CN113999105A - Preparation method of hydroxyl acidic organic ligand - Google Patents
Preparation method of hydroxyl acidic organic ligand Download PDFInfo
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- CN113999105A CN113999105A CN202111453127.5A CN202111453127A CN113999105A CN 113999105 A CN113999105 A CN 113999105A CN 202111453127 A CN202111453127 A CN 202111453127A CN 113999105 A CN113999105 A CN 113999105A
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- acid
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- carboxylic acid
- aromatic carboxylic
- bicarbonate
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- 239000013110 organic ligand Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 11
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 10
- 239000012043 crude product Substances 0.000 claims abstract description 31
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001914 filtration Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000007670 refining Methods 0.000 claims abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000012467 final product Substances 0.000 claims abstract description 3
- 150000001261 hydroxy acids Chemical class 0.000 claims abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- -1 alkali metal bicarbonate Chemical class 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 9
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 9
- 239000011736 potassium bicarbonate Substances 0.000 claims description 9
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 235000011181 potassium carbonates Nutrition 0.000 claims description 8
- UYEMGAFJOZZIFP-UHFFFAOYSA-N 3,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC(O)=C1 UYEMGAFJOZZIFP-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 229960004337 hydroquinone Drugs 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 4
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical group [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 150000001735 carboxylic acids Chemical class 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 description 21
- 239000001257 hydrogen Substances 0.000 description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 18
- 238000001228 spectrum Methods 0.000 description 18
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical class OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 description 17
- 239000007789 gas Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- CDOWNLMZVKJRSC-UHFFFAOYSA-N 2-hydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1 CDOWNLMZVKJRSC-UHFFFAOYSA-N 0.000 description 8
- 238000004537 pulping Methods 0.000 description 8
- 239000012621 metal-organic framework Substances 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- OHLSHRJUBRUKAN-UHFFFAOYSA-N 2,3-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1O OHLSHRJUBRUKAN-UHFFFAOYSA-N 0.000 description 4
- YNIWBQWSPPNHRN-UHFFFAOYSA-N 2,6-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C(O)=C1 YNIWBQWSPPNHRN-UHFFFAOYSA-N 0.000 description 4
- CYKLQLRNONSQPH-UHFFFAOYSA-N 4,6-dihydroxycyclohexa-1,5-diene-1,4-dicarboxylic acid Chemical compound OC(=O)C1=CCC(O)(C(O)=O)C=C1O CYKLQLRNONSQPH-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 150000003504 terephthalic acids Chemical class 0.000 description 2
- DNUYOWCKBJFOGS-UHFFFAOYSA-N 2-[[10-(2,2-dicarboxyethyl)anthracen-9-yl]methyl]propanedioic acid Chemical compound C1=CC=C2C(CC(C(=O)O)C(O)=O)=C(C=CC=C3)C3=C(CC(C(O)=O)C(O)=O)C2=C1 DNUYOWCKBJFOGS-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of a hydroxyl acidic organic ligand, belonging to the technical field of organic synthesis. In order to solve the problems of complex preparation method and high requirement on equipment of the existing organic ligand, the invention provides a preparation method of a hydroxy acid organic ligand, which comprises the steps of mixing dihydroxy aromatic hydrocarbon, monohydroxy aromatic carboxylic acid or dihydroxy aromatic carboxylic acid with metal alkali, alkali carbonate and alkali bicarbonate according to a certain molar ratio, and then adding the mixture into a high-pressure kettle; replacing with carbon dioxide gas, reacting at a certain temperature and pressure, reacting for a certain time to obtain a crude product, cooling the crude product to normal temperature, dissolving with hot water, adjusting with acid, filtering to obtain a carboxylic acid organic ligand, and refining with an organic solvent to obtain the final product. The method simplifies the requirements on reaction equipment and post-treatment operation, can effectively improve the yield of the organic ligand, has the yield of more than 70 percent and the purity of more than 99 percent, is suitable for industrial expanded production, and can meet the market demand.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of a hydroxy acidic organic ligand.
Background
The hydroxyl carboxyl aromatic hydrocarbon compound is a very important organic intermediate, wherein the dihydroxyterephthalic acid compound has the rigidity of a straight-chain compound of benzene rings and a hydroxyl active side group, so that the ultraviolet resistance, the composite caking property and the compression resistance of the material are ideal. Therefore, polyhydroxy terephthalic acid compounds, such as certain dihydroxy terephthalic acid compounds, replace TPA as polymer ligands, can effectively improve polymer properties, so that the polyhydroxy terephthalic acid compounds are widely applied to synthesis of medicines and functional materials, particularly high molecular modified materials, such as organic luminescent materials, modified fibers and the like, and can utilize hydrogen bonds formed by hydroxyl groups in molecules to improve some properties. The dihydroxy terephthalic acid compound has the properties of terephthalic acid and salicylic acid-like substances, has potential performance, and shows good application prospect.
Another important application of the hydroxycarboxyl aromatic hydrocarbon compound is as an Organic ligand to synthesize Metal-Organic Frameworks (MOFs), which is a new Organic-inorganic hybrid crystalline porous material grown in the last twenty years. Such porous adsorbent materials are typically obtained in a self-assembled form from metal centers or clusters and multidentate organic ligands. MOFs often have an ultra-large specific surface area, and the diversity of organic ligands enables the MOFs to have ultra-strong designability, so that the adjustment of the pore size and the topological structure can be easily realized; meanwhile, functional modification of the surface chemical environment of the pore channel can be easily realized by introducing special functional sites such as-NH 2, -OH, -CH3, open metal sites and the like. Therefore, MOFs show wide application prospects in fields of gas storage and separation, heterogeneous catalysis, fluorescence detection, drug sustained release, magnetism and the like.
As an important organic ligand for synthesizing MOFs materials, the market demand of hydroxy carboxyl aromatic hydrocarbon compounds is gradually increased, but the existing preparation method of the organic ligand is complex and has high requirement on equipment, so that the yield of the organic ligand is limited, and the market demand cannot be met.
Disclosure of Invention
The invention provides a preparation method of a hydroxy acidic organic ligand, aiming at solving the problems of complex preparation method and high requirement on equipment of the existing organic ligand.
The technical scheme of the invention is as follows:
a preparation method of hydroxy acid organic ligand is to mix dihydroxy aromatic hydrocarbon, monohydroxy aromatic carboxylic acid or dihydroxy aromatic carboxylic acid with metal alkali, alkali carbonate and alkali bicarbonate according to a certain molar ratio and then add them into a high-pressure autoclave; replacing with carbon dioxide gas, reacting at a certain temperature and pressure, reacting for a certain time to obtain a crude product, cooling the crude product to normal temperature, dissolving with hot water, adjusting the pH value to 1-2 with acid, filtering to obtain a carboxyl acidic organic ligand, and refining with an organic solvent to obtain a final product.
Further, the molar ratio of the dihydroxy aromatic hydrocarbon, the monohydroxy aromatic carboxylic acid or the dihydroxy aromatic carboxylic acid to the metal base, the alkali metal carbonate or the alkali metal bicarbonate is 1: 0-0.50: 0-0.65: 1.0-5.0.
Further, the dihydroxy aromatic hydrocarbon, the monohydroxy aromatic carboxylic acid or the dihydroxy aromatic carboxylic acid is one of 1, 4-benzenediol, 1, 2-benzenediol, 1, 3-benzenediol, 4 '-biphenyldiol, 2' -biphenyldiol, 3-hydroxybenzoic acid or 3, 5-dihydroxybenzoic acid.
Further, the metal base is one of lithium hydroxide, sodium hydroxide or potassium hydroxide.
Further, the alkali metal carbonate is lithium carbonate, sodium carbonate or potassium carbonate; the alkali metal bicarbonate is lithium bicarbonate, sodium bicarbonate or potassium bicarbonate.
Further, the reaction temperature is 180-260 ℃, the reaction pressure is 2-5 MPa, and the reaction time is 12-24 hours.
Further, the acid used for adjusting the pH value is hydrochloric acid, sulfuric acid, nitric acid, acetic acid or formic acid.
Further, the organic solvent used for refining the product is methanol, ethanol, isopropanol, ethyl acetate, acetone, chloroform or carbon tetrachloride.
The invention has the beneficial effects that:
the invention provides a preparation method of a hydroxyl acidic organic ligand, which replaces carbon dioxide environment with alkali metal bicarbonate, simplifies the requirements on reaction equipment and reduces the production cost; the treatment of the crude product does not need processes such as activated carbon decoloration, ammonia water dissolution, full stirring in hydrochloric acid, multiple times of water washing and the like, so that the post-treatment operation is simplified, the pollution to the environment is obviously reduced, the production efficiency is improved, the yield of organic ligands can be effectively improved, and the market demand is met.
The preparation method is simple and convenient, is suitable for industrial expanded production, has the yield of the prepared hydroxyl acidic organic ligand of more than 70 percent and the purity of more than 99 percent, and can be used for producing polymers and synthesizing metal-organic frameworks.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of 2, 5-dihydroxyterephthalic acid prepared in example 1;
FIG. 2 is a nuclear magnetic hydrogen spectrum of 2, 3-dihydroxy terephthalic acid prepared in example 2;
FIG. 3 is a nuclear magnetic hydrogen spectrum of 4, 6-dihydroxy terephthalic acid prepared in example 3;
FIG. 4 is a nuclear magnetic hydrogen spectrum of 4,4 '-dihydroxy-3, 3' -benzenedicarboxylic acid prepared in example 4;
FIG. 5 is a nuclear magnetic hydrogen spectrum of 2-hydroxyterephthalic acid prepared in example 5;
FIG. 6 is a nuclear magnetic hydrogen spectrum of 2, 6-dihydroxyterephthalic acid prepared in example 6.
Detailed Description
The technical solutions of the present invention are further described below with reference to the following examples, but the present invention is not limited thereto, and any modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention. The process equipment or apparatus not specifically mentioned in the following examples are conventional in the art, and if not specifically mentioned, the raw materials and the like used in the examples of the present invention are commercially available; unless otherwise specified, the technical means used in the examples of the present invention are conventional means well known to those skilled in the art.
Example 1
This example provides a process for the preparation of 2, 5-dihydroxyterephthalic acid.
Mixing 0.91mol of 1, 4-benzenediol, 0.091mol of potassium hydroxide, 0.118mol of potassium carbonate and 0.33mol of potassium bicarbonate, adding the mixture into a 1L high-pressure kettle, replacing air in the high-pressure kettle with carbon dioxide gas, reacting for 12 hours at the temperature of 220 ℃ and the pressure of 2.2MPa, dissolving a crude product obtained by the reaction in hot water at the temperature of 80 ℃, adjusting the pH value of the obtained solution to 1-2 with hydrochloric acid with the mass concentration of 36%, filtering to obtain a crude product, placing the crude product into an acetone solution, pulping at the room temperature of 25 ℃, uniformly stirring a system, and filtering to obtain a refined 2, 5-dihydroxyterephthalic acid product, wherein the purity of the product is 99.8%, and the yield is 70%.
FIG. 1 is a nuclear magnetic hydrogen spectrum of 2, 5-dihydroxyterephthalic acid prepared in this example; shown as nuclear magnetic hydrogen spectrum data in the figure1H-NMR(400MHz,DMSO)δ:7.284(s 2H),10.972(dr.s 2H)。
Example 2
This example provides a process for the preparation of 2, 3-dihydroxyterephthalic acid.
Mixing 0.91mol of 1, 2-benzenediol, 0.091mol of potassium hydroxide, 0.118mol of potassium carbonate and 0.30mol of potassium bicarbonate, adding the mixture into a 1L high-pressure kettle, replacing air in the high-pressure kettle with carbon dioxide gas, reacting for 12 hours at the temperature of 190 ℃ and the pressure of 2.0MPa, dissolving a crude product obtained by the reaction in hot water at the temperature of 80 ℃, adjusting the pH value of the obtained solution to 1-2 by using 36% sulfuric acid, filtering to obtain a crude product, placing the crude product into an acetone solution, pulping at the room temperature of 25 ℃, uniformly stirring a system, and filtering to obtain a refined 2, 3-dihydroxyterephthalic acid product, wherein the purity of the product is 99.5%, and the yield is 85.7%.
FIG. 2 is a nuclear magnetic hydrogen spectrum of 2, 3-dihydroxy terephthalic acid prepared in this example; shown as nuclear magnetic hydrogen spectrum data in the figure1H-NMR(400MHz,DMSO)δ:7.29(s 2H),12.26(dr.s 2H)。
Example 3
This example provides a process for the preparation of 4, 6-dihydroxyterephthalic acid.
Mixing 0.91mol of 1, 3-benzenediol, 0.091mol of potassium hydroxide, 0.118mol of potassium carbonate and 0.30mol of potassium bicarbonate, adding the mixture into a 1L high-pressure kettle, replacing air in the high-pressure kettle with carbon dioxide gas, reacting for 12 hours at the temperature of 190 ℃ and the pressure of 2.0MPa, dissolving a crude product obtained by the reaction in hot water at the temperature of 80 ℃, adjusting the pH value of the obtained solution to 1-2 by using nitric acid with the mass concentration of 36%, filtering to obtain a crude product, placing the crude product into an acetone solution, pulping at the room temperature of 25 ℃, uniformly stirring a system, and filtering to obtain a refined 4, 6-dihydroxyterephthalic acid product, wherein the purity of the product is 99.6%, and the yield is 87.2%.
FIG. 3 is a nuclear magnetic hydrogen spectrum of 4, 6-dihydroxyterephthalic acid prepared in this example; shown as nuclear magnetic hydrogen spectrum data in the figure1H-NMR(400MHz,DMSO)δ:,6.426(s 1H)，δ:8.315(s 1H),12.047(dr.s 2H)。
Example 4
This example provides a method for the preparation of 4,4 '-dihydroxy-3, 3' -isophthalic acid.
Mixing 0.54mol of 4,4' -benzenediol, 0.273mol of potassium hydroxide, 0.355mol of potassium carbonate and 0.22mol of potassium bicarbonate, adding the mixture into a 1L high-pressure kettle, replacing air in the high-pressure kettle with carbon dioxide gas, reacting for 24 hours at the temperature of 240 ℃ and the pressure of 3.0MPa, dissolving a crude product obtained by the reaction in hot water at the temperature of 80 ℃, adjusting the pH of the obtained solution to 1-2 with acetic acid, filtering to obtain a crude product, placing the crude product in an acetone solution, pulping at the room temperature of 25 ℃, uniformly stirring a system, and filtering to obtain a refined 4,4' -dihydroxy-3, 3 ' -benzenedicarboxylic acid product, wherein the purity of the product is 99.1%, and the yield is 70.7%.
FIG. 4 shows the nuclear magnetic hydrogen spectrum of 4,4 '-dihydroxy-3, 3' -benzenedicarboxylic acid prepared in this example; shown as nuclear magnetic hydrogen spectrum data in the figure1H-NMR (400MHz in DMSO), delta: 7.037-7.058 (s2H), delta: 7.775-7.803 (s2H), delta: 7.964-7.970 (s2H), delta: 11.369 is hydroxyl active hydrogen, and delta: 13.974 is carboxyl active hydrogen.
Example 5
This example provides a process for the preparation of 2-hydroxyterephthalic acid.
Mixing 0.725mol of m-hydroxybenzoic acid, 0.273mol of potassium hydroxide, 0.355mol of potassium carbonate and 1.03mol of potassium bicarbonate, adding the mixture into a 1L high-pressure autoclave, replacing air in the high-pressure autoclave with carbon dioxide gas, reacting for 12 hours under the conditions that the temperature is 180 ℃ and the pressure is 2.0MPa, dissolving a crude product obtained by the reaction in hot water at 80 ℃, adjusting the pH of the obtained solution to 1-2 with formic acid, filtering to obtain a crude product, placing the crude product in an acetone solution, pulping at the room temperature of 25 ℃, uniformly stirring a system, and filtering to obtain a refined 2-hydroxy terephthalic acid product, wherein the purity of the product is 99.3%, and the yield is 81.6%.
FIG. 5 shows a nuclear magnetic hydrogen spectrum of 2-hydroxyterephthalic acid prepared in this example; shown as nuclear magnetic hydrogen spectrum data in the figure1H-NMR(400MHz,DMSO)δ:7.445～7.477(s 2H),δ:7.887～7.907(s 1H)。
Example 6
This example provides a process for the preparation of 2, 6-dihydroxyterephthalic acid.
Mixing 0.727mol of 3, 5-dihydroxybenzoic acid, 0.273mol of potassium hydroxide, 0.355mol of potassium carbonate and 1.1mol of potassium bicarbonate, adding the mixture into a 1L high-pressure kettle, replacing air in the high-pressure kettle with carbon dioxide gas, reacting for 12 hours at the temperature of 200 ℃ and the pressure of 2MPa, dissolving a crude product obtained by the reaction in hot water at the temperature of 80 ℃, adjusting the pH value of the obtained solution to 1-2 with hydrochloric acid with the mass concentration of 36%, filtering to obtain a crude product, placing the crude product into an acetone solution, pulping at the room temperature of 25 ℃, uniformly stirring a system, and filtering to obtain a refined 2, 6-dihydroxy terephthalic acid product, wherein the purity of the product is 99.71%, and the yield is 88.2%.
FIG. 6 is a nuclear magnetic hydrogen spectrum of 2, 6-dihydroxyterephthalic acid prepared in this example; shown as nuclear magnetic hydrogen spectrum data in the figure1H-NMR(400MHz,DMSO)δ:6.64(s 2H),12.77(dr.s 2H)。
Example 7
This example provides a process for the preparation of 2, 5-dihydroxyterephthalic acid.
Mixing 0.91mol of 1, 4-benzenediol, 0.091mol of sodium hydroxide, 0.121mol of sodium carbonate and 0.38mol of sodium bicarbonate, adding the mixture into a 1L high-pressure kettle, replacing air in the high-pressure kettle with carbon dioxide gas, reacting for 12 hours at the temperature of 220 ℃ and the pressure of 2.2MPa, dissolving a crude product obtained by the reaction in hot water at the temperature of 80 ℃, adjusting the pH value of the obtained solution to 1-2 with hydrochloric acid with the mass concentration of 36%, filtering to obtain a crude product, placing the crude product into an acetone solution, pulping at the room temperature of 25 ℃, uniformly stirring a system, and filtering to obtain a refined 2, 5-dihydroxyterephthalic acid product, wherein the purity of the product is 99.6%, and the yield is 65%.
Example 8
This example provides a process for the preparation of 2, 5-dihydroxyterephthalic acid.
Mixing 0.91mol of 1, 4-benzenediol, 0.091mol of potassium hydroxide, 0.118mol of lithium carbonate and 0.33mol of potassium bicarbonate, adding the mixture into a 1L high-pressure kettle, replacing air in the high-pressure kettle with carbon dioxide gas, reacting for 12 hours at the temperature of 220 ℃ and the pressure of 2.2MPa, dissolving a crude product obtained by the reaction in hot water at the temperature of 80 ℃, adjusting the pH value of the obtained solution to 1-2 with hydrochloric acid with the mass concentration of 36%, filtering to obtain a crude product, placing the crude product into an acetone solution, pulping at the room temperature of 25 ℃, uniformly stirring a system, and filtering to obtain a refined 2, 5-dihydroxyterephthalic acid product, wherein the purity of the product is 99.3%, and the yield is 62%.
Claims (8)
1. A preparation method of hydroxy acid organic ligand is characterized in that dihydroxy aromatic hydrocarbon, monohydroxy aromatic carboxylic acid or dihydroxy aromatic carboxylic acid and metal alkali, alkali carbonate and alkali bicarbonate are mixed according to a certain molar ratio and then added into an autoclave; replacing with carbon dioxide gas, reacting at a certain temperature and pressure, reacting for a certain time to obtain a crude product, cooling the crude product to normal temperature, dissolving with hot water, adjusting the pH value to 1-2 with acid, filtering to obtain a carboxyl acidic organic ligand, and refining with an organic solvent to obtain a final product.
2. The method of claim 1, wherein the molar ratio of the dihydroxy aromatic hydrocarbon, the monohydroxy aromatic carboxylic acid, or the dihydroxy aromatic carboxylic acid to the metal base, the alkali metal carbonate, or the alkali metal bicarbonate is 1:0 to 0.50:0 to 0.65:1.0 to 5.0.
3. The method of claim 1 or 2, wherein the dihydroxy aromatic hydrocarbon, the monohydroxy aromatic carboxylic acid, or the dihydroxy aromatic carboxylic acid is one of 1, 4-benzenediol, 1, 2-benzenediol, 1, 3-benzenediol, 4 '-biphenyldiol, 2' -biphenyldiol, 3-hydroxybenzoic acid, or 3, 5-dihydroxybenzoic acid.
4. The method of claim 3, wherein the metal base is one of lithium hydroxide, sodium hydroxide and potassium hydroxide.
5. The method of claim 4, wherein the alkali metal carbonate is lithium carbonate, sodium carbonate or potassium carbonate; the alkali metal bicarbonate is lithium bicarbonate, sodium bicarbonate or potassium bicarbonate.
6. The method for preparing the hydroxy acidic organic ligand according to claim 5, wherein the reaction temperature is 180-260 ℃, the reaction pressure is 2-5 MPa, and the reaction time is 12-24 h.
7. The method of claim 6, wherein the acid used to adjust the pH is hydrochloric acid, sulfuric acid, nitric acid, acetic acid, or formic acid.
8. The method according to claim 7, wherein the organic solvent used for purifying the product is methanol, ethanol, isopropanol, ethyl acetate, acetone, chloroform or carbon tetrachloride.
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