CN113372231A - Preparation method of 5-amino-1, 2, 3-benzenetricarboxylic acid - Google Patents
Preparation method of 5-amino-1, 2, 3-benzenetricarboxylic acid Download PDFInfo
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- CN113372231A CN113372231A CN202110609511.3A CN202110609511A CN113372231A CN 113372231 A CN113372231 A CN 113372231A CN 202110609511 A CN202110609511 A CN 202110609511A CN 113372231 A CN113372231 A CN 113372231A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
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- 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
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
Abstract
The invention belongs to the technical field of fine chemicals, and particularly relates to a preparation method of 5-amino-1, 2, 3-benzenetricarboxylic acid, which comprises the following steps: dissolving 1,2, 3-benzene tricarboxylic acid in a nitric acid environment; reacting nitric acid solution containing 1,2, 3-benzene tricarboxylic acid with sulfuric acid; obtaining 5-nitro-1, 2, 3-benzene tricarboxylic acid; dissolving 5-nitro-1, 2, 3-benzene tricarboxylic acid in methanol; reacting the obtained mixed solution with hydrogen; filtering, concentrating, recrystallizing, and refining to obtain 5-amino-1, 2, 3-benzenetricarboxylic acid; according to the preparation method of the 5-amino-1, 2, 3-benzene tricarboxylic acid, the microchannel reactor has the characteristics of small liquid holdup, high heat exchange efficiency, good mass transfer efficiency and the like, the problems of mass transfer, heat exchange, safety and the like in the nitration reaction and the catalytic hydrogenation reaction can be effectively solved, the safety is greatly improved, the two reactions of the nitration reaction and the nitro reduction ammoniation can be continuously synthesized, the reaction can be started and stopped at any time, no amplification effect exists, and an effective method is provided for industrial safe production.
Description
Technical Field
The invention belongs to the technical field of fine chemicals, and particularly relates to a preparation method of 5-amino-1, 2, 3-benzenetricarboxylic acid.
Background
The aminobenzoic acid compounds are important fine chemical intermediates and are widely applied to pharmaceutical chemicals and MOFs material preparation. The 5-amino-1, 2, 3-benzene tricarboxylic acid is an important aminobenzoic acid compound, and is prepared mainly by using 1,2, 3-benzene tricarboxylic acid as a raw material and finally obtaining the 5-amino-1, 2, 3-benzene tricarboxylic acid through two steps of nitration reaction and nitro reduction ammoniation.
There are two main methods for the first nitration reaction: the concentrated sulfuric acid-potassium nitrate method and the concentrated sulfuric acid-concentrated nitric acid method. In patent CN106187741A, 1,2, 3-benzenetricarboxylic acid is used as a raw material, a concentrated sulfuric acid-potassium nitrate method is used for nitration reaction, before the nitration reaction, the raw material 1,2, 3-benzenetricarboxylic acid is firstly reacted with potassium hydroxide to form potassium salt, and then concentrated sulfuric acid and potassium nitrate are added for nitration reaction at high temperature; in patent CN101357891A, 1,2, 3-benzoic acid is used as a raw material, and a concentrated sulfuric acid-concentrated nitric acid method is adopted for reaction, namely, nitration reaction is carried out at 50-150 ℃ in the presence of fuming nitric acid and fuming sulfuric acid, so as to obtain 5-nitro-1, 2, 3-benzenetricarboxylic acid. Both the two nitration methods need nitration reaction at high temperature in the presence of concentrated sulfuric acid, the feeding and discharging time is long, materials are accumulated, potential safety hazards are easily caused, and the industrial scale-up production is limited.
The second step nitro group reduction ammoniation reaction has a plurality of methods, and the simple and convenient method suitable for industrial production is a catalytic hydrogenation method using palladium carbon as a catalyst. For example, in patent CN106187741A, 5-amino-1, 2, 3-benzenetricarboxylic acid is obtained by reacting palladium on carbon as a catalyst with hydrogen in methanol and water.
It can be seen from the existing literature that in the process of preparing 5-amino-1, 2, 3-benzenetricarboxylic acid, the two steps of nitration reaction and nitro group reduction ammoniation are both traditional batch preparation methods, the nitration reaction and catalytic hydrogenation are both dangerous chemical processes which are mainly regulated in China, and the traditional method has great potential safety hazard because the material quantity, reaction temperature and pressure of the reaction are difficult to control.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of 5-amino-1, 2, 3-benzenetricarboxylic acid, which has the characteristics of continuous synthesis, reaction starting/stopping at any time, no amplification effect and safe processing.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of 5-amino-1, 2, 3-benzene tricarboxylic acid comprises the following steps:
the method comprises the following steps: dissolving 1,2, 3-benzene tricarboxylic acid in a nitric acid environment;
step two: under the condition of specified temperature, respectively feeding nitric acid solution containing 1,2, 3-benzene tricarboxylic acid and sulfuric acid into a microchannel reactor through a metering pump for reaction;
step three: under the condition of specified temperature, directly flowing reaction liquid obtained from an outlet of the microchannel reactor into a collector after the reaction is finished, standing for 3-5 hours after the reaction liquid stops flowing out, filtering, washing a filter cake with an organic solvent, and drying to obtain 5-nitro-1, 2, 3-benzenetricarboxylic acid;
step four: dissolving 5-nitro-1, 2, 3-benzene tricarboxylic acid in methanol in the presence of a palladium-carbon catalyst;
step five: under the conditions of specified temperature and pressure, the mixed liquid obtained in the step four enters a micro-channel reactor through a metering pump, and then hydrogen is introduced into the micro-channel reactor for reaction;
step six: after the reaction is finished, the reaction liquid obtained from the outlet of the microchannel reactor directly flows into a collector, and the post reaction liquid is filtered, concentrated, recrystallized and refined to obtain the 5-amino-1, 2, 3-benzene tricarboxylic acid with the purity of more than 98 percent.
As a preferable technical scheme of the invention, in the first step, the molar ratio of the 1,2, 3-benzene tricarboxylic acid to the nitric acid is 1:1-5, and the mass fraction of the nitric acid is 60% -98%.
As a preferable technical scheme of the invention, the mass fraction of the sulfuric acid in the second step is 80-98% or fuming sulfuric acid.
As a preferable technical scheme of the invention, the molar ratio of the 1,2, 3-benzene tricarboxylic acid to the nitric acid to the sulfuric acid is 1:1-5: 2-7.
As a preferred technical scheme of the invention, the reaction temperature in the second step is 50-200 ℃.
In the third step, the temperature of the collector is kept at 0-5 ℃.
In the third step, the organic solvent for washing is one or more of ethyl acetate, isopropyl ether, petroleum ether, dichloromethane, acetone, etc.
As a preferable technical scheme of the invention, in the fourth step, the mass ratio of the palladium-carbon catalyst, the 5-nitro-1, 2, 3-benzenetricarboxylic acid and the methanol is 0.01-0.15:1: 10-15.
As a preferred technical scheme of the invention, the reaction temperature in the fifth step is 20-150 ℃.
As a preferable technical scheme of the invention, the reaction pressure in the fifth step is 0.1MPa-1 MPa.
Compared with the prior art, the invention has the beneficial effects that: the preparation method of the 5-amino-1, 2, 3-benzene tricarboxylic acid can effectively solve the problems of mass transfer, heat exchange, safety and the like in the nitration reaction and the catalytic hydrogenation reaction because the microchannel reactor has the characteristics of small liquid holdup, high heat exchange efficiency, good mass transfer efficiency and the like, and greatly improves the safety.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic representation of the reaction scheme of the present invention;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, the present invention provides the following technical solutions: a preparation method of 5-amino-1, 2, 3-benzene tricarboxylic acid comprises the following steps:
the method comprises the following steps: dissolving 1,2, 3-benzene tricarboxylic acid in nitric acid, wherein the molar ratio of the 1,2, 3-benzene tricarboxylic acid to the nitric acid is 1:1-5, and the mass fraction of the nitric acid is 60-98%;
step two: respectively feeding nitric acid solution containing 1,2, 3-benzene tricarboxylic acid and sulfuric acid into a microchannel reactor through a metering pump for reaction, wherein the reaction temperature is 50-200 ℃, and the mass fraction of the sulfuric acid is 80-98% or fuming sulfuric acid;
step three: under the condition of specified temperature, directly flowing reaction liquid obtained from an outlet of the microchannel reactor into a collector after the reaction is finished, keeping the temperature of the collector at 0-5 ℃, standing for 3-5 hours after the reaction liquid stops flowing out, filtering, washing a filter cake with an organic solvent, and drying to obtain 5-nitro-1, 2, 3-benzenetricarboxylic acid;
step four: dissolving 5-nitro-1, 2, 3-benzene tricarboxylic acid in methanol, and adding a palladium-carbon catalyst, wherein the mass ratio of the palladium-carbon catalyst to the 5-nitro-1, 2, 3-benzene tricarboxylic acid to the methanol is 0.01-0.15:1: 10-15;
step five: under the conditions of specified temperature and pressure, the mixed solution obtained in the step four enters a micro-channel reactor through a metering pump, then hydrogen is introduced into the micro-channel reactor for reaction, the reaction temperature of the micro-channel reactor is kept between 20 and 150 ℃, and the pressure is kept between 0.1 and 1 MPa;
step six: after the reaction is finished, the reaction liquid obtained from the outlet of the microchannel reactor directly flows into a collector, and the post reaction liquid is filtered, concentrated, recrystallized and refined to obtain the 5-amino-1, 2, 3-benzene tricarboxylic acid with the purity of more than 98 percent.
Specifically, in this example, the molar ratio of 1,2, 3-benzenetricarboxylic acid, nitric acid, and sulfuric acid is 1:1 to 5:2 to 7.
In this embodiment, in the third step, the organic solvent for washing is one or more of ethyl acetate, isopropyl ether, petroleum ether, dichloromethane, acetone, and the like, for example, ethyl acetate.
The reaction formula of the preparation method is as follows:
the raw materials referred to in this example are all commercially available.
Example 1:
the molar ratio of the 1,2, 3-benzene tricarboxylic acid to the nitric acid is 1:1, and the mass fraction of the nitric acid is 60%; the molar ratio of the 1,2, 3-benzene tricarboxylic acid to the nitric acid to the sulfuric acid is 1:1: 2; the mass ratio of the palladium-carbon catalyst to the 5-nitro-1, 2, 3-benzenetricarboxylic acid to the methanol is 0.01:1: 10.
Example 2:
the molar ratio of the 1,2, 3-benzene tricarboxylic acid to the nitric acid is 1:3, and the mass fraction of the nitric acid is 79%; the molar ratio of the 1,2, 3-benzene tricarboxylic acid to the nitric acid to the sulfuric acid is 1:3: 4.5; the mass ratio of the palladium-carbon catalyst to the 5-nitro-1, 2, 3-benzenetricarboxylic acid to the methanol is 0.08:1: 12.5.
Example 3:
the molar ratio of the 1,2, 3-benzene tricarboxylic acid to the nitric acid is 1:5, and the mass fraction of the nitric acid is 98%; the molar ratio of the 1,2, 3-benzene tricarboxylic acid to the nitric acid to the sulfuric acid is 1:5: 7; the mass ratio of the palladium-carbon catalyst to the 5-nitro-1, 2, 3-benzenetricarboxylic acid to the methanol is 0.15:1: 15.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of 5-amino-1, 2, 3-benzene tricarboxylic acid is characterized by comprising the following steps:
the method comprises the following steps: dissolving 1,2, 3-benzene tricarboxylic acid in a nitric acid environment;
step two: under the condition of specified temperature, respectively feeding nitric acid solution containing 1,2, 3-benzene tricarboxylic acid and sulfuric acid into a microchannel reactor through a metering pump for reaction;
step three: under the condition of specified temperature, directly flowing reaction liquid obtained from an outlet of the microchannel reactor into a collector after the reaction is finished, standing for 3-5 hours after the reaction liquid stops flowing out, filtering, washing a filter cake with an organic solvent, and drying to obtain 5-nitro-1, 2, 3-benzenetricarboxylic acid;
step four: dissolving 5-nitro-1, 2, 3-benzene tricarboxylic acid in methanol in the presence of a palladium-carbon catalyst;
step five: under the conditions of specified temperature and pressure, the mixed liquid obtained in the step four enters a micro-channel reactor through a metering pump, and then hydrogen is introduced into the micro-channel reactor for reaction;
step six: after the reaction is finished, the reaction liquid obtained from the outlet of the microchannel reactor directly flows into a collector, and the post reaction liquid is filtered, concentrated, recrystallized and refined to obtain the 5-amino-1, 2, 3-benzene tricarboxylic acid with the purity of more than 98 percent.
2. The process according to claim 1 for preparing 5-amino-1, 2, 3-benzenetricarboxylic acid, wherein: in the first step, the molar ratio of the 1,2, 3-benzene tricarboxylic acid to the nitric acid is 1:1-5, and the mass fraction of the nitric acid is 60-98%.
3. The process according to claim 1 for preparing 5-amino-1, 2, 3-benzenetricarboxylic acid, wherein: and the mass fraction of the sulfuric acid in the step II is 80-98% or fuming sulfuric acid.
4. The process according to claim 3, wherein the reaction mixture comprises the following components: the molar ratio of the 1,2, 3-benzene tricarboxylic acid to the nitric acid to the sulfuric acid is 1:1-5: 2-7.
5. The process according to claim 1 for preparing 5-amino-1, 2, 3-benzenetricarboxylic acid, wherein: the reaction temperature in the second step is 50-200 ℃.
6. The process according to claim 1 for preparing 5-amino-1, 2, 3-benzenetricarboxylic acid, wherein: in the third step, the temperature of the collector is kept between 0 and 5 ℃.
7. The process according to claim 1 for preparing 5-amino-1, 2, 3-benzenetricarboxylic acid, wherein: in the third step, the organic solvent for washing is one or more of ethyl acetate, isopropyl ether, petroleum ether, dichloromethane, acetone and the like.
8. The process according to claim 1 for preparing 5-amino-1, 2, 3-benzenetricarboxylic acid, wherein: in the fourth step, the mass ratio of the palladium-carbon catalyst, the 5-nitro-1, 2, 3-benzene tricarboxylic acid and the methanol is 0.01-0.15:1: 10-15.
9. The process according to claim 1 for preparing 5-amino-1, 2, 3-benzenetricarboxylic acid, wherein: the reaction temperature in the fifth step is 20-150 ℃.
10. The process according to claim 1 for preparing 5-amino-1, 2, 3-benzenetricarboxylic acid, wherein: and the reaction pressure in the fifth step is 0.1MPa-1 MPa.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114685302A (en) * | 2022-02-17 | 2022-07-01 | 河北圣雪大成制药有限责任公司 | Method for continuously synthesizing 9-amino minocycline by microreactor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357891A (en) * | 2008-09-04 | 2009-02-04 | 杭州师范大学 | 5-nitro-1,2,3-benzene tricarboxylic acid synthesizing method |
| CN106187741A (en) * | 2016-07-07 | 2016-12-07 | 扬州大学 | A kind of preparation method of 5 iodine 1,2,3 benzenetricarboxylic acids |
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- 2021-06-01 CN CN202110609511.3A patent/CN113372231A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357891A (en) * | 2008-09-04 | 2009-02-04 | 杭州师范大学 | 5-nitro-1,2,3-benzene tricarboxylic acid synthesizing method |
| CN106187741A (en) * | 2016-07-07 | 2016-12-07 | 扬州大学 | A kind of preparation method of 5 iodine 1,2,3 benzenetricarboxylic acids |
Non-Patent Citations (1)
| Title |
|---|
| 赵玉潮 等: "微化工技术在化学反应中的应用进展", 《中国科技论文在线》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114685302A (en) * | 2022-02-17 | 2022-07-01 | 河北圣雪大成制药有限责任公司 | Method for continuously synthesizing 9-amino minocycline by microreactor |
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