CN116640067A - Preparation method of aminobenzoic acid serving as EDB or EHA raw material - Google Patents
Preparation method of aminobenzoic acid serving as EDB or EHA raw material Download PDFInfo
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- CN116640067A CN116640067A CN202310582637.5A CN202310582637A CN116640067A CN 116640067 A CN116640067 A CN 116640067A CN 202310582637 A CN202310582637 A CN 202310582637A CN 116640067 A CN116640067 A CN 116640067A
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- aminobenzoic acid
- eutectic solvent
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- edb
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- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229960004050 aminobenzoic acid Drugs 0.000 title claims abstract description 29
- 239000002994 raw material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 37
- 230000005496 eutectics Effects 0.000 claims abstract description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 29
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 15
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims abstract description 14
- 235000019743 Choline chloride Nutrition 0.000 claims abstract description 14
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims abstract description 14
- 229960003178 choline chloride Drugs 0.000 claims abstract description 14
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000006479 redox reaction Methods 0.000 claims abstract description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 13
- 229910001439 antimony ion Inorganic materials 0.000 description 10
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 6
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 5
- ZDINGUUTWDGGFF-UHFFFAOYSA-N antimony(5+) Chemical compound [Sb+5] ZDINGUUTWDGGFF-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 3
- 229910000564 Raney nickel Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000003444 phase transfer catalyst Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- ZYMCJDAUBJFVSM-UHFFFAOYSA-N 6-methylheptyl 4-(dimethylamino)benzoate Chemical compound CC(C)CCCCCOC(=O)C1=CC=C(N(C)C)C=C1 ZYMCJDAUBJFVSM-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- 150000005415 aminobenzoic acids Chemical class 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 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
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012949 free radical photoinitiator Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- -1 sulfide anions Chemical class 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/12—Formation of amino and carboxyl groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of preparation of EDB or EHA raw materials, in particular to a preparation method of aminobenzoic acid serving as an EDB or EHA raw material. The invention discloses a preparation method of aminobenzoic acid serving as an EDB or EHA raw material, which comprises the following steps of: nitrotoluene is dissolved in a eutectic solvent, oxidation-reduction reaction is carried out at room temperature in the presence of elemental sulfur, sodium sulfide and alkali, methyl on a benzene ring is oxidized into carboxyl, and simultaneously nitro is reduced into amino, so that aminobenzoic acid is finally obtained; the eutectic solvent is preferably a mixture of three substances, choline chloride, ethylene glycol and antimony trichloride.
Description
Technical Field
The invention relates to the field of preparation of EDB or EHA raw materials, in particular to a preparation method of aminobenzoic acid serving as an EDB or EHA raw material.
Background
Aminobenzoic acid is an important class of fine chemical intermediates, for example, as an important raw material for the preparation of EHA (isooctyl p-dimethylaminobenzoate) or EDB (ethyl p-dimethylaminobenzoate). Isooctyl p-dimethylaminobenzoate is a good ultraviolet absorber in the UVB region with a maximum ultraviolet absorption peak of 311 nm (in ethanol). As an ultraviolet-resistant active ingredient, the composition is widely used in sun-screening cosmetics abroad, and the dosage is extremely large. The FDA in the united states ranks sunscreens containing this product ingredient as a first class of recommended cosmetics. The synthetic route for producing EHA by taking aminobenzoic acid as a raw material is as follows:
。
ethyl p-dimethylaminobenzoate (EDB) is a highly effective amine accelerator, typically used with free radical photoinitiators, and is used mainly for uv curing of varnish coating systems on paper, wood, metal and plastic surfaces, and also for uv radiation polymerization of single or multiple monomers. Therefore, the sensitizer is a sensitizer with excellent performance, is used in combination with thianthrone and acetophenone, can promote photoinitiation and effectively eliminate the interference of oxygen on photoinitiation polymerization. The synthetic route for producing EDB by taking aminobenzoic acid as a raw material is as follows:
。
in summary, aminobenzoic acid is a very important class of fine chemicals. The existing synthesis method of aminobenzoic acid series products basically takes nitrotoluene as a raw material, firstly carries out oxidation reaction to obtain nitrobenzoic acid, and then reduces nitro into amino to obtain aminobenzoic acid products. In the first step of oxidation reaction, dilute nitric acid is mainly used as an oxidant, nitrobenzoic acid is generated at high temperature (about 180 ℃) and high pressure (2 MPa), a large amount of low-concentration dilute nitric acid and a large amount of nitrogen oxide (NOx) waste gas are generated by the process, and the three-waste treatment pressure is high. Or the metal oxidizing agents such as potassium permanganate, sodium dichromate and the like are used for oxidation, and the temperature is milder than that of a dilute nitric acid method, but a large amount of wastewater containing heavy metals exists, so that the environment is seriously influenced. The second step is also a reaction which mainly reduces the nitro group to an amino group. The prior industry mainly uses iron powder reduction, and the technology has low cost and stable product quality, but generates a large amount of iron mud, and has high three-waste treatment difficulty. In recent years, the catalytic hydrogenation technology gradually replaces the iron powder reduction technology, and has the advantages of less three wastes, high atom economy, good quality and the like. The catalysts adopted in the current industrial catalytic hydrogenation technology are generally classified into Raney nickel catalysts and palladium carbon catalysts. While the Raney nickel catalyst has the advantage of lower price than palladium carbon, the Raney nickel is easy to spontaneously ignite in the production process to cause safety accidents. The palladium-carbon catalyst has noble metal palladium and has very high price, so that the large-scale industrial production of aminobenzoic acid series products is restricted.
In addition, in chinese patent CN97106992.1, a method for synthesizing p-bromobenzaldehyde has been reported in which p-nitrotoluene is used as a raw material, sodium polysulfide is used as a catalyst in an ethanol solution, and a phase transfer catalyst is added thereto to cause an intramolecular disproportionation reaction to obtain p-aminobenzoic acid. However, alcohol solvents are particularly easy to volatilize during the use process, so that organic waste gas (VOC) is discharged, rectification is needed during the recovery and purification process, more energy is consumed, and rectification residues and wastewater are generated.
Disclosure of Invention
Aiming at the problems, the invention develops a method for directly taking nitrotoluene as a raw material and simultaneously carrying out oxidation-reduction reaction to obtain aminobenzoic acid, which comprises the following specific scheme:
a preparation method of aminobenzoic acid as an EDB or EHA raw material comprises the following specific steps: nitrotoluene shown in the formula (I) is dissolved in a eutectic solvent, oxidation-reduction reaction is carried out at room temperature in the presence of elemental sulfur, sodium sulfide and alkali, methyl on a benzene ring is oxidized into carboxyl, and simultaneously nitro is reduced into amino, so that aminobenzoic acid shown in the formula (II) is finally obtained;
the nitro group in formula (I) may be ortho, meta or para to the methyl group and the amino group in formula (II) may be ortho, meta or para to the carboxyl group.
The eutectic solvent is a mixture of three substances of choline chloride, ethylene glycol and antimony trichloride.
The mass ratio of choline chloride, ethylene glycol and antimony trichloride in the eutectic solvent is as follows: 1:2-2.5:0.05-0.1.
The preparation method of the eutectic solvent comprises the following steps: mixing choline chloride, ethylene glycol and antimony trichloride in proportion, heating to 70-90 ℃, and cooling to room temperature for standby after the solid choline chloride and antimony trichloride are completely dissolved.
The alkali is inorganic alkali such as sodium hydroxide and potassium hydroxide.
The mole ratio of the elemental sulfur to the sodium sulfide is 1:0.5-2.5.
The molar ratio of the nitrotoluene to the alkali is 1:0.8-1.5.
The total quantity ratio of the nitrotoluene to the elemental sulfur to the sodium sulfide material is 1:1.0-3.0.
The mass ratio of the nitrotoluene to the eutectic solvent is 1:5-20.
The room temperature is 25-35 ℃; the time of the oxidation-reduction reaction is 2-10 hours.
The invention develops a new process for synthesizing aminobenzoic acid by using nitrotoluene as a raw material through a one-step method, and has the following advantages:
(1) In the system, the trivalent antimony of the antimony trichloride is oxidized into high-valence pentavalent antimony ions in the presence of elemental sulfur, the electron-deficient pentavalent antimony ions react with nitrotoluene serving as a raw material, methyl groups are oxidized into carboxyl groups, the pentavalent antimony ions are reduced into trivalent antimony ions, meanwhile, the trivalent antimony ions react with intermediate nitrobenzoic acid to obtain aminobenzoic acid and pentavalent antimony ions, and the pentavalent antimony ions are reduced into trivalent antimony ions in the presence of divalent sulfide anions. The antimony ions truly react with the raw material nitrotoluene in the whole process. The antimony ions can effectively reduce the reaction activation energy in the reaction process, so that the reaction temperature is relatively low, and the better yield can be obtained at room temperature. The reaction principle is as follows:
。
(2) Compared with the prior art, the method has the advantages of simple steps, mild reaction, high yield, less three wastes and the like. The existing industrial production technology of aminobenzoic acid needs to perform oxidation reaction to obtain nitrobenzoic acid, and then perform reduction reaction after separation.
(3) The system of the invention has strong polarity of the eutectic solvent and high solubility of related substances, so that a phase transfer catalyst is not needed.
(4) The choline chloride in the eutectic solvent can not only form a ternary eutectic solvent by glycol and antimony trichloride, but also act as a phase transfer catalyst in a system, so that the reaction yield is improved.
(5) The ternary eutectic solvent disclosed by the invention has a great amount of hydrogen bonds, so that the system belongs to a strong polar solvent, and therefore, the ternary eutectic solvent has better solubility to sodium sulfide and elemental sulfur than other common solvents, thus being beneficial to improving the reaction yield, reducing the loss of sodium sulfide and elemental sulfur in the solvent circulation process, reducing the production cost and reducing the environmental pollution.
(6) Common solvents such as ethanol and the like are used as reaction medium, and inorganic matters such as elemental sulfur, sodium sulfide and alkali and the like have low solubility in the common solvents. Therefore, after the product is filtered, more inorganic salt exists in the product, and further purification is needed, so that more wastewater is generated. The eutectic solvent has good solubility to inorganic matters in a reaction system, and is recovered and reused in the eutectic solvent, so that not only is the precipitated product not required to be purified, but also raw material consumption is greatly saved.
(7) The eutectic solvent is an ionic liquid and therefore has a very low vapor pressure, i.e., a very high boiling point. In the system of the invention, the addition of the ternary eutectic solvent greatly promotes the activity of the reaction, and can react at room temperature. Compared with the traditional methanol and ethanol solvents, the method avoids VOC emission and solvent consumption in the reaction process, and greatly reduces the production cost and energy consumption.
Detailed Description
Example 1
Preparation of the eutectic solvent: 100 g of choline chloride, 200 g of ethylene glycol and 5 g of antimony trichloride are mixed and heated to 90 ℃, and after all the solid choline chloride and antimony trichloride are dissolved, the mixture is cooled to room temperature for standby.
68.6 g of paranitrotoluene, 16 g of elemental sulfur, 39 g of sodium sulfide, 20 g of sodium hydroxide and 686 g of eutectic solvent are put into a three-neck flask, stirred uniformly at normal temperature (25 ℃) for 8 hours, filtered, recycled and reused, and 68.1 g of paraaminobenzoic acid is obtained after filter cake is washed and dried by a small amount of cold water, and the HPLC purity is 99.1% and the molar yield is 98.5% (relative to the paranitrotoluene).
Example 2
Preparation of the eutectic solvent: 100 g of choline chloride, 250 g of ethylene glycol and 10 g of antimony trichloride are mixed and heated to 70 ℃, and after all the solid choline chloride and antimony trichloride are dissolved, the mixture is cooled to room temperature for standby.
68.6 g of paranitrotoluene, 16 g of elemental sulfur, 19.5 g of sodium sulfide, 30 g of sodium hydroxide and 343 g of eutectic solvent are put into a three-necked flask, stirred uniformly at normal temperature, stirred for reaction for 10 hours, filtered, recycled and reused, and 67.5 g of paraaminobenzoic acid with 99.5% of HPLC purity and 98.0% of molar yield (relative to paranitrotoluene) is obtained after washing and drying filter cakes with a small amount of cold water.
Example 3
The eutectic solvent was prepared as in example 1.
68.6 g of o-nitrotoluene, 4.5 g of elemental sulfur, 28.1 g of sodium sulfide, 30 g of sodium hydroxide and 1372 g of eutectic solvent are put into a three-neck flask, stirred uniformly at normal temperature, stirred for 6 hours, filtered, recycled and reused, and the filter cake is washed and dried by a small amount of cold water to obtain 67.8 g of o-aminobenzoic acid, wherein the HPLC purity is 99.6%, and the molar yield is 98.4% (relative to the o-nitrotoluene).
Example 4
The eutectic solvent was prepared as in example 1.
68.6 g of o-nitrotoluene, 4.5 g of elemental sulfur, 28.1 g of sodium sulfide, 30 g of sodium hydroxide and 1372 g of eutectic solvent are put into a three-neck flask, stirred uniformly at normal temperature, stirred for 10 hours, filtered, recycled and reused, and the filter cake is washed and dried by a small amount of cold water to obtain 67.6 g of o-aminobenzoic acid, wherein the HPLC purity is 99.3% and the molar yield is 97.9% (relative to the o-nitrotoluene).
Example 5
The eutectic solvent was prepared as in example 2.
68.6 g of o-nitrotoluene, 16 g of elemental sulfur, 39 g of sodium sulfide, 28 g of potassium hydroxide and 686 g of eutectic solvent are put into a three-neck flask, stirred uniformly at normal temperature, reacted for 2 hours while stirring, filtered after the reaction is finished, the filtrate is recovered and reused, and the filter cake is washed and dried by a small amount of cold water to obtain 68.2 g of o-aminobenzoic acid, wherein the HPLC purity is 99.1%, and the molar yield is 98.5% (relative to the o-nitrotoluene).
The above embodiments are only for illustrating the inventive concept of the present invention and not for limiting the protection of the claims of the present invention, and all the insubstantial modifications of the present invention using the concept shall fall within the protection scope of the present invention.
Claims (10)
1. The preparation method of aminobenzoic acid as raw material of EDB or EHA is characterized by comprising the following specific steps: nitrotoluene shown in the formula (I) is dissolved in a eutectic solvent, oxidation-reduction reaction is carried out at room temperature in the presence of elemental sulfur, sodium sulfide and alkali, methyl on a benzene ring is oxidized into carboxyl, and simultaneously nitro is reduced into amino, so that aminobenzoic acid shown in the formula (II) is finally obtained;
the nitro group in formula (I) is ortho, meta or para to the methyl group and the amino group in formula (II) is ortho, meta or para to the carboxyl group.
2. The method for preparing aminobenzoic acid as in claim 1, wherein the method is characterized in that: the eutectic solvent is a mixture of three substances of choline chloride, ethylene glycol and antimony trichloride.
3. The method for preparing aminobenzoic acid as in claim 2, wherein the method is characterized in that: the mass ratio of choline chloride, ethylene glycol and antimony trichloride in the eutectic solvent is as follows: 1:2-2.5:0.05-0.1.
4. A method for preparing aminobenzoic acid as claimed in claim 3, wherein the method for preparing the eutectic solvent is as follows: mixing choline chloride, ethylene glycol and antimony trichloride in proportion, heating to 70-90 ℃, and cooling to room temperature for standby after the solid choline chloride and antimony trichloride are completely dissolved.
5. The method for preparing aminobenzoic acid as in claim 1, wherein the method is characterized in that: the alkali is inorganic alkali such as sodium hydroxide and potassium hydroxide.
6. The method for preparing aminobenzoic acid as in claim 1, wherein the method is characterized in that: the mole ratio of the elemental sulfur to the sodium sulfide is 1:0.5-2.5.
7. The method for preparing aminobenzoic acid as in claim 1, wherein the method is characterized in that: the molar ratio of the nitrotoluene to the alkali is 1:0.8-1.5.
8. The method for preparing aminobenzoic acid as in claim 1, wherein the method is characterized in that: the total quantity ratio of the nitrotoluene to the elemental sulfur to the sodium sulfide material is 1:1.0-3.0.
9. The method for preparing aminobenzoic acid as in claim 1, wherein the method is characterized in that: the mass ratio of the nitrotoluene to the eutectic solvent is 1:5-20.
10. The method for preparing aminobenzoic acid as in claim 1, wherein the method is characterized in that: the room temperature is 25-35 ℃; the time of the oxidation-reduction reaction is 2-10 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310582637.5A CN116640067A (en) | 2023-05-23 | 2023-05-23 | Preparation method of aminobenzoic acid serving as EDB or EHA raw material |
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