阅读说明：本技术 一种4-多氟代甲氧基邻苯二胺的制备方法 (Preparation method of 4-polyfluoro methoxy o-phenylenediamine ) 是由 姜维强 陈朝晖 沙里峰 于 2019-08-15 设计创作，主要内容包括：本发明涉及一种4-多氟代甲氧基邻苯二胺的制备方法,其特征在：(1)对氨基苯酚与碱按摩尔比1：0.8～1.5,-20～40℃反应0.1～24h得氨基酚盐,氨基酚盐和含氟原料按摩尔比1：1.0～3.0,20～120℃、0.01～20Mpa下反应1～72h生成4-多氟代甲氧基苯胺；(2)4-多氟代甲氧基苯胺在溶剂中与卤素和卤素化合物按摩尔比1：0.2–2.5进行卤化,-30～80℃反应0.1～24h；(3)4-多氟代甲氧基-2-卤苯胺按与氨摩尔比1：0.8～30.0加入氨水溶液或有机溶剂中,加入0.1～10%的铜催化剂,50～200℃、0.01～10Mpa下氨解1～72h。本发明优点：以对氨基苯酚为原料,通过醚化、卤化和氨解三步反应即可得到目标产物4-多氟代甲氧基邻苯二胺；工艺简短,收率高,成本低,质量好,污染轻,适宜工业化生产。(The invention relates to a preparation method of 4-polyfluoro methoxy o-phenylenediamine, which is characterized by comprising the following steps: (1) p-aminophenol and alkali in a molar ratio of 1: 0.8-1.5, reacting at-20-40 ℃ for 0.1-24 h to obtain aminophenol salt, wherein the aminophenol salt and the fluorine-containing raw material are mixed according to a molar ratio of 1: reacting at 20-120 ℃ and 0.01-20 Mpa for 1-72 h at 1.0-3.0 to generate 4-polyfluoro methoxy aniline; (2) 4-polyfluoro methoxy aniline and halogen compound in a molar ratio of 1: halogenating at 0.2-2.5, and reacting at-30-80 ℃ for 0.1-24 h; (3) 4-polyfluoro methoxy-2-halogen aniline according to the mol ratio of 1: 0.8-30.0, adding ammonia water solution or organic solvent, adding 0.1-10% of copper catalyst, and carrying out ammonolysis at 50-200 ℃ and 0.01-10 Mpa for 1-72 h. The invention has the advantages that: taking p-aminophenol as a raw material, and obtaining a target product, namely 4-polyfluoro methoxy o-phenylenediamine through three-step reactions of etherification, halogenation and aminolysis; short process, high yield, low cost, good quality, light pollution and suitability for industrial production.)

1. A preparation method of 4-polyfluoro methoxy o-phenylenediamine is characterized by comprising the following steps:

(1) etherification

P-aminophenol and alkali in a molar ratio of 1: 0.8-1.5, reacting for 0.1-24 h at-20-40 ℃ to generate aminophenol salt, and mixing the aminophenol salt and the fluorine-containing raw material according to a molar ratio of 1: 1.0-3.0, reacting at 20-120 ℃ and 0.01-20 Mpa for 1-72 h to generate 4-polyfluoro methoxy aniline; wherein the alkali is any one of sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate and sodium alkoxide; the fluorine-containing raw material is any one of difluorochloromethane, difluorobromomethane, trifluorochloromethane and trifluorobromomethane; when the aqueous solvent is used, a surfactant with the mass of 0.1-5% of that of the p-aminophenol is generally added, wherein the surfactant is any one of benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, tetrabutylammonium chloride and tetrabutylammonium bromide;

(2) halogenation

4-polyfluoro methoxy aniline and halogen compound in a molar ratio of 1: 0.2-2.5, performing halogenation reaction at the temperature of-30-80 ℃ for 0.1-24 h, and performing substitution halogenation reaction to locate at the 2-position of the 4-polyfluoro methoxy aniline to generate the 4-polyfluoro methoxy-2-haloaniline, wherein the halogen and halogen compound is any one of bromine water, liquid bromine, bromine solution, hydrobromic acid + hydrogen peroxide, bromosuccinimide, chlorine water, chlorine gas, chlorine-containing solution, hydrochloric acid + hydrogen peroxide, hypochlorous acid and chlorosuccinimide;

(3) ammonolysis

According to the mol ratio of 4-polyfluoro methoxy-2-haloaniline to ammonia of 1: 0.8-30.0, adding 4-polyfluoromethoxy-2-halogenoaniline into an ammonia water solution or an organic solvent, adding a copper catalyst with the mass of 0.1-10% of that of the 4-polyfluoromethoxy-2-halogenoaniline, and carrying out ammonolysis for 1-72 h at 50-200 ℃ and 0.01-10 Mpa to obtain a target product, namely 4-polyfluoromethoxy o-phenylenediamine; wherein the organic solvent is tetrahydrofuran or dioxane, and the ammonia content is 10-60%; the copper catalyst is any one of cupric chloride, cupric bromide, cuprous chloride and cuprous bromide.

2. The method for producing 4-polyfluoromethoxy-o-phenylenediamine according to claim 1, wherein: the solvent in the step (2) is any one of water, dichloromethane, trichloromethane or carbon tetrachloride.

Technical Field

The invention belongs to the field of preparation of medical intermediates and fine chemical intermediates, and relates to a preparation method of 4-polyfluoro methoxy o-phenylenediamine.

Technical Field

4-polyfluoro methoxy o-phenylenediamine is an important organic synthesis intermediate, can be used for synthesizing various functional fine chemical products, including benzimidazole, benzimidazolone, mercaptobenzimidazole, benzotriazole, benzophenazine, benzoquinoline and the like which are functionalized by fluorine-containing methoxy groups, and is used for carrying out fluorine-containing group modification on materials, including diisocyanate and epoxy resin curing, polymer initiation, crosslinking, chain extension, end capping and the like, so that the 4-polyfluoro methoxy o-phenylenediamine has wide market prospect.

The traditional preparation process of 4-polyfluoro methoxy o-phenylenediamine generally takes phenol as a raw material and is synthesized by 7 steps of reactions such as etherification, nitration, reduction, acylation, re-nitration, hydrolysis, reduction and the like; the improved process is that p-aminophenol is used as raw material, and under the catalysis of phase transfer, 5 steps of etherification, acetylation, nitration, hydrolysis and reduction are required to be carried out to prepare 4-polyfluoro methoxy o-phenylenediamine; the further improved process takes paracetamol (p-acetaminophenol) as a raw material, and 4-polyfluoro methoxy o-phenylenediamine can be prepared by 4 steps of reactions such as etherification, nitration, hydrolysis, reduction and the like, and the specific process route is as follows:

however, the processes still have the defects of long synthesis route, more process steps, poor stability of intermediate products and the like, so that the synthesis process of the 4-polyfluoromethoxy o-phenylenediamine has low yield, high cost, and large economic benefit and environmental protection pressure.

Disclosure of Invention

The invention aims to solve the defects of the prior art and provides a preparation method of 4-polyfluoro methoxy o-phenylenediamine, wherein the polyfluoro methoxy comprises difluoromethoxy and trifluoromethoxy; the method takes p-aminophenol as a raw material, firstly etherifies the p-aminophenol into 4-polyfluoro aniline, then halogenates the p-aminophenol into 2-halogen-4-polyfluoro aniline, and finally ammoniates halogen atoms into amino to obtain 4-polyfluoro methoxy o-phenylenediamine, wherein the reaction equation is as follows:

in order to achieve the purpose, the invention adopts the technical scheme that:

a preparation method of 4-polyfluoro methoxy o-phenylenediamine is characterized by comprising the following steps:

(1) etherification

P-aminophenol and alkali in a molar ratio of 1: 0.8-1.5, reacting for 0.1-24 h at-20-40 ℃ to generate aminophenol salt, and mixing the aminophenol salt and the fluorine-containing raw material according to a molar ratio of 1: 1.0-3.0, reacting at 20-120 ℃ and 0.01-20 Mpa for 1-72 h to generate 4-polyfluoro methoxy aniline; wherein the alkali is any one of sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate and sodium alkoxide; the fluorine-containing raw material is any one of difluorochloromethane, difluorobromomethane, trifluorochloromethane and trifluorobromomethane; when the aqueous solvent is used, a surfactant with the mass of 0.1-5% of that of the p-aminophenol is generally added, wherein the surfactant is any one of benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, tetrabutylammonium chloride and tetrabutylammonium bromide;

(2) halogenation

4-polyfluoro methoxy aniline and halogen compound in a molar ratio of 1: 0.2-2.5, performing halogenation reaction at the temperature of-30-80 ℃ for 0.1-24 h, and performing substitution halogenation reaction to locate at the 2-position of the 4-polyfluoro methoxy aniline to generate 4-polyfluoro methoxy-2-haloaniline, wherein the halogen and halogen compound is any one of bromine water, liquid bromine, bromine solution, hydrobromic acid + hydrogen peroxide, bromosuccinimide (NBS), chlorine water, chlorine-containing solution, hydrochloric acid + hydrogen peroxide, hypochlorous acid and chlorosuccinimide (NCS);

(3) ammonolysis

According to the mol ratio of 4-polyfluoro methoxy-2-haloaniline to ammonia of 1: 0.8-30.0, adding 4-polyfluoromethoxy-2-halogenoaniline into an ammonia water solution or an organic solvent, adding a copper catalyst with the mass of 0.1-10% of that of the 4-polyfluoromethoxy-2-halogenoaniline, and carrying out ammonolysis for 1-72 h at 50-200 ℃ and 0.01-10 Mpa to obtain a target product, namely 4-polyfluoromethoxy o-phenylenediamine; wherein the organic solvent is tetrahydrofuran or dioxane, and the ammonia content is 10-60%; the copper catalyst is any one of cupric chloride, cupric bromide, cuprous chloride and cuprous bromide.

The invention has the advantages that: the method takes p-aminophenol as a raw material, and obtains a target product 4-polyfluoro methoxy o-phenylenediamine through three-step reactions of etherification, halogenation and aminolysis; the process is simple and short, high in yield, low in cost, good in quality, light in pollution, suitable for industrial production and has competitive advantages compared with the same industry.

Detailed Description

A preparation method of 4-polyfluoro methoxy o-phenylenediamine comprises the following specific implementation steps: