阅读说明：本技术 一种2,3-二氯-6-硝基苯胺的制备方法 (Preparation method of 2, 3-dichloro-6-nitroaniline ) 是由 曹伟 于 2020-06-18 设计创作，主要内容包括：本发明涉及农药技术领域,具体涉及一种2,3-二氯-6-硝基苯胺的制备方法。以2,3,4-三氯硝基苯为原料,水为溶剂,加入含硫化合物为催化剂,在高压釜中与氨水反应得到2,3-二氯-6-硝基苯胺；本发明提供的2,3-二氯-6-硝基苯胺的制备方法收率高,反应选择性好,安全性高,绿色环保,生产成本低,适于工业化生产；加入少量的含硫催化剂能够取得很好的催化效果,最终能够获得99%以上的高收率,99%以上的选择性,大大缩短了反应时间,降低了生产能耗。(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.)

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.

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.