CN102311357B - Preparation method of 2-hydroxy-4-aminobenzoic acid - Google Patents
Preparation method of 2-hydroxy-4-aminobenzoic acid Download PDFInfo
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- CN102311357B CN102311357B CN201110312793.7A CN201110312793A CN102311357B CN 102311357 B CN102311357 B CN 102311357B CN 201110312793 A CN201110312793 A CN 201110312793A CN 102311357 B CN102311357 B CN 102311357B
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- alcohol
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- WUBBRNOQWQTFEX-UHFFFAOYSA-N 4-aminosalicylic acid Chemical compound NC1=CC=C(C(O)=O)C(O)=C1 WUBBRNOQWQTFEX-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 14
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 13
- 239000011734 sodium Substances 0.000 claims abstract description 11
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 11
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 9
- 238000011084 recovery Methods 0.000 claims abstract description 9
- -1 sodium alkoxide Chemical class 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012065 filter cake Substances 0.000 claims abstract description 4
- 239000000706 filtrate Substances 0.000 claims abstract description 4
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 235000011089 carbon dioxide Nutrition 0.000 claims description 12
- RGYMUBJJCDDKLR-UHFFFAOYSA-N NC1=CC=CC([Na])=C1.OC1=CC=CC=C1 Chemical compound NC1=CC=CC([Na])=C1.OC1=CC=CC=C1 RGYMUBJJCDDKLR-UHFFFAOYSA-N 0.000 claims description 9
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical group [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 3
- 239000002440 industrial waste Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 4
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 abstract 2
- LTPRVFBPLWKTRO-UHFFFAOYSA-N [Na].Nc1cccc(O)c1 Chemical compound [Na].Nc1cccc(O)c1 LTPRVFBPLWKTRO-UHFFFAOYSA-N 0.000 abstract 2
- 229940018563 3-aminophenol Drugs 0.000 abstract 1
- 238000004821 distillation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a preparation method of 2-hydroxy-4-aminobenzoic acid. The preparation method comprises the following steps that 1, m-aminophenol and a sodium alkoxide undergo a reaction in an alcoholic solution at room temperature for 0.8 to 1.2 hours to produce an m-aminophenol sodium salt alcoholic solution; and 2, the m-aminophenol sodium salt alcoholic solution is putted into a high-pressure reactor; carbon dioxide recovery gas is fed into the high-pressure reactor to undergo a reaction for 1 to 5 hours under supercritical conditions of carbon dioxide; after the reaction, the obtained reaction solution is cooled to room temperature and then is filtered; the filtrate is subjected to reduced pressure distillation so that a solvent alcohol is removed and a solid is obtained; the solid is dissolved by water to form a solution; an inorganic acid is added into the solution to adjust a pH value of the solution to a pH value of 6 to 7; and when a solid is separated out, the solution is filtered again to obtain a 2-hydroxy-4-aminobenzoic acid filter cake. The preparation method of 2-hydroxy-4-aminobenzoic acid has the characteristics of low cost, no pollution, high efficiency, high yield and the like.
Description
Technical field
The present invention relates to a kind of preparation method of 2-hydroxy-4-aminobenzoic acid.
Background technology
2-hydroxy-4-aminobenzoic acid structure, suc as formula shown in I, is important medicine and dyestuff synthetic intermediate.It mainly be take Metha Amino Phenon and is prepared as raw material.There is bibliographical information to cross with carbonic acid gas and Metha Amino Phenon reaction preparation 2-hydroxy-4-aminobenzoic acid (Bulletin of the Chemical Society of Japan, 2003, vol.76, # 11 p.2191-2196), its reaction process excess Temperature (temperature of reaction is 125～230 ℃), not only energy consumption is excessive, also has larger potential safety hazard; In this method, use pure carbon dioxide as raw material, if use carbon dioxide recovery gas instead as raw material, also contain other oxidation or reducing gas outward owing to reclaiming removing carbon dioxide in gas, therefore unnecessary side reaction can occur, thereby cause the reduction (causing yield that 60% left and right is only arranged) of ultimate yield.Separately there is other bibliographical information to react preparation 2-hydroxy-4-aminobenzoic acid (Journal of Organic Chemistry with Metha Amino Phenon with carbonic acid gas, 1958, vol.23, p.1422), although its process temperature is not high, owing to reacting in the aqueous solution, inevitably bring amino hydrolysis, cause reaction to have a small amount of 2, the 4-resorcylic acid generates, and has increased separation costs.
Summary of the invention
The technical problem to be solved in the present invention is to provide the preparation method of a kind of with low cost, clean and effective, 2-hydroxy-4-aminobenzoic acid that yield is high.
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of 2-hydroxy-4-aminobenzoic acid, comprise the following steps:
1), under room temperature, Metha Amino Phenon reacts in alcohol with sodium alkoxide 0.8～1.2 hour, obtains the alcoholic solution of m-aminophenyl sodium phenolate; The mol ratio of Metha Amino Phenon and sodium alkoxide is 1: 1～5;
2), the alcoholic solution of m-aminophenyl sodium phenolate is put into to autoclave, pass into carbon dioxide recovery gas, react 1～5 hour (more excellent is 3～5 hours) under the super critical condition of carbonic acid gas, the mol ratio of m-aminophenyl sodium phenolate and carbonic acid gas is 1: 1～10;
Reaction is down to room temperature by the reaction solution of gained after finishing, and filters, and filtrate decompression is steamed and desolventized alcohol, obtains solid; Add water by dissolution of solid (consumption of water only need make this solid dissolve get final product), obtain solution; Add inorganic acid for adjusting pH to 6～7 in gained solution, have solid to separate out, again filter, the filter cake of gained is the 2-hydroxy-4-aminobenzoic acid.
Improvement as the preparation method of 2-hydroxy-4-aminobenzoic acid of the present invention: the super critical condition of carbonic acid gas is: 50～100 ℃ of temperature, pressure 8～15Mpa (this pressure is regulated by the mode of temperature and nitrogen pressurization).
Further improvement as the preparation method of 2-hydroxy-4-aminobenzoic acid of the present invention: sodium alkoxide is sodium methylate, sodium ethylate, sodium propylate or sodium butylate.
Further improvement as the preparation method of 2-hydroxy-4-aminobenzoic acid of the present invention: alcohol with the amount ratio of Metha Amino Phenon is: the Metha Amino Phenon of alcohol/0.05mol of 80～120mL.
Further improvement as the preparation method of 2-hydroxy-4-aminobenzoic acid of the present invention: alcohol is methyl alcohol, ethanol, propyl alcohol or butanols.
Further improvement as the preparation method of 2-hydroxy-4-aminobenzoic acid of the present invention: carbon dioxide recovery gas is industrial waste gas, and the volume content of carbonic acid gas is 65～75%.
In step 1 of the present invention) in, Metha Amino Phenon can all be converted into the m-aminophenyl sodium phenolate.In the present invention, mineral acid refers to the conventional mineral acids such as hydrochloric acid, sulfuric acid, can be pure mineral acid, also can be the inorganic acid solution of various concentration; This routine techniques that is the industry.In step 1 of the present invention) in, " alcohol " in sodium alkoxide is identical with the kind of " alcohol " as solvent.
The preparation method of 2-hydroxy-4-aminobenzoic acid of the present invention is reacted under normal temperature (being room temperature), and without carrying out follow-up separating treatment; Therefore there is with low cost, environmental friendliness, the characteristics that technique is simple, yield is high.The present invention uses carbon dioxide recovery gas (for industrial waste gas) for raw material, not only can reduce costs, and can also realize the comprehensive utilization of waste gas.
Embodiment
Room temperature in the present invention refers to 10～30 ℃.
The preparation method of embodiment 1, a kind of 2-hydroxy-4-aminobenzoic acid, carry out following steps successively:
1), under room temperature, take 100mL methyl alcohol as solvent, add 5.5g Metha Amino Phenon (0.05mol), (be for example 3 batches) in batches and add 8.1g sodium methylate (0.15mol) stirring reaction 1 hour, obtain the alcoholic solution of m-aminophenyl sodium phenolate.
2), the alcoholic solution of m-aminophenyl sodium phenolate is added in autoclave, in autoclave, be filled with carbon dioxide recovery gas (the about 11g of carbon dioxide content, 0.25mol; In this carbon dioxide recovery gas, the volume content of carbonic acid gas is 70%), be warming up to 70 ℃, fill nitrogen adjusting still and be depressed into 9MPa, stirring reaction finishes reaction in 3 hours.
Reaction is down to room temperature by the reaction solution of gained after finishing, and filters, and filtrate decompression (0.02MPa) is steamed and desolventized alcohol (being methyl alcohol), obtains solid; Add water by dissolution of solid (consumption of water only needs to make this dissolution of solid to get final product), obtain settled solution; In the gained settled solution, add the dilute hydrochloric acid of mass concentration 10% to regulate pH to 6～7, have solid to separate out, again filter, collect filter cake, obtain 2-hydroxy-4-aminobenzoic acid 7.0g (purity is 97%), yield is 90.6%.
Embodiment 2-7:
Reaction times (being called for short t) in the kind (being called for short S) of solvent in change embodiment 1 (i.e. alcohol), sodium alkoxide kind (being called for short R1) and consumption (being called for short m1), the effective add-on of carbonic acid gas (abbreviation m2), temperature of reaction (being called for short T), pressure (being called for short P), autoclave, the yield that obtains corresponding 2-hydroxy-4-aminobenzoic acid is Y, purity is P, and detailed data is in Table 1.
Table 1
Finally, it is also to be noted that, what more than enumerate is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (3)
1.2-the preparation method of hydroxy-4-aminobenzoic acid is characterized in that comprising the following steps:
1), under room temperature, Metha Amino Phenon reacts in alcohol with sodium alkoxide 0.8 ~ 1.2 hour, obtains the alcoholic solution of m-aminophenyl sodium phenolate; The mol ratio of Metha Amino Phenon and sodium alkoxide is 1:1 ~ 5;
Described sodium alkoxide is sodium methylate, sodium ethylate, sodium propylate or sodium butylate, and corresponding alcohol is methyl alcohol, ethanol, propyl alcohol or butanols;
2), the alcoholic solution of described m-aminophenyl sodium phenolate is put into to autoclave, pass into carbon dioxide recovery gas, react under the super critical condition of carbonic acid gas 1 ~ 5 hour, the mol ratio of described m-aminophenyl sodium phenolate and carbonic acid gas is 1:1 ~ 10;
The super critical condition of described carbonic acid gas is: 50 ~ 100 ℃ of temperature, pressure 8 ~ 15Mpa;
Reaction is down to room temperature by the reaction solution of gained after finishing, and filters, and filtrate decompression is steamed and desolventized alcohol, obtains solid; Add water by dissolution of solid, obtain solution; Add inorganic acid for adjusting pH to 6 ~ 7 in gained solution, have solid to separate out, again filter, the filter cake of gained is the 2-hydroxy-4-aminobenzoic acid.
2. the preparation method of 2-hydroxy-4-aminobenzoic acid according to claim 1, it is characterized in that: the amount ratio of described alcohol and Metha Amino Phenon is: the Metha Amino Phenon of alcohol/0.05mol of 80 ~ 120mL.
3. the preparation method of 2-hydroxy-4-aminobenzoic acid according to claim 2, it is characterized in that: described carbon dioxide recovery gas is industrial waste gas, the volume content of carbonic acid gas is 65 ~ 75%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110312793.7A CN102311357B (en) | 2011-10-17 | 2011-10-17 | Preparation method of 2-hydroxy-4-aminobenzoic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110312793.7A CN102311357B (en) | 2011-10-17 | 2011-10-17 | Preparation method of 2-hydroxy-4-aminobenzoic acid |
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| Publication Number | Publication Date |
|---|---|
| CN102311357A CN102311357A (en) | 2012-01-11 |
| CN102311357B true CN102311357B (en) | 2014-01-08 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1137654A (en) * | 1966-02-01 | 1968-12-27 | Ile De France | 5-halosalicylic acid derivatives |
| GB1159938A (en) * | 1965-12-10 | 1969-07-30 | Ile De France | A Process for the Preparation of 5-Halobenzoic Acid Ester Derivatives |
| US5643494A (en) * | 1993-05-21 | 1997-07-01 | Hoechst Aktiengesellschaft | Process for the preparation of aromatic hydroxy carboxylic acids |
| CN102126977A (en) * | 2010-12-25 | 2011-07-20 | 浙江华海药业股份有限公司 | Method for preparing 5-aminosalicylic acid by adopting gas phase catalysis carboxylation method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR930002964B1 (en) * | 1990-10-20 | 1993-04-16 | 주식회사 코오롱 | Process for producing salicylic acid derivatives |
-
2011
- 2011-10-17 CN CN201110312793.7A patent/CN102311357B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1159938A (en) * | 1965-12-10 | 1969-07-30 | Ile De France | A Process for the Preparation of 5-Halobenzoic Acid Ester Derivatives |
| GB1137654A (en) * | 1966-02-01 | 1968-12-27 | Ile De France | 5-halosalicylic acid derivatives |
| US5643494A (en) * | 1993-05-21 | 1997-07-01 | Hoechst Aktiengesellschaft | Process for the preparation of aromatic hydroxy carboxylic acids |
| CN102126977A (en) * | 2010-12-25 | 2011-07-20 | 浙江华海药业股份有限公司 | Method for preparing 5-aminosalicylic acid by adopting gas phase catalysis carboxylation method |
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| CN102311357A (en) | 2012-01-11 |
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Effective date of registration: 20160223 Address after: 200436 322, 1363, 1345, 323, Hu Tai Road, Shanghai, Zhabei District Patentee after: SHANGHAI HONGYUAN XINCHUANG MATERIAL TECHNOLOGY CO., LTD. Patentee after: Zhejiang Hongsheng Chemical Research Limited Patentee after: Zhejiang Longsheng Chemicals Co., Ltd. Address before: 201206 31F01-3102 new Jinqiao Building, room 28, new Jinqiao Road, Shanghai, Pudong New Area Patentee before: Shanghai Annuo Aromatic Amine Chemical Co., Ltd. Patentee before: Zhejiang Hongsheng Chemical Research Limited Patentee before: Zhejiang Amino-Chem Co., Ltd. Patentee before: Zhejiang Longsheng Group Co., Ltd. |