CN111646907A - Preparation method of 2, 3-dichloro-6-nitroaniline - Google Patents
Preparation method of 2, 3-dichloro-6-nitroaniline Download PDFInfo
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- CN111646907A CN111646907A CN202010562588.5A CN202010562588A CN111646907A CN 111646907 A CN111646907 A CN 111646907A CN 202010562588 A CN202010562588 A CN 202010562588A CN 111646907 A CN111646907 A CN 111646907A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0217—Mercaptans or thiols
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0229—Sulfur-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0214
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4283—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using N nucleophiles, e.g. Buchwald-Hartwig amination
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Abstract
The invention relates to the technical field of pesticides, and particularly relates to a preparation method of 2, 3-dichloro-6-nitroaniline. Taking 2,3, 4-trichloronitrobenzene as a raw material, water as a solvent, adding a sulfur-containing compound as a catalyst, and reacting with ammonia water in a high-pressure kettle to obtain 2, 3-dichloro-6-nitroaniline; the preparation method of the 2, 3-dichloro-6-nitroaniline has the advantages of high yield, good reaction selectivity, high safety, environmental friendliness and low production cost, and is suitable for industrial production; a small amount of sulfur-containing catalyst is added, so that a good catalytic effect can be achieved, a high yield of more than 99% and selectivity of more than 99% can be finally obtained, the reaction time is greatly shortened, and the production energy consumption is reduced.
Description
Technical Field
The invention relates to the technical field of pesticides, and particularly relates to a preparation method of 2, 3-dichloro-6-nitroaniline.
Background
The molecular formula of the 2, 3-dichloro-6-nitroaniline is C6H4Cl2N2O2Is an intermediate of the pesticide aclonifen. The Chinese patent CN106854162A discloses that 2,3, 4-trichloronitrobenzene is used as a raw material and is subjected to ammonolysis reaction with ammonia water in an organic solvent chlorobenzene at the temperature of 120-150 ℃ in an autoclave, the yield and the purity are high, and the defects that chlorobenzene has inhibition and anesthesia effects on a central nervous system and irritation on skin and mucosa are overcome. It has serious harm to environment and can cause pollution to water, soil and atmosphere. The autoclave has high reaction temperature and low safety.
The international application with publication number WO2016040764A1 introduces that 2,3, 4-trichloronitrobenzene is used as raw material and is made into the product by ammonolysis reaction with ammonia water in organic solvent dioxane at 120 ℃ in a sealed tube, and the yield is 81%. The method has the disadvantages of high tube sealing reaction temperature, low safety, low yield, complicated operation and difficult realization of industrial production, and the product needs column chromatography for purification.
Journal (j.med.chem.) discloses papers named as follows: structure-activity relationships 2-terminated 5, 6-dichoro-, 4, 6-dichoro-, and4, 5-dichoro-1- [ (2-hydroxyoxy) methyl ] -and-1- [ (1, 3-dihydroxy-2-methoxy) methyl ] benzimidazoles, wherein 2,3, 4-trichloronitrobenzene is used as a raw material and is subjected to an ammonolysis reaction with a methanol ammonia solution at 120 ℃ in an autoclave, and the yield is 80%. The disadvantages are high autoclave reaction temperature and low safety. Low yield, complex post-treatment operation and high production cost.
Therefore, a preparation method of 2, 3-dichloro-6-nitroaniline with mild reaction conditions, better environmental protection and better yield is urgently needed in the current production.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a preparation method of 2, 3-dichloro-6-nitroaniline with mild reaction conditions, better environmental protection and yield.
The technical scheme for solving the technical problems is as follows:
a preparation method of 2, 3-dichloro-6-nitroaniline comprises the following steps: the method is characterized in that 2,3, 4-trichloronitrobenzene is used as a raw material, water is used as a solvent, a sulfur-containing compound is added as a catalyst, and the raw material reacts with ammonia water in a high-pressure kettle to obtain the catalyst; the specific reaction formula is as follows:
preferably, the sulfur-containing compound is p-hydroxybenzene sulfonic acid, m-hydroxybenzene sulfonic acid or 2, 4-bisphenol sulfur; preferably p-hydroxybenzenesulfonic acid.
Preferably, the mass ratio of the 2,3, 4-trichloronitrobenzene to the water in the reaction is 1: 1-10; further, in the reaction, the mass ratio of the 2,3, 4-trichloronitrobenzene to the water is 1: 1-5; furthermore, the mass ratio of the 2,3, 4-trichloronitrobenzene to the water in the reaction is 1: 1.5 to 3.
Preferably, the mass ratio of the 2,3, 4-trichloronitrobenzene to the ammonia water in the reaction is 1: 0.5 to 10; further, in the reaction, the mass ratio of the 2,3, 4-trichloronitrobenzene to the ammonia water is 1: 0.5 to 5; furthermore, in the reaction, the mass ratio of the 2,3, 4-trichloronitrobenzene to the ammonia water is 1: 1 to 2.5.
Preferably, the mass ratio of the 2,3, 4-trichloronitrobenzene to the catalyst in the reaction is 1: 0.01 to 0.2; further, in the reaction, the mass ratio of the 2,3, 4-trichloronitrobenzene to the catalyst is 1: 0.02 to 0.1.
Preferably, the reaction temperature of the reaction is 60-100 ℃; further, the reaction temperature is 60-90 ℃.
Preferably, the reaction pressure is 0.2-0.5 Mpa; further, the reaction pressure is 0.3-0.4 MPa.
The Chinese naming of the compound of the invention conflicts with the structural formula, and the structural formula is taken as the standard; except for obvious errors in the formula.
The preparation method of the 2, 3-dichloro-6-nitroaniline has the advantages of high yield, good reaction selectivity, high safety, environmental friendliness and low production cost, and is suitable for industrial production; a small amount of sulfur-containing catalyst is added, so that a good catalytic effect can be achieved, a high yield of more than 99% and selectivity of more than 99% can be finally obtained, the reaction time is greatly shortened, and the production energy consumption is reduced.
Detailed Description
The invention is illustrated but not limited by the following examples. The technical solutions protected by the present invention are all the simple replacements or modifications made by the skilled person in the art.
Example 1
Adding 240g of water, 240g of 30% ammonia water, 120g of 2,3, 4-trichloronitrobenzene and 6g of p-hydroxybenzene sulfonic acid into an autoclave, stirring, keeping the temperature at 80 ℃ for reaction for 6 hours at the pressure of 0.3Mpa, cooling to room temperature after the reaction is finished, carrying out suction filtration, washing with water, and drying to obtain 108.7g of the target product 2, 3-dichloro-6-nitroaniline. The purity of the liquid phase was 99.5% and the yield was 99.1%. And continuously introducing ammonia gas into the filtrate until the reaction concentration is reached, and directly putting the filtrate into the next batch.
Example 2
Adding 360g of water, 120g of 30% ammonia water, 120g of 2,3, 4-trichloronitrobenzene and 6g of p-hydroxybenzene sulfonic acid into an autoclave, stirring, keeping the temperature at 80 ℃, reacting for 6 hours at 0.4Mpa, cooling to room temperature, carrying out suction filtration, washing with water, and drying to obtain 108.6g of the target product 2, 3-dichloro-6-nitroaniline. The purity of the liquid phase was 99.3% and the yield was 99.0%. And continuously introducing ammonia gas into the filtrate until the reaction concentration is reached, and directly putting the filtrate into the next batch.
Example 3
Adding 240g of water, 480g of 30% ammonia water, 120g of 2,3, 4-trichloronitrobenzene and 6g of p-hydroxybenzene sulfonic acid into an autoclave, stirring, keeping the temperature at 80 ℃, reacting for 6 hours at 0.3Mpa, cooling to room temperature, carrying out suction filtration, washing with water, and drying to obtain 108.9g of the target product 2, 3-dichloro-6-nitroaniline. The purity of the liquid phase was 99.6% and the yield was 99.3%. And continuously introducing ammonia gas into the filtrate until the reaction concentration is reached, and directly putting the filtrate into the next batch.
Example 4
Adding 180g of water, 300g of 30% ammonia water, 120g of 2,3, 4-trichloronitrobenzene and 6g of m-hydroxybenzene sulfonic acid into an autoclave, stirring, keeping the temperature at 80 ℃ for reaction for 6 hours at the pressure of 0.3Mpa, cooling to room temperature, carrying out suction filtration, washing with water, and drying to obtain 108.9g of the target product 2, 3-dichloro-6-nitroaniline. The purity of the liquid phase was 99.2% and the yield was 99.3%. And continuously introducing ammonia gas into the filtrate until the reaction concentration is reached, and directly putting the filtrate into the next batch.
Example 5
Adding 240g of water, 240g of 30% ammonia water, 120g of 2,3, 4-trichloronitrobenzene and 3g of 2, 4-bisphenol sulfur into a high-pressure kettle, stirring, keeping the reaction temperature at 80 ℃, reacting for 6 hours at 0.3Mpa, cooling to room temperature after the reaction is finished, carrying out suction filtration, washing with water, and drying to obtain 108.7g of the target product 2, 3-dichloro-6-nitroaniline. The purity of the liquid phase was 99.3% and the yield was 99.1%. And continuously introducing ammonia gas into the filtrate until the reaction concentration is reached, and directly putting the filtrate into the next batch.
Example 6
Adding 240g of water, 240g of 30% ammonia water, 120g of 2,3, 4-trichloronitrobenzene and 12g of p-hydroxybenzene sulfonic acid into an autoclave, stirring, keeping the temperature at 80 ℃, reacting for 6 hours at 0.3Mpa, cooling to room temperature, carrying out suction filtration, washing with water, and drying to obtain 109.1g of the target product 2, 3-dichloro-6-nitroaniline. The purity of the liquid phase was 99.7% and the yield was 99.5%. And continuously introducing ammonia gas into the filtrate until the reaction concentration is reached, and directly putting the filtrate into the next batch.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications are all within the scope of the present invention.
Claims (10)
1. A preparation method of 2, 3-dichloro-6-nitroaniline is characterized by comprising the following steps: the method is characterized in that 2,3, 4-trichloronitrobenzene is used as a raw material, water is used as a solvent, a sulfur-containing compound is added as a catalyst, and the raw material reacts with ammonia water in a high-pressure kettle to obtain the catalyst; the specific reaction formula is as follows:
2. the process for producing 2, 3-dichloro-6-nitroaniline according to claim 1, wherein the sulfur-containing compound is p-hydroxybenzenesulfonic acid, m-hydroxybenzenesulfonic acid, or 2, 4-bisphenolsulfur; preferably p-hydroxybenzenesulfonic acid.
3. The method for producing 2, 3-dichloro-6-nitroaniline according to claim 1, wherein the mass ratio of 2,3, 4-trichloronitrobenzene to water in the reaction is 1: 1 to 10.
4. The process for producing 2, 3-dichloro-6-nitroaniline according to claim 3, wherein the mass ratio of 2,3, 4-trichloronitrobenzene to water in the reaction is 1: 1 to 5.
5. The method for preparing 2, 3-dichloro-6-nitroaniline according to claim 1, wherein the mass ratio of 2,3, 4-trichloronitrobenzene to ammonia water in the reaction is 1: 0.5 to 10.
6. The method for producing 2, 3-dichloro-6-nitroaniline according to claim 5, wherein the mass ratio of 2,3, 4-trichloronitrobenzene to ammonia water in the reaction is 1: 0.5 to 5.
7. The method for preparing 2, 3-dichloro-6-nitroaniline according to claim 1, wherein the mass ratio of the 2,3, 4-trichloronitrobenzene to the catalyst in the reaction is 1: 0.01 to 0.2.
8. The method of claim 7, wherein the mass ratio of 2,3, 4-trichloronitrobenzene to catalyst in the reaction is 1: 0.02 to 0.1.
9. The method for producing 2, 3-dichloro-6-nitroaniline according to claim 1, wherein the reaction temperature is 60 to 100 ℃.
10. The process for producing 2, 3-dichloro-6-nitroaniline according to any one of claims 1 to 9, wherein the reaction pressure is 0.2 to 0.5 Mpa.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010562588.5A CN111646907B (en) | 2020-06-18 | 2020-06-18 | Preparation method of 2, 3-dichloro-6-nitroaniline |
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| CN202010562588.5A CN111646907B (en) | 2020-06-18 | 2020-06-18 | Preparation method of 2, 3-dichloro-6-nitroaniline |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106854162A (en) * | 2016-12-13 | 2017-06-16 | 浙江海正化工股份有限公司 | A kind of nitroaniline of 2,3 dichloro 6 and preparation method thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106854162A (en) * | 2016-12-13 | 2017-06-16 | 浙江海正化工股份有限公司 | A kind of nitroaniline of 2,3 dichloro 6 and preparation method thereof |
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