CN108191682B

CN108191682B - Synthetic method of 2, 2-bis [4- (3-aminophenoxy) phenyl ] propane

Info

Publication number: CN108191682B
Application number: CN201810078566.4A
Authority: CN
Inventors: 胡国宜; 胡锦平; 黄华银; 李喜龙; 奚小金
Original assignee: Changzhou Sunlight Pharmaceutical Co ltd
Current assignee: Changzhou Sunlight Pharmaceutical Co ltd
Priority date: 2018-01-26
Filing date: 2018-01-26
Publication date: 2020-09-22
Anticipated expiration: 2038-01-26
Also published as: CN108191682A

Abstract

The invention discloses a method for synthesizing 2, 2-bis [4- (3-aminophenoxy) phenyl ] propane, which is prepared by one-step condensation reaction of bisphenol A and 3-halogenated aniline in the presence of an organic solvent, an alkaline catalyst and a phase transfer catalyst. Wherein, the 3-halogenated aniline is 3-chloroaniline or 3-bromoaniline; the organic solvent is toluene or xylene; the alkaline catalyst is sodium hydroxide or potassium hydroxide; the phase transfer catalyst is tetraethylammonium chloride or tetrabutylammonium bromide. The method has the advantages of simple operation, high process safety, convenient post-treatment, low production cost, small environmental pollution, high reaction yield and high product purity, and is suitable for industrial production.

Description

Synthetic method of 2, 2-bis [4- (3-aminophenoxy) phenyl ] propane

Technical Field

The invention belongs to the technical field of organic synthesis, and particularly relates to a synthetic method of 2, 2-bis [4- (3-aminophenoxy) phenyl ] propane.

Background

The binary amino compound containing aromatic rings in the molecular structure is an important raw material for preparing materials such as high-temperature-resistant polyimide polymer, carbon fiber reinforced composite material matrix resin, liquid crystal orientation agent, ultra-large-scale integrated circuit passivation coating and the like. Polyimide containing aromatic rings has excellent stability, radiation resistance, excellent mechanical properties, organic solvent resistance and the like, and thus has very wide application in the very important national economic fields of electronics, aviation and the like.

2, 2-bis [4- (3-aminophenoxy) phenyl ] propane is an important one of aromatic ring-containing diamine compounds, and has a wide market prospect.

Currently, the synthesis method of 2, 2-bis [4- (3-aminophenoxy) phenyl ] propane is to use bisphenol a and m-dinitrobenzene as starting materials, obtain 2, 2-bis [4- (3-nitrophenoxy) phenyl ] propane through nucleophilic substitution reaction, and obtain 2, 2-bis [4- (3-aminophenoxy) phenyl ] propane through reduction reaction [ see documents 1 to 3 ], and the synthesis route is as follows:

。

the method has the following disadvantages:

(1) the nucleophilic substitution reaction is not only longer, but also lower in yield and purity due to lower activity of m-dinitrobenzene, and is not suitable for industrial production.

(2) For a reduction system adopting hydrazine hydrate and ferric trichloride, hydrochloric acid is used for salifying after reduction, and then alkali is added to free a target product; on one hand, the hydrochloride is viscous and difficult to pump and filter, and on the other hand, the hydrochloric acid has large corrosion to equipment and pollution to the environment, so that three wastes are more, and the hydrochloride is not suitable for industrial production.

(3) For a reduction system adopting hydrazine hydrate and palladium-carbon catalyst, the palladium-carbon catalyst is expensive, so that the production cost is high, and the method is not suitable for industrial production.

Document 1: U.S. patent document US5077436A, published 1991, 12 and 31.

Document 2: "Synthesis of 2,2' -bis [4- (3-aminophenoxy) phenyl ] propane", Huang Ying et al, chemical world, Vol.49, No. 4, p.229, 232, p.2008, 12/31.

Document 3: "Synthesis and application of 2, 2-bis [4- (3-aminophenoxy) phenyl ] propane", Zhou super et al, insulation Material, Vol 42, No. 5, p 24-27, p 12/31, 2009.

Disclosure of Invention

The invention aims to solve the problems and provide a synthetic method of 2, 2-bis [4- (3-aminophenoxy) phenyl ] propane, which has the advantages of low production cost, less environmental pollution, high product purity and yield and suitability for industrial production.

The technical scheme for realizing the purpose of the invention is as follows: a process for synthesizing 2, 2-bis [4- (3-aminophenoxy) phenyl ] propane includes one-step condensation reaction between biphenol A and 3-halophenylamine.

The specific synthetic route is as follows:

。

the molar ratio of the 3-halogenated aniline to the bisphenol A is 2: 1-5: 1, and preferably 2: 1-2.1: 1.

The 3-halogenated aniline is 3-chloroaniline, 3-bromoaniline or 3-iodoaniline, preferably 3-chloroaniline or 3-bromoaniline, and more preferably 3-chloroaniline.

The condensation reaction is carried out in the presence of an organic solvent; the organic solvent is one or more (including two) of benzene, toluene, xylene, mesitylene, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, ethylene glycol dimethyl ether, acetone and acetonitrile, and is preferably toluene or xylene, and more preferably xylene.

The weight ratio of the organic solvent to the 3-halogenated aniline is 1: 1-5: 1.

The condensation reaction is carried out in the presence of a basic catalyst; the basic catalyst is one or more (including two) of sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate and potassium bicarbonate, preferably sodium hydroxide or potassium hydroxide, and more preferably potassium hydroxide.

The molar ratio of the alkaline catalyst to the bisphenol A is 2: 1-5: 1, preferably 2: 1-2.5: 1, and more preferably 2.2: 1.

The condensation reaction is carried out in the presence of a phase transfer catalyst; the phase transfer catalyst is one or more (including two) of tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetramethylammonium bromide and tetrabutylphosphonium bromide, preferably tetraethylammonium chloride or tetrabutylammonium bromide, and more preferably tetrabutylammonium bromide.

The molar ratio of the phase transfer catalyst to the bisphenol A is 0.01: 1-1: 1, preferably 0.05: 1-0.5: 1, and more preferably 0.1: 1.

The invention has the following positive effects: the method has the advantages of simple operation, high process safety, convenient post-treatment, low production cost, small environmental pollution, high reaction yield and high product purity, and is suitable for industrial production.

Detailed Description

(example 1)

The synthesis method of 2, 2-bis [4- (3-aminophenoxy) phenyl ] propane of this example is specifically as follows:

under the protection of nitrogen, 262.0g of 3-chloroaniline (2.05 mol), 228.0g of bisphenol A (1.0 mol), 32.2g of tetrabutylammonium bromide (0.1 mol), 500mL of xylene and 440g of 28wt% potassium hydroxide solution (2.2 mol) are sequentially added into a reaction kettle, stirred and heated to reflux, and the reaction is completed.

After the reaction, the reaction system was cooled to room temperature (20. + -. 5 ℃ C.), then 500mL of water was added and stirred for 1 hour, the mixture was allowed to stand for separation, the organic layer was crystallized overnight at 0 to 5 ℃ C, and then filtered, and the filter cake was washed with toluene (50 mL. times.2) and n-hexane (50 mL. times.2) in this order, preferably dried under vacuum, to obtain 340.3g of 2, 2-bis [4- (3-aminophenoxy) phenyl ] propane with a yield of 83.0% and a purity of 99.6% (HPLC).

(examples 2 to 5)

The synthesis method of each example is substantially the same as that of example 1 except for the differences shown in table 1.

TABLE 1

	Example 1	Example 2	Example 3	Example 4	Example 5
						3-halo Aniline	3-chloroaniline 262g	3-bromoaniline 353g	3-chloroaniline 262g	3-chloroaniline 262g	3-chloroaniline 262g
Organic solvent Agent for treating cancer	Xylene 500mL	Xylene 500mL	Toluene 500mL	Xylene 500mL	Xylene 500mL
						Alkaline catalyst Agent for chemical treatment	28wt% hydrogen hydroxide 440g of potassium solution	28wt% hydrogen hydroxide 440g of potassium solution	28wt% hydrogen hydroxide 440g of potassium solution	32% by weight of hydrogen hydroxide 275g of sodium solution	28wt% hydrogen hydroxide 440g of potassium solution
Phase transfer Catalyst and process for preparing same	Tetrabutyl bromide Ammonium 32.2g	Tetrabutyl bromide Ammonium 32.2g	Tetrabutyl bromide Ammonium 32.2g	Tetrabutyl bromide Ammonium 32.2g	Tetraethyl chloride Ammonium 16.6g
						The product is heavy Measurement of	340.3g	307.5g	323.9g	328.0g	295.2
Yield of	83.0%	75.0%	79.0%	80.0%	72.0%
						Purity of	99.7%	99.3%	99.5%	99.5%	99.3%

Claims

1. A synthetic method of 2, 2-bis [4- (3-aminophenoxy) phenyl ] propane is characterized in that: it is prepared by one-step condensation reaction of bisphenol A and 3-halogenated aniline; the condensation reaction is carried out in the presence of an organic solvent; the organic solvent is toluene or xylene; the condensation reaction is carried out in the presence of a basic catalyst; the alkaline catalyst is sodium hydroxide or potassium hydroxide; the condensation reaction is carried out in the presence of a phase transfer catalyst; the phase transfer catalyst is tetraethylammonium chloride or tetrabutylammonium bromide; the molar ratio of the 3-halogenated aniline to the bisphenol A is 2: 1-2.1: 1.

2. The method for synthesizing 2, 2-bis [4- (3-aminophenoxy) phenyl ] propane according to claim 1, characterized in that: the 3-halogenated aniline is 3-chloroaniline or 3-bromoaniline.

3. The method for synthesizing 2, 2-bis [4- (3-aminophenoxy) phenyl ] propane according to claim 1, characterized in that: the organic solvent is xylene.

4. The method for synthesizing 2, 2-bis [4- (3-aminophenoxy) phenyl ] propane according to claim 1, characterized in that: the alkaline catalyst is potassium hydroxide.

5. The method for synthesizing 2, 2-bis [4- (3-aminophenoxy) phenyl ] propane according to claim 1, characterized in that: the phase transfer catalyst is tetrabutylammonium bromide.