CN115232011B - Method for synthesizing p-nitrobenzoic acid - Google Patents
Method for synthesizing p-nitrobenzoic acid Download PDFInfo
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- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims description 148
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 72
- 238000006243 chemical reaction Methods 0.000 claims description 52
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 38
- 239000000376 reactant Substances 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 33
- 238000000967 suction filtration Methods 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 29
- 239000000706 filtrate Substances 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 25
- 239000002244 precipitate Substances 0.000 claims description 25
- 238000001914 filtration Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 16
- 239000012043 crude product Substances 0.000 claims description 14
- 239000005457 ice water Substances 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 150000007524 organic acids Chemical class 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 150000002531 isophthalic acids Chemical class 0.000 claims description 5
- 229910001507 metal halide Inorganic materials 0.000 claims description 5
- 150000005309 metal halides Chemical group 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- DPFUYQIOKHUWON-UHFFFAOYSA-N benzene-1,3-dicarboxylic acid;iron Chemical compound [Fe].OC(=O)C1=CC=CC(C(O)=O)=C1 DPFUYQIOKHUWON-UHFFFAOYSA-N 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 15
- 239000002184 metal Substances 0.000 abstract description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 11
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 22
- 229910052802 copper Inorganic materials 0.000 description 22
- 239000010949 copper Substances 0.000 description 22
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 13
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
- 230000005291 magnetic effect Effects 0.000 description 8
- 229910000859 α-Fe Inorganic materials 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- -1 benzoic acid radical ion Chemical class 0.000 description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 229910001509 metal bromide Inorganic materials 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 229910001512 metal fluoride Inorganic materials 0.000 description 2
- RJWPKQQDNYEAEA-UHFFFAOYSA-N n-[3-hydroxy-2-(hydroxymethyl)-1-(4-nitrophenyl)-1-oxopropan-2-yl]acetamide Chemical compound CC(=O)NC(CO)(CO)C(=O)C1=CC=C([N+]([O-])=O)C=C1 RJWPKQQDNYEAEA-UHFFFAOYSA-N 0.000 description 2
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 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 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- HCBIBCJNVBAKAB-UHFFFAOYSA-N Procaine hydrochloride Chemical compound Cl.CCN(CC)CCOC(=O)C1=CC=C(N)C=C1 HCBIBCJNVBAKAB-UHFFFAOYSA-N 0.000 description 1
- QCTBMLYLENLHLA-UHFFFAOYSA-N aminomethylbenzoic acid Chemical compound NCC1=CC=C(C(O)=O)C=C1 QCTBMLYLENLHLA-UHFFFAOYSA-N 0.000 description 1
- 229960003375 aminomethylbenzoic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 229960001309 procaine hydrochloride Drugs 0.000 description 1
- 238000013094 purity test Methods 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/16—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing p-nitrobenzoic acid, which combines a nitric acid oxidation method and an air oxidation method by a one-step method, does not independently add nitric acid under the combined action of an initiator, a valence-variable metal salt, ferric salt and oxygen, and can react at a lower temperature and a lower pressure to obtain the p-nitrobenzoic acid.
Description
Technical Field
The invention relates to the field of chemical product production, in particular to a method for synthesizing p-nitrobenzoic acid.
Background
P-nitrobenzoic acid is an important intermediate for synthesizing organic matters, and is used for producing procaine hydrochloride, p-aminomethylbenzoic acid and other medical products, active red and violet fuel, color film coupler and other fine chemicals. The methods for synthesizing nitrobenzoic acid are mainly divided into two types: 1. oxidized nitrotoluene and 2. Nitrobenzoic acid. The main method for synthesizing p-nitrobenzoic acid is to oxidize nitrotoluene. HNO (HNO) 3 The oxidation method is widely used because of low production cost, simple process and high yield, and is suitable for industrial production. However, the reaction is required to be carried out under high temperature and high pressure conditions, and the condition that nitric acid has strong corrosiveness to equipment and large waste gas and waste acid amount is a problem to be solved in the current production.
Chinese patent CN 108658777A discloses a method for synthesizing p-nitrobenzoic acid, which uses 2-p-nitrobenzoyl-2-acetamido-1, 3-propanediol and nitric acid as raw materials and water as solvent, and can react to obtain p-nitrobenzoic acid under normal pressure and 100 ℃, but the raw material 2-p-nitrobenzoyl-2-acetamido-1, 3-propanediol has high preparation cost, formaldehyde used in the preparation process is a substance with higher toxicity, and is unfavorable for industrial production.
Disclosure of Invention
The invention aims to provide a synthetic method of p-nitrobenzoic acid, which has high production purity and simple process and is suitable for popularization.
Aiming at the defects in the prior art, the synthetic method of the p-nitrobenzoic acid comprises the following steps:
1. the method comprises the steps of (1) placing a valence-variable metal salt and an organic acid into a heatable closed grinding device, uniformly mixing, grinding, adding an organic solvent, continuously grinding, adding paranitrotoluene and an initiator, and introducing oxygen; heating the heatable closed grinding device while continuously grinding, reacting for a period of time at a constant temperature, cooling one by one, and reacting for a period of time at constant temperature at different temperatures to obtain a reactant I;
2. pouring the reactant I into an ice-water mixture, melting ice cubes, performing suction filtration to obtain filter residue I, washing with water, and drying to obtain a p-nitrobenzoic acid crude product;
3. adding the p-nitrobenzoic acid crude product into water, dropwise adding a NaOH solution under the stirring condition until the liquid is red, standing, then dropwise adding anhydrous acetic acid until the solution is colorless, standing, and carrying out suction filtration to obtain a filtrate I;
4. and (3) dropwise adding sulfuric acid aqueous solution into the filtrate I under the stirring condition to generate precipitate, continuously dropwise adding the precipitate without increasing, carrying out suction filtration to obtain filter residue II, and drying the filter residue II to obtain the p-nitrobenzoic acid pure product.
Preferably, the synthetic method of the p-nitrobenzoic acid comprises the following steps:
1. putting 4-8 parts of variable valence metal salt and 2-4 parts of organic acid into a heatable closed grinding device according to parts by mol, uniformly mixing, setting the rotating speed to be 80-200rpm, grinding for 30-60min, adding 5-10 parts of organic solvent, continuously grinding for 5-10min, adding 1-2 parts of paranitrotoluene and 0.5-1 part of initiator, ensuring that the volume of reactants in the heatable closed grinding device is 15-30% of the total volume in the heatable closed grinding device at the moment, introducing oxygen to the heatable closed grinding device, keeping the pressure in the heatable closed grinding device to be 0.1-0.3MPa, and keeping the pressure fluctuation range in the heatable closed grinding device in the subsequent reaction process to be 0.02-0.03 MPa;
2. heating the heatable closed grinding device to 130-150 ℃ at the speed of 3-5 ℃/min for reacting for 2-3h while continuously grinding, cooling to 80-100 ℃ at the speed of 1-3 ℃/min for reacting for 1-2h, cooling to 40-60 ℃ at the speed of 1-3 ℃/min, and standing for reacting for 1-2h to obtain a reactant I;
3. pouring the reactant I into an ice-water mixture according to the mass ratio of 1:3-5, melting ice cubes, performing suction filtration to obtain filter residue I, washing with water, and drying to obtain a p-nitrobenzoic acid crude product;
4. adding the crude p-nitrobenzoic acid into water according to the feed liquid ratio of 1:20-50 mL, dropwise adding 10-18wt% of NaOH aqueous solution at the speed of 0.5-1 drop/s under the stirring condition of 200-400rpm until the liquid is red, standing for 20-40s, dropwise adding anhydrous acetic acid at the speed of 0.5-1 drop/s until the solution is colorless, standing for 20-40s, and carrying out suction filtration to obtain filtrate I;
5. and (3) dropwise adding 40-60wt% sulfuric acid aqueous solution into the filtrate I at the speed of 0.5-1 drop/s under the stirring condition of 200-400rpm to generate precipitate, continuously dropwise adding the precipitate without increasing, carrying out suction filtration to obtain filter residue II, and drying the filter residue II in a 50-60 ℃ oven to obtain the p-nitrobenzoic acid pure product.
The interior of the heatable airtight grinding device is made of copper, and the grinding rod is a copper rod.
The valence-changing metal salt is valence-changing metal nitrate.
Preferably, the valence-variable metal salt is at least one of cobalt nitrate, manganese nitrate, cadmium nitrate, copper nitrate, chromium nitrate, nickel nitrate and ferric nitrate.
The organic solvent is at least one of ethanol, glycol, glycerol and isopropanol.
The organic acid is citric acid.
The initiator is a metal halide.
Preferably, the initiator is one of a metal fluoride, a metal bromide or a metal chloride.
Further preferably, the initiator is one of NaF, naF, naBr, naCl, KBr, KCl.
The valence-variable metal salt reacts with organic acid to generate complex, nitric acid and water to form acid environment, the paranitrotoluene absorbs heat energy converted from mechanical energy in the grinding process, local high temperature is generated at the contact point with a grinding rod during grinding, free radicals are formed under the action of an initiator, and paranitrobenzoic acid is generated through the catalysis of the valence-variable metal salt, the joint oxidation of nitric acid and oxygen. Nitric acid is reduced to produce nitric oxide after participating in oxidation, oxygen in the reaction device is oxidized into nitrogen dioxide, nitric acid is generated when meeting water, a circulating system is formed, the nitric acid concentration in the reaction system is kept in a certain range, the temperature, the pressure and the acid concentration are not too high, and the corrosion to equipment is small. The waste gas and the waste liquid are less in emission, convenient for subsequent treatment, environment-friendly and energy-saving. Compared with the conventional process for oxidizing paranitrotoluene by nitric acid to generate paranitrobenzoic acid or the process for oxidizing paranitrotoluene by oxygen to generate paranitrobenzoic acid, the reaction can be carried out at lower temperature and lower pressure, the yield of the paranitrobenzoic acid can reach more than 85%, and the purity can reach more than 92%.
As a more preferable technical scheme of the invention, a method for synthesizing p-nitrobenzoic acid comprises the following steps:
1. 2-3 parts of valence-variable metal salt, 2-5 parts of ferric salt and 2-4 parts of organic acid are put into a heatable airtight grinding device, after being uniformly mixed, the rotating speed is set to be 80-200rpm, grinding is carried out for 30-60min, 5-10 parts of organic solvent is added for continuously grinding for 5-10min, then 1-2 parts of paranitrotoluene and 0.5-1 part of initiator are added, the volume of reactants in the heatable airtight grinding device is ensured to be 15-30% of the total volume in the heatable airtight grinding device at the moment, then oxygen is introduced into the heatable airtight grinding device until the pressure in the heatable airtight grinding device is 0.1-0.3MPa, and the pressure fluctuation range in the heatable airtight grinding device in the subsequent reaction process is kept within 0.02-0.03 MPa;
2. heating the heatable closed grinding device to 60-70 ℃ at the speed of 3-5 ℃/min for reacting for 2-3h while continuously grinding, cooling to 40-50 ℃ at the speed of 1-3 ℃/min for reacting for 1-2h, cooling to 20-25 ℃ at the speed of 1-3 ℃/min, and standing for reacting for 1-2h to obtain a reactant I;
3. reactant I is prepared according to the mass ratio of 1: (3-5) pouring the mixture into an ice-water mixture, melting ice cubes, performing suction filtration to obtain filter residue I, and washing and drying to obtain a p-nitrobenzoic acid crude product;
4. adding the crude p-nitrobenzoic acid into water according to the feed liquid ratio of 1:20-50 mL, dropwise adding 10-18wt% of NaOH aqueous solution at the speed of 0.5-1 drop/s under the stirring condition of 200-400rpm until the liquid is red, standing for 20-40s, dropwise adding anhydrous acetic acid at the speed of 0.5-1 drop/s until the solution is colorless, standing for 20-40s, and carrying out suction filtration to obtain filtrate I;
5. and (3) dropwise adding 40-60wt% sulfuric acid aqueous solution into the filtrate I at the speed of 0.5-1 drop/s under the stirring condition of 200-400rpm to generate precipitate, continuously dropwise adding the precipitate without increasing, carrying out suction filtration to obtain filter residue II, and drying the filter residue II in a 50-60 ℃ oven to obtain the p-nitrobenzoic acid pure product.
The interior of the heatable airtight grinding device is made of copper, and the grinding rod is a copper rod.
The valence-changing metal salt is valence-changing metal nitrate.
Preferably, the valence-variable metal salt is one of cobalt nitrate, manganese nitrate, cadmium nitrate, copper nitrate, chromium nitrate, nickel nitrate and ferric nitrate.
The ferric salt is at least one of ferric nitrate, ferric oxalate, ferric acetate, ferric isophthalate and polynuclear ferric isophthalic acid complex.
The preparation method of the ferric salt of isophthalic acid comprises the following steps:
3-5 parts of isophthalic acid is dissolved in an organic solvent according to the mole parts to form 30-45wt% of isophthalic acid solution, 1-2 parts of ferric trichloride is dissolved in the organic solvent to form 20-30wt% of ferric trichloride solution, the isophthalic acid solution is dripped into the ferric trichloride solution at the speed of 0.5-1 drop/s, then the reaction is carried out for 8-16h at the temperature of 75-80 ℃, the filtration is carried out to obtain filter residue A, and the filtration is carried out for 4-6h at the temperature of 80-90 ℃ to obtain ferric isophthalate.
The preparation method of the polynuclear isophthalic acid complex comprises the following steps:
s1, dissolving 3-5 parts of isophthalic acid in an organic solvent to form 30-45wt% of isophthalic acid solution, dissolving 1-2 parts of ferric trichloride in the organic solvent to form 20-30wt% of ferric trichloride solution, dripping the isophthalic acid solution into the ferric trichloride solution at the speed of 0.5-1 drop/s, reacting at 75-80 ℃ for 8-16h, filtering to obtain filter residue A, and drying at 80-90 ℃ for 4-6h to obtain ferric isophthalate salt;
s2, 1 to 2 parts of ferric salt of isophthalic acid and 0.5 to 1 part of Cr (NO) 3 ) 3 Heating and refluxing in 8-14 acetone at 60-75deg.C for 25-50min, naturally cooling to 40-45deg.C, filtering, standing at room temperature for crystallization, filtering to obtain residue B, washing with water, and oven drying to obtain polynuclear isophthalic acid complex.
The organic acid is citric acid.
The organic solvent is at least one of ethanol, glycol, glycerol and isopropanol.
The initiator is a metal halide.
Preferably, the initiator is one of a metal fluoride, a metal bromide or a metal chloride.
Further preferably, the initiator is one of NaF, naF, naBr, naCl, KBr, KCl.
The addition of ferric salt, which reacts with organic acid to form complex, acid and water, and iron is also a valence-variable metal, which has the function of catalyzing the oxidation of paranitrotoluene to generate paranitrobenzoic acid. However, in the experiment, unexpected findings that after the ferric salt is added, the effect is not only to improve the catalytic efficiency, but also to realize that the target product can be generated at a lower reaction temperature: the yield of the p-nitrobenzoic acid can reach more than 95 percent, and the purity can reach more than 99 percent.
The complex formed by ferric salt and organic acid reacts with complex formed by valence-variable metal salt under the action of oxygen to generate a new substance: ferrite, and in the presence of metal halides, ferrite forms a specific crystal form, and has better catalysis effect on paranitrotoluene. The ferrite forms a magnetic field in the reaction device, and when the reaction device is grinded, the grinding rod cuts the magnetic induction wire to generate current, so that a thermal effect and a magnetic effect are generated. On the basis of the heat energy converted from mechanical energy generated by grinding, the heat energy is further provided for a reaction system, so that the oxidation reaction can be caused to occur at a lower reaction temperature.
The polynuclear isophthalic acid complex contains benzoic acid radical ion, nitrate radical ion and acetone molecule, and is bridged with iron ion through hydrogen bond interaction, and takes oxygen atom as center to form stable space conformation, and the polynuclear isophthalic acid complex has certain magnetism by performing magnetic exchange. More gaps are formed in the further generated ferrite unit cells, which is beneficial to doping and substitution of valence-variable metal, and is beneficial to improving magnetic performance and catalytic effect.
The beneficial effects are that: the method for synthesizing the p-nitrobenzoic acid has the advantages of simple process, environmental protection, energy saving, high purity of target products and suitability for popularization.
Detailed Description
The raw materials used in the examples are as follows:
cobalt nitrate, co (NO) 3 ) 2 ·6H 2 O, CAS:10026-22-9, 99% pure, shanghai Ala Biochemical technologies Co., ltd.
Nickel nitrate, ni (NO) 3 ) 2 ·6H 2 O, CAS:13478-00-7, purity 98%, shanghai Ala Biochemical technologies Co., ltd.
Ferric nitrate, fe (NO) 3 ) 3 ·9H 2 O, CAS:7782-61-8, purity 99.9%, shanghai Ala Biochemical technologies Co., ltd.
Iron oxalate, fe 2 (C 2 O 4 ) 3 ·5H 2 O, CAS:2944-66-3, 99% pure, shanghai Ala Biochemical technologies Co., ltd.
Sodium benzoate, CAS:532-32-1, purity 99%, shanghai Ala Biochemical technologies Co., ltd.
Ferric trichloride, feCl 3 ·6H 2 O, CAS:10025-77-1, 99% pure, shanghai Ala Biochemical technologies Co., ltd.
Citric acid, C 6 H 8 O 7 ·H 2 O, CAS:5949-29-1, purity 99.9%, shanghai Ala Biochemical technologies Co., ltd.
Ethylene glycol, CAS:107-21-1, 99.5% pure, shanghai Ala Biochemical technologies Co., ltd.
Para-nitrotoluene, CAS:99-99-0, purity 99.5%, shanghai Ala Biochemical technologies Co., ltd.
KBr, CAS:7758-02-3, purity 99%, shanghai Ala Biochemical technologies Co., ltd.
Example 1
1. Based on the molar parts, 4 parts Co (NO 3 ) 2 ·6H 2 Placing O and 4 parts of citric acid into a heatable closed grinding device, uniformly mixing, setting the rotating speed to 100rpm, grinding for 40min, adding 8 parts of ethylene glycol, continuously grinding for 8min, then adding 1.4 parts of paranitrotoluene and 0.6 part of KBr, ensuring that the volume of reactants in the heatable closed grinding device is 20% of the total volume in the heatable closed grinding device at the moment, introducing oxygen to the heatable closed grinding device, wherein the pressure is 0.2MPa, and keeping the pressure fluctuation range in the heatable closed grinding device in the subsequent reaction process within 0.02 MPa;
2. heating the heatable closed grinding device to 140 ℃ at a speed of 4 ℃/min for reaction for 3 hours while continuously grinding, cooling to 90 ℃ at a speed of 2 ℃/min for reaction for 1.5 hours, cooling to 50 ℃ at a speed of 2 ℃/min, and standing for reaction for 2 hours to obtain a reactant I;
3. pouring the reactant I into an ice-water mixture according to the mass ratio of 1:4, melting ice cubes, performing suction filtration to obtain filter residue I, and washing and drying to obtain a p-nitrobenzoic acid crude product;
4. adding the crude p-nitrobenzoic acid into water according to the feed liquid ratio of 1:40 mL, dropwise adding 15wt% of NaOH aqueous solution at the speed of 1 drop/s under the stirring condition of 300rpm until the liquid is red, standing for 30s, dropwise adding anhydrous acetic acid at the speed of 1 drop/s until the solution is colorless, standing for 40s, and suction-filtering to obtain filtrate I;
5. and (3) dropwise adding 50wt% sulfuric acid aqueous solution into the filtrate I at a speed of 1 drop/s under the stirring condition of 300rpm to generate precipitate, continuously dropwise adding the precipitate without increasing, carrying out suction filtration to obtain filter residue II, and drying the filter residue II in a 60 ℃ oven to obtain the pure p-nitrobenzoic acid product.
The interior of the heatable airtight grinding device is made of copper, and the grinding rod is a copper rod.
Example 2
1. Based on the mole fraction, 4 parts of Ni (NO 3 ) 2 ·6H 2 O and 4 parts of citric acid are put into a heatable closed grinding device, after being uniformly mixed, the mixture is ground for 40min at a rotating speed of 100rpm, 8 parts of ethylene glycol is added for continuous grinding for 8min, then 1.4 parts of paranitrotoluene and 0.6 part of KBr are added, and the volume of reactants in the heatable closed grinding device at the moment is ensured to beIntroducing oxygen into the heatable sealed grinding device until the pressure in the heatable sealed grinding device is 0.2MPa, and keeping the pressure fluctuation range in the heatable sealed grinding device in the subsequent reaction process within 0.02 MPa;
2. heating the heatable closed grinding device to 140 ℃ at a speed of 4 ℃/min for reaction for 3 hours while continuously grinding, cooling to 90 ℃ at a speed of 2 ℃/min for reaction for 1.5 hours, cooling to 50 ℃ at a speed of 2 ℃/min, and standing for reaction for 2 hours to obtain a reactant I;
3. pouring the reactant I into an ice-water mixture according to the mass ratio of 1:4, melting ice cubes, performing suction filtration to obtain filter residue I, and washing and drying to obtain a p-nitrobenzoic acid crude product;
4. adding the crude p-nitrobenzoic acid into water according to the feed liquid ratio of 1:40 mL, dropwise adding 15wt% of NaOH aqueous solution at the speed of 1 drop/s under the stirring condition of 300rpm until the liquid is red, standing for 30s, dropwise adding anhydrous acetic acid at the speed of 1 drop/s until the solution is colorless, standing for 40s, and suction-filtering to obtain filtrate I;
5. and (3) dropwise adding 50wt% sulfuric acid aqueous solution into the filtrate I at a speed of 1 drop/s under the stirring condition of 300rpm to generate precipitate, continuously dropwise adding the precipitate without increasing, carrying out suction filtration to obtain filter residue II, and drying the filter residue II in a 60 ℃ oven to obtain the pure p-nitrobenzoic acid product.
The interior of the heatable airtight grinding device is made of copper, and the grinding rod is a copper rod.
Example 3
1. Based on the molar parts, 4 parts of Fe (NO 3 ) 3 ·9H 2 Placing O and 4 parts of citric acid into a heatable closed grinding device, uniformly mixing, setting the rotating speed to 100rpm, grinding for 40min, adding 8 parts of ethylene glycol, continuously grinding for 8min, then adding 1.4 parts of paranitrotoluene and 0.6 part of KBr, ensuring that the volume of reactants in the heatable closed grinding device is 20% of the total volume in the heatable closed grinding device at the moment, introducing oxygen to the heatable closed grinding device, wherein the pressure is 0.2MPa, and keeping the pressure fluctuation range in the heatable closed grinding device in the subsequent reaction process within 0.02 MPa;
2. heating the heatable closed grinding device to 140 ℃ at a speed of 4 ℃/min for reaction for 3 hours while continuously grinding, cooling to 90 ℃ at a speed of 2 ℃/min for reaction for 1.5 hours, cooling to 50 ℃ at a speed of 2 ℃/min, and standing for reaction for 2 hours to obtain a reactant I;
3. pouring the reactant I into an ice-water mixture according to the mass ratio of 1:4, melting ice cubes, performing suction filtration to obtain filter residue I, and washing and drying to obtain a p-nitrobenzoic acid crude product;
4. adding the crude p-nitrobenzoic acid into water according to the feed liquid ratio of 1:40 mL, dropwise adding 15wt% of NaOH aqueous solution at the speed of 1 drop/s under the stirring condition of 300rpm until the liquid is red, standing for 30s, dropwise adding anhydrous acetic acid at the speed of 1 drop/s until the solution is colorless, standing for 40s, and suction-filtering to obtain filtrate I;
5. and (3) dropwise adding 50wt% sulfuric acid aqueous solution into the filtrate I at a speed of 1 drop/s under the stirring condition of 300rpm to generate precipitate, continuously dropwise adding the precipitate without increasing, carrying out suction filtration to obtain filter residue II, and drying the filter residue II in a 60 ℃ oven to obtain the pure p-nitrobenzoic acid product.
The interior of the heatable airtight grinding device is made of copper, and the grinding rod is a copper rod.
Example 4
1. Based on the molar parts, 2 parts Ni (NO 3 ) 2 ·6H 2 O, 2 parts of Fe (NO) 3 ) 3 ·9H 2 O,4 parts of citric acid are put into a heatable closed grinding device, after being uniformly mixed, the rotating speed is set to be 100rpm, grinding is carried out for 40min, 8 parts of ethylene glycol is added for continuous grinding for 8min, then 1.4 parts of paranitrotoluene and 0.6 part of KBr are added, the volume of reactants in the heatable closed grinding device is ensured to be 20% of the total volume in the heatable closed grinding device at the moment, then oxygen is introduced into the heatable closed grinding device until the pressure in the heatable closed grinding device is 0.2MPa, and the pressure fluctuation range in the heatable closed grinding device in the subsequent reaction process is kept within 0.02 MPa;
2. heating the heatable closed grinding device to 70 ℃ at the speed of 4 ℃/min for reaction for 3 hours while continuously grinding, cooling to 40 ℃ at the speed of 2 ℃/min for reaction for 1.5 hours, cooling to 25 ℃ at the speed of 2 ℃/min, and standing for reaction for 2 hours to obtain a reactant I;
3. pouring the reactant I into an ice-water mixture according to the mass ratio of 1:4, melting ice cubes, performing suction filtration to obtain filter residue I, and washing and drying to obtain a p-nitrobenzoic acid crude product;
4. adding the crude p-nitrobenzoic acid into water according to the feed liquid ratio of 1:40 mL, dropwise adding 15wt% of NaOH aqueous solution at the speed of 1 drop/s under the stirring condition of 300rpm until the liquid is red, standing for 30s, dropwise adding anhydrous acetic acid at the speed of 1 drop/s until the solution is colorless, standing for 40s, and suction-filtering to obtain filtrate I;
5. and (3) dropwise adding 50wt% sulfuric acid aqueous solution into the filtrate I at a speed of 1 drop/s under the stirring condition of 300rpm to generate precipitate, continuously dropwise adding the precipitate without increasing, carrying out suction filtration to obtain filter residue II, and drying the filter residue II in a 60 ℃ oven to obtain the pure p-nitrobenzoic acid product.
The interior of the heatable airtight grinding device is made of copper, and the grinding rod is a copper rod.
Example 5
1. Based on the molar parts, 2 parts Ni (NO 3 ) 2 ·6H 2 O, 2 parts of Fe 2 (C 2 O 4 ) 3 ·5H 2 O,4 parts of citric acid are put into a heatable closed grinding device, after being uniformly mixed, the rotating speed is set to be 100rpm, grinding is carried out for 40min, 8 parts of ethylene glycol is added for continuous grinding for 8min, then 1.4 parts of paranitrotoluene and 0.6 part of KBr are added, the volume of reactants in the heatable closed grinding device is ensured to be 20% of the total volume in the heatable closed grinding device at the moment, then oxygen is introduced into the heatable closed grinding device until the pressure in the heatable closed grinding device is 0.2MPa, and the pressure fluctuation range in the heatable closed grinding device in the subsequent reaction process is kept within 0.02 MPa;
2. heating the heatable closed grinding device to 70 ℃ at the speed of 4 ℃/min for reaction for 3 hours while continuously grinding, cooling to 40 ℃ at the speed of 2 ℃/min for reaction for 1.5 hours, cooling to 25 ℃ at the speed of 2 ℃/min, and standing for reaction for 2 hours to obtain a reactant I;
3. pouring the reactant I into an ice-water mixture according to the mass ratio of 1:4, melting ice cubes, performing suction filtration to obtain filter residue I, and washing and drying to obtain a p-nitrobenzoic acid crude product;
4. adding the crude p-nitrobenzoic acid into water according to the feed liquid ratio of 1:40 mL, dropwise adding 15wt% of NaOH aqueous solution at the speed of 1 drop/s under the stirring condition of 300rpm until the liquid is red, standing for 30s, dropwise adding anhydrous acetic acid at the speed of 1 drop/s until the solution is colorless, standing for 40s, and suction-filtering to obtain filtrate I;
5. and (3) dropwise adding 50wt% sulfuric acid aqueous solution into the filtrate I at a speed of 1 drop/s under the stirring condition of 300rpm to generate precipitate, continuously dropwise adding the precipitate without increasing, carrying out suction filtration to obtain filter residue II, and drying the filter residue II in a 60 ℃ oven to obtain the pure p-nitrobenzoic acid product.
The interior of the heatable airtight grinding device is made of copper, and the grinding rod is a copper rod.
Example 6
1. Based on the molar parts, 2 parts Ni (NO 3 ) 2 ·6H 2 O, 2 parts of ferric isophthalic acid salt and 4 parts of citric acid are put into a heatable closed grinding device, after being uniformly mixed, the stirring speed is set to 100rpm for grinding for 40min, 8 parts of ethylene glycol is added for grinding for 8min, then 1.4 parts of paranitrotoluene and 0.6 part of KBr are added, the volume of reactants in the heatable closed grinding device at the moment is ensured to be 20 percent of the total volume in the heatable closed grinding device, then oxygen is introduced into the heatable closed grinding device, the pressure is 0.2MPa, and the pressure fluctuation range in the heatable closed grinding device in the subsequent reaction process is kept to be within 0.02 MPa;
2. heating the heatable closed grinding device to 70 ℃ at the speed of 4 ℃/min for reaction for 3 hours while continuously grinding, cooling to 40 ℃ at the speed of 2 ℃/min for reaction for 1.5 hours, cooling to 25 ℃ at the speed of 2 ℃/min, and standing for reaction for 2 hours to obtain a reactant I;
3. pouring the reactant I into an ice-water mixture according to the mass ratio of 1:4, melting ice cubes, performing suction filtration to obtain filter residue I, and washing and drying to obtain a p-nitrobenzoic acid crude product;
4. adding the crude p-nitrobenzoic acid into water according to the feed liquid ratio of 1:40 mL, dropwise adding 15wt% of NaOH aqueous solution at the speed of 1 drop/s under the stirring condition of 300rpm until the liquid is red, standing for 30s, dropwise adding anhydrous acetic acid at the speed of 1 drop/s until the solution is colorless, standing for 40s, and suction-filtering to obtain filtrate I;
5. and (3) dropwise adding 50wt% sulfuric acid aqueous solution into the filtrate I at a speed of 1 drop/s under the stirring condition of 300rpm to generate precipitate, continuously dropwise adding the precipitate without increasing, carrying out suction filtration to obtain filter residue II, and drying the filter residue II in a 60 ℃ oven to obtain the pure p-nitrobenzoic acid product.
The preparation method of the ferric salt of isophthalic acid comprises the following steps:
and (3) dissolving 4 parts of isophthalic acid in absolute ethyl alcohol to form a 35wt% isophthalic acid solution, dissolving 2 parts of ferric trichloride in absolute ethyl alcohol to form a 25wt% ferric trichloride solution, dripping the isophthalic acid solution into the ferric trichloride solution at a speed of 1 drop/s, reacting at 77 ℃ for 12 hours, filtering to obtain filter residue A, and drying at 90 ℃ for 5 hours to obtain ferric isophthalate.
The interior of the heatable airtight grinding device is made of copper, and the grinding rod is a copper rod.
Example 7
1. Based on the molar parts, 2 parts Ni (NO 3 ) 2 ·6H 2 Placing O, 2 parts of polynuclear isophthalic acid complex and 4 parts of citric acid into a heatable closed grinding device, uniformly mixing, setting the rotating speed to be 100rpm, grinding for 40min, adding 8 parts of ethylene glycol, continuously grinding for 8min, then adding 1.4 parts of paranitrotoluene and 0.6 part of KBr, ensuring that the volume of reactants in the heatable closed grinding device is 20% of the total volume in the heatable closed grinding device, introducing oxygen into the heatable closed grinding device, keeping the pressure in the heatable closed grinding device to be 0.2MPa, and keeping the pressure fluctuation range in the heatable closed grinding device in the subsequent reaction process to be 0.02 MPa;
2. heating the heatable closed grinding device to 70 ℃ at the speed of 4 ℃/min for reaction for 3 hours while continuously grinding, cooling to 40 ℃ at the speed of 2 ℃/min for reaction for 1.5 hours, cooling to 25 ℃ at the speed of 2 ℃/min, and standing for reaction for 2 hours to obtain a reactant I;
3. pouring the reactant I into an ice-water mixture according to the mass ratio of 1:4, melting ice cubes, performing suction filtration to obtain filter residue I, and washing and drying to obtain a p-nitrobenzoic acid crude product;
4. adding the crude p-nitrobenzoic acid into water according to the feed liquid ratio of 1:40 mL, dropwise adding 15wt% of NaOH aqueous solution at the speed of 1 drop/s under the stirring condition of 300rpm until the liquid is red, standing for 30s, dropwise adding anhydrous acetic acid at the speed of 1 drop/s until the solution is colorless, standing for 40s, and suction-filtering to obtain filtrate I;
5. and (3) dropwise adding 50wt% sulfuric acid aqueous solution into the filtrate I at a speed of 1 drop/s under the stirring condition of 300rpm to generate precipitate, continuously dropwise adding the precipitate without increasing, carrying out suction filtration to obtain filter residue II, and drying the filter residue II in a 60 ℃ oven to obtain the pure p-nitrobenzoic acid product.
The preparation method of the polynuclear isophthalic acid complex comprises the following steps:
s1, dissolving 4 parts of isophthalic acid in absolute ethyl alcohol to form an isophthalic acid solution with the weight percent of 35%, dissolving 2 parts of ferric trichloride in absolute ethyl alcohol to form an iron trichloride solution with the weight percent of 25%, dripping the isophthalic acid solution into the iron trichloride solution at the speed of 1 drop/s, reacting for 12 hours at the temperature of 77 ℃, filtering to obtain filter residue A, and drying at the temperature of 90 ℃ for 5 hours to obtain ferric isophthalate salt;
s2, 2 parts of ferric isophthalate and 0.8 part of Cr (NO 3 ) 3 Heating and refluxing in 10 parts of acetone at 65 ℃ for 40min, naturally cooling to 42 ℃, filtering, standing the obtained filtrate B at room temperature for 24h for crystallization, filtering to obtain filter residue B, and washing the filter residue B with water and drying the filter residue B at 80 ℃ for 24h to obtain the polynuclear isophthalic acid complex.
The interior of the heatable airtight grinding device is made of copper, and the grinding rod is a copper rod.
Comparative example 1
1. Based on the molar parts, 4 parts of Fe (NO 3 ) 3 ·9H 2 O,4 parts of citric acid are put into a heatable closed grinding device, after being uniformly mixed, the rotating speed is set to be 100rpm, grinding is carried out for 40min, 8 parts of ethylene glycol is added for continuous grinding for 8min, then 1.4 parts of paranitrotoluene and 0.6 part of KBr are added, the volume of reactants in the heatable closed grinding device is ensured to be 20% of the total volume in the heatable closed grinding device at the moment, then oxygen is introduced into the heatable closed grinding device until the pressure in the heatable closed grinding device is 0.2MPa, and the pressure fluctuation range in the heatable closed grinding device in the subsequent reaction process is kept within 0.02 MPa;
2. heating the heatable closed grinding device to 70 ℃ at the speed of 4 ℃/min for reaction for 3 hours while continuously grinding, cooling to 40 ℃ at the speed of 2 ℃/min for reaction for 1.5 hours, cooling to 25 ℃ at the speed of 2 ℃/min, and standing for reaction for 2 hours to obtain a reactant I;
3. pouring the reactant I into an ice-water mixture according to the mass ratio of 1:4, melting ice cubes, performing suction filtration to obtain filter residue I, and washing and drying to obtain a p-nitrobenzoic acid crude product;
4. adding the crude p-nitrobenzoic acid into water according to the feed liquid ratio of 1:40 mL, dropwise adding 15wt% of NaOH aqueous solution at the speed of 1 drop/s under the stirring condition of 300rpm until the liquid is red, standing for 30s, dropwise adding anhydrous acetic acid at the speed of 1 drop/s until the solution is colorless, standing for 40s, and suction-filtering to obtain filtrate I;
5. and (3) dropwise adding 50wt% sulfuric acid aqueous solution into the filtrate I at a speed of 1 drop/s under the stirring condition of 300rpm to generate precipitate, continuously dropwise adding the precipitate without increasing, carrying out suction filtration to obtain filter residue II, and drying the filter residue II in a 60 ℃ oven to obtain the pure p-nitrobenzoic acid product.
The interior of the heatable airtight grinding device is made of copper, and the grinding rod is a copper rod.
Comparative example 2
1. Putting 4 parts of polynuclear iron isophthalic acid complex by mass, namely 4 parts of citric acid into a heatable closed grinding device, uniformly mixing, setting the rotating speed to be 100rpm, grinding for 40min, adding 8 parts of ethylene glycol, continuously grinding for 8min, then adding 1.4 parts of paranitrotoluene and 0.6 part of KBr, ensuring that the volume of reactants in the heatable closed grinding device is 20% of the total volume in the heatable closed grinding device, introducing oxygen into the heatable closed grinding device, keeping the pressure in the heatable closed grinding device to be 0.2MPa, and keeping the pressure fluctuation range in the heatable closed grinding device in the subsequent reaction process to be within 0.02 MPa;
2. heating the heatable closed grinding device to 70 ℃ at the speed of 4 ℃/min for reaction for 3 hours while continuously grinding, cooling to 40 ℃ at the speed of 2 ℃/min for reaction for 1.5 hours, cooling to 25 ℃ at the speed of 2 ℃/min, and standing for reaction for 2 hours to obtain a reactant I;
3. pouring the reactant I into an ice-water mixture according to the mass ratio of 1:4, melting ice cubes, performing suction filtration to obtain filter residue I, and washing and drying to obtain a p-nitrobenzoic acid crude product;
4. adding the crude p-nitrobenzoic acid into water according to the feed liquid ratio of 1:40 mL, dropwise adding 15wt% of NaOH aqueous solution at the speed of 1 drop/s under the stirring condition of 300rpm until the liquid is red, standing for 30s, dropwise adding anhydrous acetic acid at the speed of 1 drop/s until the solution is colorless, standing for 40s, and suction-filtering to obtain filtrate I;
5. and (3) dropwise adding 50wt% sulfuric acid aqueous solution into the filtrate I at a speed of 1 drop/s under the stirring condition of 300rpm until no precipitate is generated, carrying out suction filtration to obtain filter residue II, and drying the filter residue II in a 60 ℃ oven to obtain the pure p-nitrobenzoic acid product.
The preparation method of the polynuclear isophthalic acid complex comprises the following steps:
s1, dissolving 4 parts of isophthalic acid in ethanol by mass to form a 35wt% isophthalic acid solution, dissolving 2 parts of ferric trichloride in ethanol to form a 25wt% ferric trichloride solution, dripping the isophthalic acid solution into the ferric trichloride solution at a speed of 1 drop/s, reacting at 77 ℃ for 12 hours, filtering to obtain filter residue A, and drying at 90 ℃ for 5 hours to obtain ferric isophthalate salt;
s2, 2 parts of ferric isophthalate and 0.8 part of Cr (NO 3 ) 3 Heating and refluxing in acetone at 65 ℃ for 40min, naturally cooling to 42 ℃, filtering, standing the obtained filtrate B at room temperature for 24h for crystallization, filtering to obtain filter residue B, washing the filter residue B with water, and drying at 80 ℃ for 24h to obtain the polynuclear isophthalic acid complex.
The interior of the heatable airtight grinding device is made of copper, and the grinding rod is a copper rod.
Test case
The yields of p-nitrobenzoic acid prepared in examples and comparative examples were calculated and tested for purity by high performance liquid chromatography. The specific operation is as follows: adopting an Agilent 1260 general type high performance liquid chromatograph; column model: z0RBAX SB-C18,5 μm, 4.6X1250 mm; detection wavelength: 254nm; mobile phase: a-methanol, B-0.8% acetic acid aqueous solution; elution gradient: 0min,30% A. Fwdarw.10 min, 50A%. Fwdarw.20 min,60% A. Fwdarw.30 min,60A%. And calculating the purity of the p-nitrobenzoic acid by an area normalization method. The test results are shown in Table 1.
Table 1: results of P-nitrobenzoic acid yield and purity test
In the invention, local high temperature is generated by grinding under the oxygen atmosphere, so that a reaction substrate paranitrotoluene forms free radicals under the action of an initiator, and paranitrobenzoic acid is generated under lower temperature and lower pressure by the catalysis of valence-changing metal salt, the joint oxidation of nitric acid and oxygen. As can be seen from comparative example 1 and example 3, when the variable metal nitrate or iron salt is used alone, the initial reaction temperature is set at 70℃to obtain the objective p-nitrobenzoic acid with low yield and purity.
In the embodiment 4, the variable-valence metal nitrate and the ferric salt are compounded on the basis of the embodiment 2 to form ferrite, and when the metal halide exists, the ferrite forms a specific crystal form, so that the catalytic efficiency is improved, and in the grinding process, the magnetic effect of the ferrite converts heat energy, so that p-nitrobenzoic acid can be generated at a lower reaction temperature, and the yield and purity are obviously improved. Comparative example 2 self-made polynuclear isophthalic acid complex as ferric salt contains benzoate ion, nitrate ion and acetone molecule, and is bridged with iron ion through hydrogen bond interaction, and takes oxygen atom as center to form stable space conformation for magnetic exchange, and the polynuclear isophthalic acid complex has certain magnetism and has better catalytic effect compared with comparative example 1. In example 7, the addition of the valence-variable metal nitrate on the basis of comparative example 2 forms more gaps in the generated ferrite unit cells than in examples 4, 5 and 6, which is beneficial to doping and substitution of the valence-variable metal, further improves the magnetic performance and improves the catalytic efficiency.
Claims (3)
1. A method for synthesizing p-nitrobenzoic acid, comprising the steps of:
(1) 2-3 parts of variable valence metal nitrate, 2-5 parts of ferric salt and 2-4 parts of organic acid are put into a heatable airtight grinding device according to parts by mol, after being uniformly mixed, the mixture is ground for 30-60min at a rotating speed of 80-200rpm, 5-10 parts of organic solvent is added for continuously grinding for 5-10min, then 1-2 parts of paranitrotoluene and 0.5-1 part of initiator are added, the volume of reactants in the heatable airtight grinding device at the moment is ensured to be 15-30% of the total volume in the heatable airtight grinding device, then oxygen is introduced into the heatable airtight grinding device until the pressure in the heatable airtight grinding device is 0.1-0.3MPa, and the pressure fluctuation range in the heatable airtight grinding device in the subsequent reaction process is kept within 0.02-0.03 MPa;
(2) Heating the heatable closed grinding device to 60-70 ℃ at the speed of 3-5 ℃/min for reacting for 2-3h while continuously grinding, cooling to 40-50 ℃ at the speed of 1-3 ℃/min for reacting for 1-2h, cooling to 20-25 ℃ at the speed of 1-3 ℃/min, and standing for reacting for 1-2h to obtain a reactant I;
(3) The reactant I is prepared by the following steps of: (3-5) pouring the mixture into an ice-water mixture, melting ice cubes, performing suction filtration to obtain filter residue I, and washing and drying to obtain a p-nitrobenzoic acid crude product;
(4) The crude p-nitrobenzoic acid product is prepared according to the feed liquid ratio of 1: (20-50) mL of water, dropwise adding 10-18wt% of NaOH aqueous solution at a speed of 0.5-1 drop/s under the stirring condition of 200-400rpm until the liquid is red, standing for 20-40s, dropwise adding anhydrous acetic acid at a speed of 0.5-1 drop/s until the solution is colorless, standing for 20-40s, and carrying out suction filtration to obtain filtrate I;
(5) Dripping 40-60wt% sulfuric acid water solution into the filtrate I at the speed of 0.5-1 drop/s under the stirring condition of 200-400rpm to generate precipitate, continuously dripping the solution into the precipitate without increasing, carrying out suction filtration to obtain filter residue II, and drying the filter residue II in a 50-60 ℃ oven to obtain pure p-nitrobenzoic acid;
the valence-variable metal nitrate is nickel nitrate;
the ferric salt is polynuclear iron isophthalic acid complex; the preparation method of the polynuclear isophthalic acid complex comprises the following steps:
s1, dissolving 3-5 parts of isophthalic acid in an organic solvent to form 30-45wt% of isophthalic acid solution, dissolving 1-2 parts of ferric trichloride in the organic solvent to form 20-30wt% of ferric trichloride solution, dripping the isophthalic acid solution into the ferric trichloride solution at the speed of 0.5-1 drop/s, reacting at 75-80 ℃ for 8-16h, filtering to obtain filter residue A, and drying at 80-90 ℃ for 4-6h to obtain ferric isophthalate salt;
s2, 1 to 2 parts of ferric salt of isophthalic acid and 0.5 to 1 part of Cr (NO) 3 ) 3 Heating and refluxing in 8-14 acetone at 60-75deg.C for 25-50min, naturally cooling to 40-45deg.C, filtering, standing at room temperature for crystallization, filtering to obtain residue B, washing with water, and oven drying to obtain polynuclear isophthalic acid complex.
2. The method for synthesizing p-nitrobenzoic acid as claimed in claim 1, wherein the organic solvent is at least one of ethanol, ethylene glycol, glycerol and isopropanol.
3. The method of synthesizing p-nitrobenzoic acid of claim 1 wherein the initiator is a metal halide.
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