阅读说明：本技术 2,2-双（3-氨基-4-羟基苯基）六氟丙烷的合成方法 (Synthesis method of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane ) 是由 胡国宜 胡锦平 吴建华 王凯 于 2020-12-31 设计创作，主要内容包括：本发明公开了一种2,2-双(3-氨基-4-羟基苯基)六氟丙烷的合成方法,它是以邻氨基苯酚为起始原料,先经乙酰化得到邻乙酰氨基苯酚,然后与六氟丙酮三水合物缩合得到2,2-双(3-乙酰氨基-4-羟基苯基)六氟丙烷,最后脱乙酰基得到2,2-双(3-氨基-4-羟基苯基)六氟丙烷。本发明的合成路线既不需要催化氢化,也不需要硝化,与现有合成2,2-双(3-氨基-4-羟基苯基)六氟丙烷的路线相比,安全性更高,对环境更友好,生产成本更低,而收率基本相当,从而更适合工业化大生产。(The invention discloses a synthesis method of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, which comprises the steps of using o-aminophenol as a starting material, firstly performing acetylation to obtain o-acetaminophenol, then condensing with hexafluoroacetone trihydrate to obtain 2, 2-bis (3-acetamido-4-hydroxyphenyl) hexafluoropropane, and finally performing deacetylation to obtain 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane. The synthetic route of the invention does not need catalytic hydrogenation or nitration, and compared with the existing synthetic route of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, the synthetic route has the advantages of higher safety, more environmental friendliness, lower production cost and basically equivalent yield, thereby being more suitable for industrial mass production.)

1. A synthetic method of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is characterized by comprising the following steps: the method comprises the steps of firstly acetylating o-aminophenol serving as an initial raw material to obtain o-acetaminophenol, then condensing the o-acetaminophenol with hexafluoroacetone trihydrate to obtain 2, 2-bis (3-acetamido-4-hydroxyphenyl) hexafluoropropane, and finally deacetylating to obtain the 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.

2. The method for synthesizing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane as claimed in claim 1, wherein: the acetylation is carried out in ethyl acetate solvent; the acetylation reagent adopted in the acetylation is one of acetic anhydride, acetyl chloride, chloroacetyl chloride, dichloroacetyl chloride and trichloroacetyl chloride; the mol ratio of the o-aminophenol to the acetylation reagent is 1: 1-1: 2.

3. The method for synthesizing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane as claimed in claim 2, wherein: the acetylation reagent adopted in the acetylation is acetic anhydride; the mol ratio of the o-aminophenol to the acetylation reagent is 1: 1-1: 1.5; the reaction temperature of acetylation is 15-30 ℃.

4. The method for synthesizing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane as claimed in claim 1, wherein: the molar ratio of the o-acetamidophenol to the hexafluoroacetone trihydrate is 1: 0.45-1: 0.6.

5. The method for synthesizing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane as claimed in claim 1, wherein: the condensation is carried out in the presence of hydrofluoric acid; the molar ratio of the o-acetamidophenol to the hydrofluoric acid is 1: 5-1: 10.

6. The method for synthesizing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane as claimed in claim 1, wherein: the reaction temperature of the condensation is 100-110 ℃; the reaction pressure of the condensation is 0.5-1.0 MPa.

7. The method for synthesizing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane as claimed in claim 1, wherein: the method for synthesizing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane as claimed in claim 1, wherein: the deacetylation comprises acidic deacetylation and basic deacetylation; the deacetylation reagent adopted for the acid deacetylation is hydrochloric acid; the deacetylation reagent adopted for the alkaline deacetylation is lithium hydroxide, sodium hydroxide or potassium hydroxide; the molar ratio of the 2, 2-bis (3-acetamido-4-hydroxyphenyl) hexafluoropropane to the deacetylation reagent is 1: 2-1: 5.

8. The method for synthesizing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane as claimed in claim 7, wherein: the reaction temperature of the acidic deacetylation is 90-100 ℃; the acidic deacetylation is carried out in a 1, 4-dioxane solvent.

9. The method for synthesizing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane as claimed in claim 7, wherein: the reaction temperature of the alkaline deacetylation is 50-80 ℃; the alkaline deacetylation is carried out in a mixed solvent of ethanol and water; the volume ratio of the ethanol to the water is 1: 1-3: 1.

Technical Field

The invention belongs to the technical field of organic synthesis, and particularly relates to a synthetic method of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.

Background

2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, also known as 5,5' - (hexafluoroisopropyl) -bis- (2-aminophenol), white crystals, melting point: 243-246 ℃, and the molecular formula is as follows: c₁₅H₁₂F₆N₂O₂The relative component: 366.26. the product is nontoxic and can be stored in a room temperature environment in a dark place and isolated from air.

2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHPFP) is an important polyimide monomer, can be particularly used as a monomer for preparing special high-molecular functional materials of polyimide, is mainly used for raw materials of heat-resistant polymers, particularly electronic materials, such as raw materials of computer chips and the like, and has wide application.

The existing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is basically prepared by catalytic hydrogenation of 2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane [ see chinese patent documents CN1948273A, CN101481318A, CN101492381A, CN101643427A and CN105218387A ].

The catalytic hydrogenation belongs to high-risk reaction, has low safety, and needs a noble metal catalyst with higher price, thus leading to higher production cost.

For 2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane, the existing synthesis method mainly has the following two routes:

(1) halogen benzene method: halogen benzene is used as an initial raw material, firstly condensed with hexafluoroacetone gas to obtain 2, 2-bis (4-halophenyl) hexafluoropropane, then the 2, 2-bis (3-nitro-4-fluorophenyl) hexafluoropropane is obtained through nitration, and finally the 2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane is obtained through hydrolysis [ see Chinese patent document CN111302944A ].

(2) Phenol method: phenol is used as a starting material, and is firstly condensed with hexafluoroacetone gas to obtain 2, 2-bis (4-hydroxyphenyl) hexafluoropropane (also called bisphenol AF) [ see Chinese patent document CN101870641A ], and then is nitrified to obtain 2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane [ see Chinese patent documents CN103102272A, CN105218387A and CN105753710A ].

The disadvantages of the prior art methods are:

(1) the method needs nitration reaction, and the nitration also belongs to high-risk reaction, has low safety, and particularly generates a large amount of waste acid due to nitration, so that the method is not environment-friendly, and has high treatment cost, thereby causing high production cost.

(2) The halogen benzene method has more reaction steps, the yield in the three steps of the chlorobenzene method can reach 83.5 percent, and the yield in the three steps of the fluorobenzene method is only 70.7 percent.

(3) The nitration reaction yield of bisphenol AF is not high.

Disclosure of Invention

The invention aims to solve the problems and provide a synthetic method of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, which has higher yield, higher safety, more environmental friendliness and lower production cost and is more suitable for industrial mass production.

The technical scheme for realizing the purpose of the invention is as follows: a synthetic method of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane takes o-aminophenol as a starting material, and comprises the steps of acetylating to obtain o-acetaminophenol, condensing with hexafluoroacetone trihydrate to obtain 2, 2-bis (3-acetamido-4-hydroxyphenyl) hexafluoropropane, and deacetylating to obtain 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.

The acetylation reagent adopted in the acetylation is one of acetic anhydride, acetyl chloride, chloroacetyl chloride, dichloroacetyl chloride and trichloroacetyl chloride, and acetic anhydride is preferred.

The mol ratio of the o-aminophenol to the acetylation reagent is 1: 1-1: 2, and preferably 1: 1-1: 1.5.

The acetylation is carried out in ethyl acetate solvent.

The reaction temperature of acetylation is 15-30 ℃.

The molar ratio of the o-acetamidophenol to the hexafluoroacetone trihydrate is 1: 0.45-1: 0.6.

The condensation is carried out in the presence of hydrofluoric acid; the molar ratio of the o-acetamidophenol to the hydrofluoric acid is 1: 5-1: 10.

The reaction temperature of the condensation is 100-110 ℃.

The reaction pressure of the condensation is 0.5-1.0 MPa.

The deacetylation includes acidic deacetylation and basic deacetylation.

The deacetylation reagent adopted in the acidic deacetylation is hydrochloric acid.

The acidic deacetylation is carried out in a 1, 4-dioxane solvent.

The reaction temperature of the acidic deacetylation is 90-100 ℃.

The deacetylation reagent adopted in the alkaline deacetylation is lithium hydroxide, sodium hydroxide or potassium hydroxide, and preferably sodium hydroxide.

The alkaline deacetylation is carried out in a mixed solvent of ethanol and water; the volume ratio of the ethanol to the water is 1: 1-3: 1.

The reaction temperature of the alkaline deacetylation is 50-80 ℃.

The molar ratio of the 2, 2-bis (3-acetamido-4-hydroxyphenyl) hexafluoropropane to the deacetylation reagent is 1: 2-1: 5.

The invention has the following positive effects: the synthetic route of the invention does not need catalytic hydrogenation or nitration, and compared with the existing synthetic route of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, the synthetic route has the advantages of higher safety, more environmental friendliness, lower production cost and basically equivalent yield, thereby being more suitable for industrial mass production.

Detailed Description

(example 1)

The synthetic route of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane in this example is as follows:

。

the specific method comprises the following steps:

adding 218.3g (2.0 mol) of o-aminophenol and 2L of ethyl acetate into a 5L three-necked bottle, stirring and dissolving, cooling to 5 +/-1 ℃, dropwise adding 208mL (2.2 mol) of acetic anhydride at the temperature, slowly heating to 20-25 ℃ after dropwise adding, and stirring and reacting to complete reaction (about 2.5 h).

After the reaction is finished, 600mL of water is added into a reaction system, the mixture is stirred for 1-2 h at the temperature of 20-25 ℃, then the mixture is kept stand for layering, an organic layer is added into a 3L single-mouth bottle, the mixture is concentrated to 500mL in batches under reduced pressure, 1L of n-heptane is dropwise added at the temperature of 20-25 ℃, solid is separated out, the mixture is continuously stirred for 1-2 h and then filtered, a filter cake is rinsed by a small amount of n-heptane and then is dried under reduced pressure at the temperature of 75 +/-1 ℃, 294.2g of white-like solid o-acetaminophenol is obtained, and the yield is 97.3%.

Adding 250g (1.66 mol) of o-acetaminophenol prepared in the step I into a 2L Hastelloy reaction kettle, then cooling to-30-35 ℃, dropwise adding 187g (0.85 mol) of hexafluoroacetone trihydrate, replacing 3 times with nitrogen, adding 200g (10.0 mol) of hydrofluoric acid, stirring and heating to 105 +/-1 ℃, wherein the pressure can be increased to 0.85MPa at the maximum during the period, and keeping the temperature at 105 +/-1 ℃ for reaction till the reaction is complete.

After the reaction is finished, 3L of water is added into a 5L three-necked bottle, the temperature is reduced to 5 +/-1 ℃, the reaction system is slowly dripped under stirring, the stirring is continued for 1 to 2 hours after the dripping is finished, the filtration is carried out, a filter cake is rinsed by a small amount of water, and the pressure is reduced and dried at the temperature of 75 +/-1 ℃ to obtain 323.5g of white solid 2, 2-bis (3-acetamido-4-hydroxyphenyl) hexafluoropropane, wherein the yield is 86.8%.

③ 150g (0.33 mol) of the 2, 2-bis (3-acetamido-4-hydroxyphenyl) hexafluoropropane obtained in the step II is added into a 2L three-necked bottle, then 600mL of ethanol and 300mL of water are added, then 128g (0.96 mol) of 30wt% sodium hydroxide aqueous solution is dripped at the temperature of 20 +/-1 ℃, and the temperature is raised to 75 +/-1 ℃ after the dripping is finished, and the reaction is stirred until the reaction is completed (about 18 h).

After the reaction was completed, the reaction system was cooled to 20 ± 1 ℃, 4mol/L aqueous hydrochloric acid was added dropwise at that temperature until pH =7.5 ± 0.1, then 600mL dichloromethane was added, the mixture was stirred for 1 hour, and then allowed to stand for delamination, 200mL water was added to the organic layer, the mixture was stirred for 1 hour, and then allowed to stand for delamination again, the organic layer was concentrated to 250mL, 600mL n-heptane was added dropwise, the mixture was stirred for 1 hour and then filtered, the filter cake was rinsed with a small amount of n-heptane, and then dried under reduced pressure at 75 ± 1 ℃ to obtain 114.3g of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane as a white solid with a yield of 93.7%.

(example 2)

The synthetic route of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane in this example is as follows:

。

wherein, the step (i) and the step (ii) are the same as the embodiment 1, and the step (iii) is the following concrete method: 150g (0.33 mol) of 2, 2-bis (3-acetamido-4-hydroxyphenyl) hexafluoropropane prepared in the step II is added into a 2L three-necked bottle, then 750mL of 1, 4-dioxane is added, 250mL (1.0 mol) of hydrochloric acid aqueous solution with the concentration of 4mol/L is dropwise added at the temperature of 25 +/-1 ℃, the temperature is raised to 95 +/-1 ℃ after the dropwise addition, and the reaction is stirred until the reaction is completed (about 18 h).

After the reaction is finished, cooling the reaction system to 25 +/-1 ℃, adding 250mL of ethyl acetate at the temperature, standing for layering, washing an organic layer with 300mL of water, standing for layering again, combining water layers, adding the water layers into a 1L three-necked bottle, controlling the temperature to be 25 +/-1 ℃, dropwise adding 30wt% of sodium hydroxide aqueous solution until the pH is =7.5 +/-0.1, continuously stirring for 2-3 h, filtering, rinsing a filter cake with a small amount of water, and drying under reduced pressure at the temperature of 75 +/-1 ℃ to obtain 103.8g of white solid 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane with the yield of 85.1%.