JP2010159233A - Method for producing 1,3-bis(3-aminophenoxy)benzene - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low-cost and industrially advantageous method for producing high-purity 1,3-bis(3-aminophenoxy)benzene useful as a raw material for a highly heat-resistant polymer such as polyimide, etc. <P>SOLUTION: The method for producing 1,3-bis(3-aminophenoxy)benzene includes heating a 2,4-bis(3-aminophenoxy)benzenesulfonic acid, 2,4-bis(3-acylaminophenoxy)benzenesulfonic acid represented by formula (wherein X is amino or acylamino; and Y is hydrogen or an alkali metal atom) or an alkali metal salt thereof in sulfuric acid to eliminate a sulfonic acid group, and if an acyl group exist, the acyl group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing 1,3-bis (3-aminophenoxy) benzene.

1,3-bis (3-aminophenoxy) benzene is a useful compound as a raw material for high heat-resistant polymers such as polyimide, and in particular, polyimide obtained by using this is widely used bis (4-aminophenyl). ) There is a tendency that the glass transition temperature tends to be lower than that of a polyimide obtained using ether or the like. Therefore, it is useful as an adhesive polyimide to have excellent adhesion performance to a metal or the like (see Patent Document 1).

  As a method for producing 1,3-bis (3-aminophenoxy) benzene, a method in which 1,3-dibromobenzene and 3-aminophenol are reacted in the presence of an alkali (see Patent Document 2), or in the presence of an alkali. A method of reacting resorcinol with 3-bromoaniline (see Patent Document 3) is known, but the yield is only 65% and 58%, respectively, due to low reactivity. I wanted to.

  In addition, a method of reacting 1,3-difluorobenzene and 3-aminophenol in the presence of an alkali (see Patent Document 4 and Patent Document 5) has been proposed, but a high temperature of 200 ° C. or more and a long reaction time are proposed. And is accompanied by the production of by-products that are difficult to separate, requiring complicated purification operations.

On the other hand, 1,3-bis (3-aminophenoxy) -5-chlorobenzene obtained by reacting 1,3,5-trichlorobenzene and 3-aminophenol in the presence of alkali is reduced in the presence of alkali. Although the method of substituting a chlorine atom for a hydrogen atom by performing is known (patent documents 6, 7, and 8), it involves generation of by-products that are difficult to separate even in this method. A complicated purification process such as distillation (Patent Documents 7 and 8) was required.

JP 61-143477 A U.S. Pat. No. 4,222,962 PCT International Application WO92 / 12118 JP 2003-267935 A JP 2006-28081 A JP 60-87247 A JP-A-3-255058 JP-A-4-154746

  An object of the present invention is to provide a low-cost and industrially advantageous method for producing high-purity 1,3-bis (3-aminophenoxy) benzene.

  The present inventors converted 2,4-dihalogenobenzenesulfonic acid or 2,4-dihalogenobenzenesulfonic acid salt, which is a sulfonation product of 1,3-dihalogenobenzene, into 3-acetaminophenol in the presence of alkali. Alternatively, 2,4-bis (3-acetaminophenoxy) benzenesulfonate or 2,4-bis (3-aminophenoxy) benzenesulfonate easily obtained by reaction with 3-aminophenol is used to form a sulfonic acid group and The present invention was completed by paying attention to the removal of the acetyl group to obtain high-purity 1,3-bis (3-aminophenoxy) benzene.

（１）
（式中、Ｘはアミノ基またはアシルアミノ基を示す。Ｙは水素原子またはアルカリ金属原子を示す。）
で表される２，４−ビス（３−アミノフェノキシ）ベンゼンスルホン酸、２，４−ビス（３−アシルアミノフェノキシ）ベンゼンスルホン酸、あるいはそれらのアルカリ金属塩からスルホン酸基、およびアシル基がある場合にはそのアシル基を脱離させることを特徴とする下記構造式（２）

（２）
で表される１，３−ビス（３−アミノフェノキシ）ベンゼンの製造方法に関するものである。 That is, the present invention relates to the general formula (1)

(1)
(In the formula, X represents an amino group or an acylamino group. Y represents a hydrogen atom or an alkali metal atom.)
A sulfonic acid group and an acyl group represented by 2,4-bis (3-aminophenoxy) benzenesulfonic acid, 2,4-bis (3-acylaminophenoxy) benzenesulfonic acid, or an alkali metal salt thereof. In some cases, the acyl group is eliminated and the following structural formula (2)

(2)
It is related with the manufacturing method of 1,3-bis (3-aminophenoxy) benzene represented by these.

  It is possible to provide a method for producing high-purity 1,3-bis (3-aminophenoxy) benzene, which uses a raw material cheaper than known methods as a starting material and does not require a complicated purification step.

  The 2,4-dihalogenobenzenesulfonic acid OLE_LINK3 or 2,4-dihalogenobenzenesulfonic acid alkali metal salt used as a raw material of the present invention may be produced by any method. The alkali metal salt is preferably a sodium salt or a potassium salt.

2,4-Dihalogenobenzenesulfonic acid that can be used in the method of the present invention includes 2,4-difluorobenzenesulfonic acid, 2,4-dichlorobenzenesulfonic acid, 2,4-dibromobenzenesulfonic acid, and 2 , 4-diiodobenzenesulfonic acid, preferably 2,4-difluorobenzenesulfonic acid or 2,4-dichlorobenzenesulfonic acid.

The m-acylaminophenol or m-aminophenol used in the present invention may be reacted with 2,4-dihalogenobenzenesulfonic acid or 2,4-dihalogenobenzenesulfonic acid alkali metal salt in advance as an alkali metal salt. In addition, m-acylaminophenol or m-aminophenol and an alkali agent, 2,4-dihalogenobenzenesulfonic acid or 2,4-dihalogenobenzenesulfonic acid alkali metal salt, etc. are charged all at once into the reactor and reacted. Also good.

Examples of the alkali agent that can be used in the method of the present invention include an alkali hydroxide or an alkali carbonate, such as sodium hydroxide, sodium carbonate, potassium hydroxide, and potassium carbonate.

  The amount of m-acylaminophenol or m-aminophenol used is usually 2-fold mol, preferably 2.1 mol per mol of 2,4-dihalogenobenzenesulfonic acid or 2,4-dihalogenobenzenesulfonic acid alkali metal salt. It is good to use at ~ 3.0 mol.

Examples of the solvent that can be used in the method of the present invention include aprotic polar solvents. Specifically, dimethylformamide (DMF), dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), 1, 3-dimethyl-2-imidazolidinone (DMI), 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone (DMPU), dimethyl sulfoxide (DMSO), sulfolane, hexamethylphospho Lutriamide (HMPA) or the like can be used.

Although there is no restriction | limiting in particular in the usage-amount of a solvent, It is good to use normally 1-20 mass times with respect to the usage-amount of m-acetaminophenol or m-aminophenol, Preferably it is 3-10 mass times.

In order to carry out the method of the present invention, it is more preferable to remove azeotropically the water produced during the reaction in the presence of toluene, xylene and the like in the reaction system.

The amount of toluene and xylene used is not particularly limited as long as it can be azeotropically dehydrated and varies depending on the reaction temperature, but is usually 0.05 to 1 times by mass, preferably 0.05 to 0 times the solvent used. It is good to use at 5 mass times.

The reaction can be carried out in the range of 120 ° C to 220 ° C, preferably in the range of 140 ° C to 200 ° C, more preferably in the range of 160 ° C to 180 ° C.

The sulfuric acid concentration in the hydrolysis is preferably in the range of 55% to 70%, more preferably the sulfuric acid concentration is 62% to 65%. If the sulfuric acid concentration is low, the hydrolysis rate is slow, and if the sulfuric acid concentration is high, sulfuric acid oxidation occurs, which is not desirable.

The reaction temperature in the hydrolysis is 100 ° C. to 130 ° C., corresponding to the reflux temperature of each sulfuric acid concentration.

[Example]
The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples.

In a 300 mL flask equipped with a Dean-Stark trap equipped with a stirrer, a thermometer, and a condenser, 18.0 g (0.065 mol) of sodium 2,4-dichlorobenzenesulfonate and 29.1 g (0.174 mol) of m-acetaminophenol ), 11.6 g (0.176 mol) of potassium hydroxide (purity 85%), 5.0 g (0.036 mol) of potassium carbonate, 100 g of NMP, 43 g of toluene and 15 g of water, and 150 while collecting water and toluene. It was made to react at -180 degreeC for 31 hours. After the reaction, the solvent was recovered by distillation under reduced pressure to obtain a distillation residue containing sodium 2,4-bis (3-acetaminophenoxy) benzenesulfonate.
This distillation residue was charged with 100.0 g (0.637 mol) of 62.5% sulfuric acid and reacted at 122 to 126 ° C. for 26 hours to simultaneously remove sulfonic acid groups and acetyl groups. The reaction solution was cooled to 25 ° C., 40.0 g of water was added, and 80.0 g (0.790 mol) of 36% hydrochloric acid was added dropwise over 1 hour, further cooled to 5 ° C. and filtered, and the LC purity was 92.1. % Of 1,3-bis (3-aminophenoxy) benzene hydrochloride 50.1 g · wet was obtained.
To 50.1 g · wet of hydrochloride of 1,3-bis (3-aminophenoxy) benzene, 100.0 g (0.475 mol) of a 19.0 wt% aqueous sodium hydroxide solution was added and stirred at room temperature for 1 hour. The cake was taken out by filtration, 100.0 g (0.075 mol) of a 3.0 wt% aqueous sodium hydroxide solution was added to the cake, and the mixture was stirred at room temperature for 1 hour and filtered. The cake was slurry washed with 100.0 g of water, filtered and dried to obtain 9.8 g of crude 1,3-bis (3-aminophenoxy) benzene having an LC purity of 98.8%. Total yield of condensation, desulfonation and hydrolysis reactions based on sodium 2,4-dichlorobenzenesulfonate 46.4%.
To 9.8 g of crude 1,3-bis (3-aminophenoxy) benzene, 36 g of toluene and 56.0 g (0.070 mol) of 5.0% aqueous sodium hydroxide solution were added, the temperature was raised to 75 ° C., and the mixture was heated and stirred for 15 minutes. did. The lower aqueous layer was removed by standing, and the upper toluene layer was washed twice with 10.0 g (0.012 mol) of 5.0 wt% sodium hydroxide aqueous solution and then with 10 g of water 5 times. Washed. 1.0 g · wet of activated carbon was added to 46.0 g of the toluene layer, and the mixture was stirred at room temperature for 15 minutes and filtered. The filtrate was concentrated to 25.0 g, filtered and dried to obtain 8.5 g of 1,3-bis (3-aminophenoxy) benzene having an LC purity of 99.5%. Purification yield 86.7%. Mp 107-108 ° C. OLE_LINK2
OLE_LINK2

In a 300 mL flask with a Dean-Stark trap equipped with a stirrer, thermometer, and condenser, 29.1 g (0.174 mol) of m-acetaminophenol and 11.6 g (0.176 mol) of potassium hydroxide (purity 85%) , NMP 100 g, toluene 43 g, and water 15 g were charged and dehydrated at 120 to 150 ° C. to recover 21 g of water. After cooling to 100 ° C., 14.1 g (0.065 mol) of 2,4-difluorobenzenesulfone sodium was charged, and the mixture was reacted at 150 to 185 for 35 hours while collecting water and toluene. After the reaction, the solvent was recovered by distillation under reduced pressure to obtain 78.0 g of sodium 2,4-bis (3-acetaminophenoxy) benzenesulfonate having an LC purity of 69.5% as a distillation residue.
This distillation residue was charged with 100.0 g (0.637 mol) of 62.5% sulfuric acid, reacted at 122-125 ° C. for 14 hours to simultaneously remove sulfonic acid groups and acetyl groups, and then treated in the same manner as in the examples. And dried to obtain 15.4 g of crude 1,3-bis (3-aminophenoxy) benzene having an LC purity of 99.5%. Total yield of condensation, desulfonation and hydrolysis reactions based on sodium 2,4-difluorobenzenesulfonate is 73.0%.
The product was purified in the same manner as in Example 1 and dried to obtain 12.6 g of 1,3-bis (3-aminophenoxy) benzene having an LC purity of 99.6%. Purification yield 81.8%. Mp 105-106 ° C.

The reaction was carried out at 150 to 180 ° C. for 31 hours in the same manner as in Example 1 except that 19.1 g (0.174 mol) of m-aminophenol was used instead of m-acetaminophenol. After the reaction, 84.0 g of sodium 2,4-bis (3-aminophenoxy) benzenesulfonate having an LC purity of 53.5% was obtained as a distillation residue by distillation under reduced pressure.
The distillation residue was charged with 138.2 g (0.851 mol) of 60.4% sulfuric acid, reacted at 106 to 119 ° C. for 25 hours to remove sulfonic acid groups, and then treated in the same manner as in Example 1. By drying, 8.5 g of crude 1,3-bis (3-aminophenoxy) benzene having an LC purity of 99.2% was obtained. Total yield of condensation, desulfonation and hydrolysis reactions based on sodium 2,4-dichlorobenzenesulfonate is 40.3%.
Furthermore, it refine | purified like Example 1 and it dried and obtained 6.7 g of 1, 3-bis (3-aminophenoxy) benzene of LC purity 99.6%. Purification yield 78.8%. Mp 105-106 ° C.
(Comparative Example 1)

In a 100 mL flask equipped with a Dean-Stark trap equipped with a stirrer, thermometer, nitrogen inlet tube, and condenser tube, 12.0 g (0.174 mol) of m-aminophenol and 7.3 g of potassium hydroxide (88% purity) (0. 115 mol), 50 g of NMP, 6 g of toluene, and 10 g of water. The temperature was raised to 170 ° C. under a nitrogen stream, and 13 g of water and 6 g of toluene were recovered. Once cooled to 160 ° C., 7.4 g (0.050 mol) of m-dichlorobenzene was charged, and the temperature was raised stepwise and reacted at 185 ° C. for 20 hours and 195 ° C. for 7 hours. As a result of GC analysis, m-dichlorobenzene 0.5%, m-aminophenol 14.1%, 3-amino-3'-chlorodiphenyl ether 45.0%, 1,3-bis (3-aminophenoxy) benzene 7 .5%. This result clearly shows the activation effect of the sulfonic acid group.

Claims (3)

General formula (1)

(1)
(In the formula, X represents an amino group or an acylamino group. Y represents hydrogen or an alkali metal atom.)
A sulfonic acid group and an acyl group are represented by 2,4-bis (3-aminophenoxy) benzenesulfonic acid, 2,4-bis (3-acylaminophenoxy) benzenesulfonic acid represented by the following formula: In some cases, the acyl group is eliminated and the following structural formula (2)

(2)
The manufacturing method of 1,3-bis (3-aminophenoxy) benzene represented by these. The 2,4-bis (3-aminophenoxy) benzenesulfonic acid, 2,4-bis (3-acylaminophenoxy) benzenesulfonic acid, or an alkali metal salt thereof is heated in sulfuric acid. The method according to 1.   The method according to claim 1 or 2, wherein the acylamino group is an acetamino group.