economic advantages, and can not be used as an industrial application technique.
Patents WO2004058698a1, WO2007099450a2, CN101503383A and CN102584650A disclose methods for catalytically oxidizing o-nitro-p-methylsulfonylmethane to 2-nitro-4-methylsulfonylbenzoic acid in sulfuric acid by using hydrogen peroxide as an oxidant, which is a green solvent and oxidant, but the methods have the disadvantages of large hydrogen peroxide consumption, high cost, low yield, high risk and the like.
Chinese patent CN103787934A discloses a method for catalytic oxidation of o-nitro-p-methylsulfonyl methyl to 2-nitro-4-methylsulfonylbenzoic acid under the action of a multi-element homogeneous catalysis system composed of heteropoly acid-transition metal-halide, which does not use fuming sulfuric acid, reduces the operation risk, reduces corrosion, eliminates the pollution of nitrogen oxide waste gas generated by nitric acid reduction, can be recycled, reduces wastewater pollution, and reduces production cost, but the product produced by the method has poor quality and low purity, increases the operability of the process, and the heteropoly acid used in the method contains phosphorus element, which can cause phosphorus pollution.
Disclosure of Invention
The invention aims to provide a new process for oxidizing o-nitro-p-methylsulfonyl toluene into 2-nitro-4-methylsulfonylbenzoic acid by molecular oxygen catalysis, which comprises the following steps: organic polar solvent is used as solvent, cobalt salt and manganese salt are used as metal catalyst, molecular oxygen is used as oxidant, and o-nitro-p-methylsulfonyl methyl is catalyzed and oxidized into 2-nitro-4-methylsulfonyl benzoic acid under the action of nitroxide free radical initiator and accelerator. The process has the advantages of less environmental pollution, light equipment corrosion, strong process controllability and industrial application value.
The chemical mechanism of the present invention is N-hydroxyphthalimide (NHPI) and its analogs, such as: n-hydroxyphthalimide, N, N' -dihydroxypyromellimide, N-acetoxynaphthalimide have been used as effective electron carriers for electrochemical oxidation, and because O-H bonds in NHPI are easy to be homolytic to generate free radicals-N-hydroxyphthalimide free radicals which are easy to deprive H from C-H bonds in organic reaction substrates to enable the substrates to be homolytic to generate carbon free radicals, the free radical chain reaction is initiated. As a free radical initiator, NHPI generates a single electron free radical intermediate PINO with the help of oxygen and other promoters, and is widely applied to the molecular oxygen oxidation reaction of aromatic hydrocarbon, alkane, alkene, alcohol, ether, amine and aromatic heterocyclic compounds. The 2-nitro-4-methylsulfonylbenzoic acid is prepared by using NHPI initiator and cocatalyst and molecular oxygen to catalyze and oxidize o-nitro-p-methylsulfonyl toluene.
The invention is realized by the following modes: a method for preparing 2-nitro-4-methylsulfonylbenzoic acid by molecular oxygen catalytic oxidation is characterized by comprising the following steps: in a reactor, taking o-nitro-p-methylsulfonyl toluene as a raw material, taking a polar solvent, cobalt salt and manganese salt as metal catalysts, and then adding a nitroxide free radical initiator and an accelerator to oxidize the o-nitro-p-methylsulfonyl toluene into 2-nitro-4-methylsulfonyl benzoic acid; wherein,
the cobalt salt is cobalt naphthenate, cobalt nitrate, cobalt bromide, cobalt neodecanoate or cobalt acetate and the like, and cobalt acetate or cobalt naphthenate is preferred;
the manganese salt is manganese dioxide, manganese acetate, manganese bromide, manganese chloride or manganese hydroxide and the like, preferably manganese acetate or manganese bromide;
the accelerant is acetaldehyde, nitrogen dioxide, sodium nitrite or nitrous acid and the like.
The initiator is N-hydroxyphthalimide, N' -dihydroxypyromellitic imide, N-acetoxynaphthalimide, N-hydroxynaphthalimide or 3-picolyl-N-hydroxyphthalimide, etc., preferably N-hydroxyphthalimide or N-acetylphthalimide.
Preferably, the gas/liquid volume flow ratio in the reactor is 1: 1-1: 2, the mass concentration of o-nitro-p-methylsulfonyl toluene in the reactor is 5-15%, the mass concentration of cobalt salt in the reactor is 0.1-1.0%, the mass concentration of manganese salt in the reactor is 0.1-1.0%, the mass concentration of an accelerator in the reactor is 0.05-0.8%, and the mass concentration of an initiator in the reactor is 0.1-1.5%.
Preferably, the mass concentration of o-nitro-p-methylsulfonyl toluene in the reactor is 6-10%.
Preferably, the mass concentration of the accelerator in the reactor is 0.1-0.5%.
Preferably, the mass concentration of the initiator in the reactor is 0.5-1.0%.
Preferably, the cobalt salt and the manganese salt in the reactor are 1-10% of the o-nitro-p-methylsulfonyl toluene in the reactor by mass.
Preferably, the reaction temperature in the reactor is 100-250 ℃, the optimal temperature value is 180 ℃, the reaction pressure is 0-3 MPa, and the reaction time is 3-20 hours.
Preferably, the reactor is a stainless steel polytetrafluoroethylene high-pressure reactor.
Preferably, the polar solvent is acetic acid, acetonitrile or ethyl acetate, etc., preferably acetic acid.
Compared with the existing preparation method of 2-nitro-4-methylsulfonylbenzoic acid, the preparation method has the following advantages that the organic polar solvent is used as a solvent, the cobalt salt and the manganese salt are used as metal catalysts, molecular oxygen is used as an oxidant, and the o-nitro-p-methylsulfonylmethane is catalytically oxidized into the 2-nitro-4-methylsulfonylbenzoic acid under the action of a nitroxide free radical initiator and an accelerator:
(1) the method is green and environment-friendly, abandons the nitric acid oxidation process, does not use sulfuric acid as a solvent and nitric acid as an oxidant, avoids a large amount of sulfuric acid waste water to be discharged into the environment, reduces the corrosion to process equipment, and eliminates the pollution of oxynitride waste gas to the atmosphere; the use of a catalyst containing phosphorus and vanadium is avoided, and phosphorus pollution and the harm of heavy metal vanadium to the soil water body are avoided;
(2) the production cost is low. The method adopts cheap and easily available oxygen for oxidation, has mild reaction conditions, short process flow, simple operation and low consumption of used chemical substances, greatly reduces the raw materials and production cost, and has obvious economic advantages;
(3) the product has good quality and high purity. Compared with other oxidation processes, the content of the product in the crude product produced by the process is over 99 percent, the conversion rate can reach 94-97 percent, the selectivity can reach 90-92 percent, and the yield can reach 67-73 percent.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1
Adding 100mL of acetic acid, 1.2g of N-hydroxyphthalimide and 0.2g of accelerator acetaldehyde into a 250mL stainless steel lining tetrafluoro high-pressure reactor, adding 1g of cobalt acetate and 0.8g of manganese acetate metal catalyst, adding 10g of 2-nitro-4-methylsulfonyl toluene raw material, installing a stirring device, a thermometer and a rotating speed tester on the reactor, covering a kettle cover for sealing, starting stirring, adjusting the stirring rotating speed to 150r/min, replacing gas in the kettle with oxygen for 2-3 times, heating to 150 ℃, pressurizing to 1.2MPa, carrying out heat preservation reaction for 16 hours, cooling the reactor to room temperature after the detection reaction is finished, decompressing, diluting with 500mL of water, filtering to obtain a crude product, carrying out liquid phase detection analysis, wherein the conversion rate of the 2-nitro-4-methylsulfonyl toluene is 96%, the selectivity is 90%, then carrying out refining separation and purification procedures, 7.7g of the product is obtained, the content of the product in the crude product is 99.2 percent, and the yield is 68 percent.
Example 2
Adding 100mL of acetic acid, 0.5 gNN-hydroxyphthalimide and 0.1g of accelerant sodium nitrite into a 250mL stainless steel lining tetrafluoro high-pressure reactor, then adding 0.3g of cobalt acetate and 0.2g of manganese acetate catalyst, adding 6g of 2-nitro-4-methylsulfonyl toluene raw material, installing a stirring device, a thermometer and a rotating speed tester on the reactor, covering a kettle cover for sealing, starting stirring, adjusting the stirring rotating speed to 120r/min, replacing gas in the kettle with oxygen for 2-3 times, then heating to 180 ℃, pressurizing to 1.2MPa, preserving heat for reacting for 18 hours, cooling the reactor to room temperature after the detection reaction is finished, decompressing, diluting with 600mL of water, filtering to obtain a crude product, obtaining the 2-nitro-4-methylsulfonyl toluene with the conversion rate of 95% and the selectivity of 90% through liquid phase detection analysis, then performing refining separation and purification procedures, 4g of the product is obtained, the content of the product in the crude product is 99.1 percent, and the yield is 72 percent.
Example 3
Adding 120mL of acetic acid, 0.8g of N-acetylphthalimide and 0.5g of accelerator acetaldehyde into a 250mL stainless steel lining tetrafluoro high-pressure reactor, adding 1.2g of cobalt acetate and 1g of manganese acetate metal catalyst, adding 15g of 2-nitro-4-methylsulfonyl toluene raw material, installing a stirring device, a thermometer and a rotating speed tester on the reactor, covering a kettle cover for sealing, starting stirring, adjusting the stirring rotating speed to 150r/min, replacing gas in the kettle with oxygen for 2-3 times, heating to 150 ℃, pressurizing to 1.0MPa, carrying out heat preservation reaction for 16 hours, cooling the reactor to room temperature after the detection reaction is finished, decompressing, diluting with 500mL of water, filtering to obtain a crude product, carrying out liquid phase detection analysis, wherein the conversion rate of the 2-nitro-4-methylsulfonyl toluene is 97%, the selectivity is 92%, then carrying out refining separation purification procedures, 11.9g of the product was obtained, the content of the product in the crude product was 99.5%, and the yield was 70%.
Example 4
Adding 100mL of acetic acid, 0.7g of N-acetylphthalimide and 0.3g of accelerator acetaldehyde into a 250mL stainless steel lining tetrafluoro high-pressure reactor, adding 0.8g of cobalt acetate and 0.6g of manganese acetate metal catalyst, adding 12g of 2-nitro-4-methylsulfonyl toluene raw material, installing a stirring device, a thermometer and a rotating speed tester on the reactor, covering a kettle cover for sealing, starting stirring, adjusting the stirring rotating speed to 120r/min, replacing gas in the kettle with oxygen for 2-3 times, heating to 170 ℃, pressurizing to 1.5MPa, carrying out heat preservation reaction for 16 hours, cooling the reactor to room temperature after the detection reaction is finished, decompressing, diluting with 500mL of water, filtering to obtain a crude product, carrying out liquid phase detection analysis, wherein the conversion rate of the 2-nitro-4-methylsulfonyl toluene is 95%, the selectivity is 90%, then carrying out refining separation and purification procedures, 9.2g of the product is obtained, the content of the product in the crude product is 99%, and the yield is 67%.
Example 5
Adding 250mL of acetic acid, 2g of N-hydroxyphthalimide and 0.5g of accelerator acetaldehyde into a 500mL stainless steel lining tetrafluoro high-pressure reactor, then adding 1g of cobalt acetate and 0.8g of manganese acetate metal catalyst, adding 20g of 2-nitro-4-methylsulfonyl toluene raw material, installing a stirring device and a thermometer on the reactor, measuring the rotating speed by a rotating speed tester, covering a kettle cover, sealing, starting stirring, adjusting the stirring rotating speed to 120r/min, replacing the gas in the kettle with oxygen for 2-3 times, then heating to 180 ℃, pressurizing to 1.2MPa, carrying out heat preservation reaction for 16 hours, cooling the reactor to room temperature after the detection reaction is finished, decompressing, diluting with 300mL of water, filtering to obtain a crude product, obtaining the 2-nitro-4-methylsulfonyl toluene with the conversion rate of 94% and the selectivity of 90% through liquid phase detection and analysis, then carrying out refining, separation and purification procedures, 16.6g of the product was obtained, the content of the product in the crude product was 99.4%, and the yield was 73%.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-described embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (9)
1. A method for preparing 2-nitro-4-methylsulfonylbenzoic acid by molecular oxygen catalytic oxidation is characterized by comprising the following steps: in a reactor, taking o-nitro-p-methylsulfonyl toluene as a raw material, taking a polar solvent, cobalt salt and manganese salt as metal catalysts, and then adding a nitroxide free radical initiator and an accelerator to oxidize the o-nitro-p-methylsulfonyl toluene into 2-nitro-4-methylsulfonyl benzoic acid; wherein,
the cobalt salt is cobalt naphthenate, cobalt nitrate, cobalt bromide, cobalt neodecanoate or cobalt acetate;
the manganese salt is manganese dioxide, manganese acetate, manganese bromide, manganese chloride or manganese hydroxide;
the accelerant is acetaldehyde, nitrogen dioxide, sodium nitrite or nitrous acid;
the initiator is N-hydroxyphthalimide, N' -dihydroxypyromellitic imide, N-acetoxynaphthalimide, N-hydroxynaphthalimide or 3-picolyl-N-hydroxyphthalimide.
2. The method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation of molecular oxygen according to claim 1, wherein: the gas/liquid volume flow ratio in the reactor is 1: 1-1: 2, the mass concentration of o-nitro-p-methylsulfonyl toluene in the reactor is 5-15%, the mass concentration of cobalt salt in the reactor is 0.1-1.0%, the mass concentration of manganese salt in the reactor is 0.1-1.0%, the mass concentration of an accelerant in the reactor is 0.05-0.8%, and the mass concentration of an initiator in the reactor is 0.1-1.5%.
3. The method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation of molecular oxygen according to claim 2, wherein: the mass concentration of o-nitro-p-methylsulfonyl toluene in the reactor is 6-10%.
4. The method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation of molecular oxygen according to claim 2, wherein: the mass concentration of the accelerator in the reactor is 0.1-0.5%.
5. The method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation of molecular oxygen according to claim 2, wherein: the mass concentration of the initiator in the reactor is 0.5-1.0%.
6. The method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation of molecular oxygen according to claim 2, wherein: and the cobalt salt and the manganese salt in the reactor are both 1-10% of the mass of the o-nitro-p-methylsulfonyl toluene in the reactor.
7. The method for preparing 2-nitro-4-methylsulfonylbenzoic acid by molecular oxygen catalytic oxidation according to claims 1 to 6, characterized in that: the reaction temperature in the reactor is 100-250 ℃, the optimal temperature value is 180 ℃, the reaction pressure is 0-3 MPa, and the reaction time is 3-20 hours.
8. The method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation of molecular oxygen according to claim 1, wherein: the reactor is a stainless steel polytetrafluoroethylene high-pressure reactor with a lining.
9. The method for preparing 2-nitro-4-methylsulfonylbenzoic acid by catalytic oxidation of molecular oxygen according to claim 1, wherein: the polar solvent is acetic acid, acetonitrile or ethyl acetate.
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| CN115745851A (en) * | 2022-11-04 | 2023-03-07 | 武汉强丰新特科技有限公司 | Preparation method of o-carboxybenzene sulfonamide |
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