JPH04108767A - Production of bis(3-aminophenoxy) compound - Google Patents

Abstract

PURPOSE:To obtain the title compound useful as a raw material component for heat-resistant high polymer in high purity and good yield by subjecting a bis(3-nitrophenoxy) compound to catalytic reduction while adding the above- mentioned compound to a reactor in which an aprotic polar solvent and carried platinum group catalyst are charged. CONSTITUTION:A compound expressed by formula I [X is 1-10C divalent hydrocarbon group, C(CF3)2, CO, S, SO, SO2 or single bond] is reacted, by adding thereof in a rate corresponding to the progress of reaction, to a reactor in which an aprotic solvent and a platinum group catalyst carried on a support (preferably alumina or magnesium oxide) consisting of a metal oxide, sulfate and carbonate are previously charged, at ordinary pressure to a slight pressurization of about 1000mmH2 at 50-100 deg.C to provide the objective compound. According to the above-mentioned method, nitroso and hydroxylamine concentration in the system is maintained in low state and the subsidiary production of an azo compound by condensation of these compounds can be suppressed and filtration leakage of the catalyst is prevented.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to the general formula (I) [wherein, X is a divalent hydrocarbon group having 1 to IO carbon atoms, or -C(CF, -CO-1-S-, -5O
-1-SO, - or -〇- represents a divalent group. Alternatively, X may be directly bonded with a single bond. ] When carrying out catalytic reduction of the bis(3-nitrophenoxy) compound represented by The reaction is carried out while adding the bis(3-nitrophenoxy) compound represented by the general formula (I) into a reactor containing a reaction solvent and a catalyst in advance. n) [wherein, X has the same meaning as in general formula (I). ]
The present invention relates to a method for producing a bis(3-aminophenoxy) compound represented by:

The bis(3-aminophenoxy) compound represented by the general formula (rl) is an important compound as a monomer for heat-resistant polymers, particularly as a raw material component for polyamide, polyimide, polyamideimide, and the like.

For example, a polyamide-imide copolymer made from a compound represented by formula (II) (Japanese Patent Laid-Open No. 58-79019)
, polyimidehydantoin (JP-A-52-63998)
, polyimide (Japanese Unexamined Patent Publication No. 58-76425) has been disclosed, and it has already been reported that it can be used as a heat-resistant resin. Moreover, an adhesive having excellent heat resistance can be obtained from polyimide' containing this compound as a diamine component.

(Prior art) In the above general formula (I) C, X is a divalent hydrocarbon group having 1 to 10 carbon atoms, or -C(CFs)z-, -CO-5-S-, -5O −
Indicates a divalent group of 1-SO□- or -〇-. or X
may be directly bonded with a single bond. General formula (I[) by reducing the bis(3-nitrophenoxy) compound represented by ] [wherein, X has the same meaning as in general formula (I)]. ]
A method for producing the bis(3-aminophenoxy) compound represented by is already known from JP-A-61-194055. Furthermore, JP-A-62-70347 discloses a method for producing 4,4'-bis(3-aminophenoxy)biphenyl by reducing 4,4'-bis(3-nitrophenoxy)biphenyl. ing.

According to these publications, the desired bis(3-aminophenoxy) compound can be obtained in the reaction by a conventional method of reducing a nitro group to an amino group, industrially preferably by catalytic reduction or hydrazine reduction. can.

Furthermore, according to the publication, as a method using catalytic reduction,
- Using a metal catalyst used for catalytic reduction in boat fishing, the reaction can be carried out in a solvent inert to the reaction at a reaction temperature of 20 to 200°C and a hydrogen pressure of normal pressure to 50 kg/cdG.

[Problem to be solved by the invention]

By following the reduction method described above, the desired bis(3-aminophenoxy) compound can be obtained relatively easily and in a good yield, but among these methods, the contact method is the most industrially efficient method. When the reaction is carried out according to the reduction method (see Patent Example 2 above), the general formula (
I[[] [wherein,
It represents a divalent group of S-, -5O-1-502- or -O-. Or X may be directly bonded with a single bond, R
represents a 3-aminophenyl group. ] It was found that the Ab compound represented by the following was produced as a by-product at a rate of about 0.5 to 0.8% of the total product.

In the method using catalytic reduction, trace amounts of other by-products are also observed, but by-products other than the azo compound can be easily converted to the target bisproduct by normal purification operations such as recrystallization following the reaction. (3-aminophenoxy) compound, whereas the Ab compound contaminates the product bis(3-aminophenoxy) compound as an impurity, which cannot be removed by these purification operations.

These impurities cause deterioration in the physical properties of polyimide obtained using the product diamine as a raw material.

Furthermore, when carrying out this catalytic reduction method, it has been found that when a specific solvent and a specific catalyst are used, filtration leakage occurs when the catalyst is filtered out from the reaction solution. It has been found that especially in the case of carbon-supported platinum group catalysts that use aprotic polar solvents and are commonly used in catalytic reduction methods, this tendency is particularly significant and poses a problem in the recycling of the catalysts.

[Means for solving the problem: In view of this situation, the present inventors used the industrially most advantageous catalytic reduction method to suppress the production of azo compounds, which are by-products unique to catalytic reduction. In order to provide a method for producing the desired bis(3-aminophenoxy) compound while also preventing the catalyst from leaking through filtration, we conducted intensive studies on the catalytic reduction of bis(3-nitrophenoxy) compounds. . As a result, we used an aprotic polar solvent and a platinum group catalyst supported on a carrier consisting of metal oxides, sulfates, and carbonates as catalysts, and simultaneously introduced hydrogen gas into a reactor that had been charged with these in advance. The present invention was completed by discovering that by carrying out the reaction while adding the bis(3-nitrophenoxy) compound as a raw material, the production of such by-products can be suppressed and the desired product can be produced without leaking the catalyst through filtration. I ended up doing it.

That is, the present invention relates to the general formula (]) [wherein, X is a divalent hydrocarbon group having 1 to 10 carbon atoms, or -C(Ch)z-1-CO-1-s-, -5o-1
-so□= or -0- represents a divalent group. Alternatively, X may be directly bonded with a single bond. ] screws (
When catalytically reducing a compound (3-nitrophenoxy),
An aprotic polar solvent is used as the reaction solvent, and a platinum group catalyst supported on a carrier consisting of a metal oxide, sulfate, or carbonate is used as the catalyst, and a general Bis(3) represented by formula (I)
General formula (I [) [wherein, X has the same meaning as in general formula (I)], characterized in that the reaction is carried out while adding a -nitrophenoxy) compound. ]
This is a method for producing a bis(3-aminophenoxy) compound represented by

The formation mechanism of ab compounds in the reduction reaction of nitro compounds is explained as follows: azoxy compounds are produced by the condensation reaction of nitroso compounds, which are intermediates for the reduction of nitro compounds to amines, and hydroxylamine, and then this is reduced to produce azo compounds. has been done.

If the reaction conditions are such that the raw material bis(3-nitrophenoxy) compound is prepared and charged into the reaction system all at once, and then the reaction is started, as in the conventional technique described above, during the reaction of the nitroso compound and hydroxylamine. The concentration of the azo compound in the system cannot be controlled, and the rate of the reduction reaction of the compound is not large enough compared to the reaction rate of the azoxy compound production reaction by condensation of the compound. It is expected that it will not be possible to suppress the generation of

Under the reaction conditions newly provided by the present invention, by carrying out the reaction while supplying the raw material bis(3-nitrophenoxy) compound at a rate commensurate with the reaction rate of the reduction reaction, nitroso and Since the reaction proceeds in a state where the concentration of hydroxylamine is low and the condensation reaction of these compounds can be suppressed, it is possible to produce the target bis with extremely high purity and high yield, which is extremely advantageous industrially. It became possible to produce a (3-aminophenoxy) compound.

The compound produced by the method of the present invention is a bis(3-aminophenoxy) compound represented by the general formula (n).

Specifically, 4.4”-bis(3-aminophenoxy)
Biphenyl, 4,4゛-bis(3-aminophenoxy)
Diphenylmethane, 2,2-bis(4-(3-aminophenoxy)phenyl)propane, 2,4-bis(4-(
3-aminophenoxy)phenyl]-2-methylpentane, 2.4-bis(4-(3-aminophenoxy)phenyl)-4-methyl-1-pentene, 2.2-bis(4
-(3-aminophenoxy)]hexafluoropropane, 4,4゛-bis(3-aminophenoxy)benzophenone, 4,4゛-bis(3-aminophenoxy)diphenyl sulfide, 4,4゛-bis(3-aminophenoxy)diphenylsulfide, -aminophenoxy) diphenyl sulfoxide, 4,4'-bis(3-aminophenoxy) diphenyl sulfone, and 4'4'-bis(3-aminophenoxy) diphenyl ether.

The compound used as a raw material in the present invention has the general formula (
It is a bis(3-nitrophenoxy) compound represented by I). Specifically, 4,4'-hys(3-nitrophenoxy)biphenyl, 4,4'-hys(3-nitrophenoxy)diphenylmethane, 2,2-bis[4-(3-nitrophenoxy)biphenyl
-nitrophenoxy)phenyl]furonoman, 2.4-
His[4-(3-nitrophenoxy)phenyl] = 2-
Methylpentane, 2,4-bis(4-(3-nitrophenoxy)phenyl]-4-methyl-1-hentene, 2゜2obis(4-(3-nitrophenoxy))hexafluoropropane, 4,4゛-Bis(3-nitrophenoxy)benzophenone, 4.4'-bis(3-nitrophenoxy)diphenyl sulfide, 4,4'-bis(3-nitrophenoxy)diphenyl sulfoxide, 4.4'-
Bis(3-nitrophenoxy)diphenylsulfone, 4
．． Examples include 4'-bis(3-nitrophenoxy)diphenyl ether.

These bis(3-nitrophenoxy) compounds are described, for example, in JP-A-61-194050 and JP-A-62-45.
As described in Japanese Patent No. 563, it can be obtained by condensing the corresponding 4゜4゛-bisphenols and m-dinitrohenzene in an aprotic polar solvent in the presence of a base.

The reduction catalyst used in the present invention includes a platinum group catalyst such as palladium, platinum, rhodium, ruthenium, cobalt, etc., supported by a metal oxide, sulfate, or carbonate, such as silica gel, alumina, chromium oxide, zirconium oxide, etc. , a catalyst supported on magnesium oxide, barium sulfate, barium carbonate, magnesium carbonate, celite, etc., more preferably a catalyst supported on alumina or magnesium oxide.

There is no particular restriction on the amount of catalyst used, but it is usually 0.01 to 10.0% relative to the raw material bis(3-nitrophenoxy) compound.
It is sufficient to use % by weight.

The aprotic polar solvent used in the method of the present invention is not particularly limited as long as it is inert to the reaction.
Examples include N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, l-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and the like.

The total amount of solvent to be used is not particularly limited, and is usually 0% to the raw material bis(3-nitrophenoxy) compound.
．． 5 to 10 weights! Double is enough.

Although the reaction temperature is not particularly limited, it can usually be carried out at about 50 to 100°C. Further, the hydrogen pressure during the reaction is not particularly limited, but the reaction normally proceeds sufficiently under normal pressure to slightly increased pressure of about 1000 mg+HgO. If you want to increase the reaction speed, use 50k.
The reaction can also be carried out under pressure of about 100 g/cdG.

When carrying out the present invention, a reaction solvent and a reduction catalyst are charged in advance, and the reaction system is gas-substituted under a hydrogen gas atmosphere. Under stirring, the raw material bis(3-nitrophenoxy) compound is gradually added to the reaction system. The manner in which the raw materials are added is not particularly limited, but a method in which a solution of the raw materials dissolved in the reaction solvent is added dropwise is easy to operate and can be said to be a preferable method. .

The raw material needs to be added at a rate commensurate with the reaction rate. If the addition rate is too fast, the concentration of nitroso and hydroxylamine in the system cannot be sufficiently controlled, and the by-product of the Ab compound cannot be suppressed.

Specifically, the entire amount of raw materials is added over 4.5 hours or more when the reaction temperature is 50°C, and the entire amount is added over 2 hours or more when the reaction temperature is 85°C, under a slight pressurization of about 1000ssHzO from normal pressure. It is desirable to do so.

A typical preferred embodiment of the invention is as follows. A reduction catalyst and a predetermined amount of reaction solvent are charged into a reactor equipped with a hydrogen gas introduction device, an exhaust device, a dropping device, a mercury seal stirrer, and a thermometer, and a predetermined amount of raw material bis (3-
Prepare a solution in which a (nitrophenoxy) compound is dissolved in a predetermined amount of a reaction solvent. After replacing the inside of the reaction system with a hydrogen gas atmosphere, the temperature of the reaction solution is raised to a predetermined temperature while stirring.

After raising the temperature, while stirring is continued, dropping of the raw material solution is started from the dropping device at a predetermined dropping rate.

During this time, hydrogen gas is absorbed by reaction; accordingly, hydrogen gas is added to the hydrogen gas reservoir as appropriate. After hydrogen absorption has stopped, continue stirring for 30 minutes to 1 hour.

After the reaction is completed, the inside of the reactor is replaced with nitrogen gas, and the reaction solution is
After removing the catalyst by filtration, the filtrate is analyzed by high performance liquid chromatography (hereinafter abbreviated as HPLC). Water is added to this filtrate to precipitate crystals, and then the crystals are filtered off to obtain the desired bis(3-aminophenoxy) compound.

〔Effect of the invention〕

According to the method of the present invention, the reaction proceeds while the concentration of nitroso and hydroxylamine in the reaction system is low, and the by-product of azo compounds due to condensation of these compounds can be suppressed. In addition, since the target product can be produced without the catalyst leaking through filtration, it is possible to produce the target bis(3-aminophenoxy) compound with extremely high purity and high yield, and is industrially extremely advantageous. It is extremely valuable as an industrial manufacturing method.

;Example: Hereinafter, the present invention will be specifically explained using Examples and Comparative Examples.

Example 1 90 sheets of N,N-dimethylformamide (hereinafter abbreviated as DMF) and 1.40 g were placed in a 300-meter flask equipped with a hydrogen gas introduction device, an exhaust device, a dropping device, a mercury-sealed stirrer, and a thermometer. Add 5% palladium/alumina catalyst (manufactured by NE Chemcat) and add 60g to the dropping device.
Add a solution of (0.14 mol) of 4,4"-bis(3-nitrophenoxy)biphenyl dissolved in 90 g of DMF. After replacing the reaction system with a hydrogen gas atmosphere, do not stir the reaction solution. The temperature was raised to 85°C.

Next, while stirring was continued, the raw material solution was added dropwise from a dropping device over a period of 2 hours. During this time, hydrogen was introduced into the reaction system in response to hydrogen absorption. Hydrogen absorption stopped almost at the same time as the dropping was completed. After the completion of the dropwise addition, stirring was continued for 30 minutes, the stirring was stopped, the inside of the reaction system was replaced with nitrogen, and the catalyst was filtered from the reaction solution. No leakage of the catalyst was observed during filtration of the catalyst.

80 g of water was added to this filtrate, and the precipitated crystals were filtered and dried, and the purity was 99.9%, containing no azo compound.
45.6 g of 4,4'-bis(3-aminophenoxy)biphenyl having a content of 7% were obtained.

(Yield 96.9%).

Examples 2 to 6 The bis(3-nitrophenoxy) compound used as a raw material was changed to 2,2-bis(4-(3-nitrophenoxy)phenyl)propane in Example 2, and 2,4-bis(4-(3-nitrophenoxy)phenyl)propane in Example 3.
-bis[4-(3-nitrophenoxy)phenyl2]
-Methylpentane, in Example 4, 2,2-bis[4-
(3-nitrophenoxy)phenyl]hexafluoropropane, 4,4゛-bis(3-nitrophenoxy)benzophenone in Example 5, and 4,4゛-bis(3-nitrophenoxy)benzophenone in Example 6.
The reaction was carried out in the same manner as in Example I except that bis(3-nitrophenoxy)diphenylsulfone was used.

The reaction results are shown in Table 1.

Examples 7 to 12 5% palladium/magfium oxide (manufactured by NE Chemcat) was used as a catalyst, and bis(
3-nitrophenoxy) compound to 4,4'-bis(3-nitrophenoxy)biphenyl in Example 7, and 2,2'-bisC4-(3-nitrophenoxy) in Example 8.
phenyl]propane, and in Example 9, 284-bis[4
-(3-nitrophenoxy)phenyl to 2-methylpentane, in Example 10 to 2,2-bisC4-(3-nitrophenoxy)phenyl]hexafluoropropane, in Example 11 to 4,4'-bis (3-nitrophenoxy)benzophenone was replaced with 4,4゛-bis(3-nitrophenoxy)diphenylsulfone in Example 12,
The reaction was carried out in the same manner as in Example 1.

The reaction results are shown in Table 1.

Comparative Example 1 The dropping device was removed from the reactor used in Example 1,
The reaction was carried out in the same manner as in Example 1, except that the raw material solution was also charged into the reactor.

As a result of analysis, 4.4°-bis(3-aminophenoxy)
The yield of biphenyl was 95.5% (purity 98.8%), and the content of aphids was 0.265%.

Comparative Example 2 A reaction was carried out in the same manner as in Example 1 except that 5% palladium/carbon (manufactured by NE Chemcat) was used as a catalyst, but when the catalyst was filtered out, the catalyst leaked, and the product taken out was , it was colored black due to the contamination of the catalyst.

(Hereafter, margin) １　　　　　〜　　・、 Patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, X is a divalent hydrocarbon group having 1 to 10 carbon atoms, or -C(CF_3 )_2-, -CO-, -S-, -S
Indicates a divalent group of O-, -SO_2- or -O-. Alternatively, X may be directly bonded with a single bond. ] When carrying out catalytic reduction of the bis(3-nitrophenoxy) compound represented by The reaction is carried out while adding the bis(3-nitrophenoxy) compound represented by the general formula (I) into a reactor containing a reaction solvent and a catalyst in advance. II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) [In the formula, X has the same meaning as in the general formula (I).
] A method for producing a bis(3-aminophenoxy) compound represented by: