JP2023058417A - Method for producing aromatic diamine compound - Google Patents

Abstract

To provide a method for producing an aromatic diamine compound that can produce the aromatic diamine compound at high yield and high purity and a recycling method for copper 8-quinolinol complex catalysts.SOLUTION: A method for producing an aromatic diamine compound includes reacting a dihalogenated aryl compound with ammonia water in the presence of a copper 8-quinolinol complex catalyst of such an amount that the mol of copper atoms becomes at least 0.01 times the mol of the dihalogenated aryl compound, represented by the following formula (where X is a halogen atom and R is a hydrogen atom or a hydrocarbon group).SELECTED DRAWING: None

Description

The present invention relates to a method for producing an aromatic diamine compound.

Aromatic diamine compounds such as p-phenylenediamine and m-phenylenediamine are compounds useful as raw materials for polymeric materials, pharmaceuticals or dyes, and in recent years have attracted attention as raw materials for heat-resistant polyamide compounds, especially aramids. The phenylenediamine can be obtained by reacting dichlorobenzene and aqueous ammonia using a copper compound as a catalyst.

For example, Patent Document 1 discloses that p-dichlorobenzene is heated at a high temperature of 210° C. or higher for several hours in the presence of cupric chloride dihydrate of two times the molar amount and about 50 times the molar amount of 28% aqueous ammonia. to obtain p-phenylenediamine with a yield of 90%.
Further, in Patent Document 2, p-hydroxyaniline, etc., is produced by adding ammonium chloride while charging p-dichlorobenzene at a relatively low concentration and simultaneously increasing the molar ratio of ammonia to p-dichlorobenzene. It is described that the yield of p-phenylenediamine is improved by suppressing the formation of by-products.
Furthermore, in Patent Document 3, in the presence of a catalyst consisting of water and copper oxides and chlorides in an amount of 2 times or more moles relative to the aromatic dihalide, ammonia in the aqueous phase at the start of the reaction is increased to 40 to 70% by weight. It is described that p-phenylenediamine can be obtained in a high yield of 90% or more with a p-dichlorobenzene conversion rate of almost 100% by reacting at a high temperature and high pressure of about 200 ° C. and 9.2 MPa. .

JP-A-51-095026 Japanese Patent Application Laid-Open No. 56-016449 JP-A-53-077023

The method described in Patent Document 1 requires a large amount of catalyst for p-dichlorobenzene, and has the problem that a large amount of intermediate (precursor) p-dichloroaniline remains.
In addition, the method described in Patent Document 2 has a low productivity with a yield of p-phenylenediamine of about 5% by weight, uses a large amount of catalyst, and is not easy to recover and reuse as it is. There is a problem that leads to an increase in the cost of
Furthermore, in the method described in Patent Document 3, high-concentration ammonia water must be prepared from liquid ammonia and water in a pressure-resistant vessel, and an expensive high-pressure-resistant reactor is also required, increasing equipment costs. There's a problem.

As described above, the conventional methods have various problems in industrialization, and although p-dichlorobenzene, m-dichlorobenzene and aqueous ammonia are all inexpensively available and economical, full-scale did not lead to commercial production. The following problems have been pointed out as reasons for this.
(1) In order to improve selectivity and yield, a high concentration and a high molar ratio of ammonia to p-dichlorobenzene or m-dichlorobenzene are required, resulting in a high pressure reaction using liquid ammonia and a high pressure reaction. In addition to increasing equipment costs depending on the reactor, the concentration of phenylenediamine in the reactor also decreases, resulting in a decrease in productivity.
(2) Since the copper catalyst is reductively decomposed and easily deactivated, it is necessary to add a large amount of the catalyst to p-dichlorobenzene or m-dichlorobenzene, and it is difficult to recover and reuse the catalyst. A large amount of waste is produced as a by-product.

In view of the above circumstances, the present invention provides a method for producing an aromatic diamine compound capable of suppressing the production of by-products and obtaining an aromatic diamine compound in high yield and high purity, and a copper 8-quinolinol complex catalyst. An object of the present invention is to provide a recycling method.

As a result of intensive studies to solve the above problems, the present inventors found that a copper 8-quinolinol complex catalyst was used as a catalyst for obtaining an aromatic diamine compound by reacting a dihalogenated aryl compound having a specific structure with aqueous ammonia. By reacting in the presence of, the formation of by-products can be suppressed even at a relatively low concentration of ammonia water and under relatively mild reaction conditions, and the desired aromatic diamine can be obtained in high yield and high purity. It was found that compounds were obtained.
The present invention was completed by studying this method in detail.

That is, the above problems are solved by the following means.
[1]
In the presence of a copper 8-quinolinol complex catalyst in an amount such that the molar amount of copper atoms is at least 0.01 times the molar amount of the dihalogenated aryl compound represented by the following formula (1), the dihalogenated aryl compound and ammonia water to obtain an aromatic diamine compound.

In formula (1), X represents a halogen atom and R represents a hydrogen atom or a hydrocarbon group.
[2]
The method for producing an aromatic diamine compound according to [1], wherein the copper 8-quinolinol complex catalyst has a molar amount of 8-quinolinol that is 0.6 to 2.1 times the molar amount of copper atoms.
[3]
The aromatic diamine compound according to [1] or [2], wherein the copper 8-quinolinol complex catalyst has a molar amount of 8-quinolinol that is 1.0 to 2.0 times the molar amount of copper atoms. Production method.
[4]
The method for producing an aromatic diamine compound according to any one of [1] to [3], wherein the copper 8-quinolinol complex catalyst contains bis(8-quinolinolato)copper.
[5]
In the presence of a copper 8-quinolinol complex catalyst in an amount such that the molar amount of copper atoms is 0.01 to 0.3 times the molar amount of the dihalogenated aryl compound, the dihalogenated aryl compound and aqueous ammonia are mixed. The method for producing an aromatic diamine compound according to any one of [1] to [4], wherein
[6]
The method for producing an aromatic diamine compound according to any one of [1] to [5], wherein the dihalogenated aryl compound is p-dichlorobenzene and/or m-dichlorobenzene.
[7]
The method for producing an aromatic diamine compound according to any one of [1] to [6], wherein the aromatic diamine compound is p-phenylenediamine and/or m-phenylenediamine.
[8]
The copper 8-quinolinol complex catalyst in the method for producing an aromatic diamine compound according to any one of [1] to [7] is recovered after the reaction, and the recovered copper 8-quinolinol complex catalyst is used in a chemical reaction. A method of recycling a copper 8-quinolinol complex catalyst, comprising reusing.
[9]
The recycling method according to [8], wherein the chemical reaction is a reaction of obtaining an aromatic diamine compound by reacting the dihalogenated aryl compound represented by the formula (1) with aqueous ammonia.
[10]
A method for producing an aromatic diamine compound, comprising obtaining the aromatic diamine compound through the recycling method according to [8] or [9].

In the present invention, a numerical range represented by "-" means a range including the numerical value as a lower limit and an upper limit. For example, when "A to B" is described, the numerical range is "A or more and B or less".

INDUSTRIAL APPLICABILITY According to the present invention, a method for producing an aromatic diamine compound and a method for recycling a copper 8-quinolinol complex catalyst, which can obtain an aromatic diamine compound with high yield and high purity while suppressing the production of by-products, are provided. can do.

Hereinafter, the method for producing an aromatic diamine compound of the present invention (hereinafter also referred to as the production method of the present invention) will be described in detail based on a preferred embodiment thereof.

The production method of the present invention includes reacting a dihalogenated aryl compound having a specific structure described later with ammonia water in the presence of a copper 8-quinolinol complex catalyst to obtain an aromatic diamine compound.
Regarding the above reaction in the production method of the present invention, the reaction formula is shown below, taking as an example the case where the dihalogenated aryl compound is p-dichlorobenzene (PDCB) or m-dichlorobenzene (MDCB). This reaction can yield p-phenylenediamine (PPDA) or m-phenylenediamine (MPDA). In addition, the present invention is not limited to the reactions described below, except as specified in the present invention.

The above copper 8-quinolinol complex catalyst is a copper complex compound represented by the following formula (2), n 8-quinolinol is coordinated to m copper atoms, and The average coordination number (n/m) of 8-quinolinol is preferably 0.6 to 2.1, more preferably 1.0 to 2.0. Copper 8-quinolinol complexes that are a single chemical species include bis(8-quinolinolato)copper (commonly known as oxine copper) with n/m equal to 2.

A copper 8-quinolinol complex catalyst can be prepared using an inorganic copper salt and 8-quinolinol, and this copper 8-quinolinol complex catalyst can be added to the above reaction system. Alternatively, by separately adding an inorganic copper salt and 8-quinolinol to the reaction system, a copper 8-quinolinol complex catalyst can be produced in the reaction system.
Inorganic copper salts include, for example, monovalent or divalent copper compounds. Suitable examples of such a copper compound include cuprous oxide, cupric oxide, cuprous chloride, and copper (II) sulfate.
In the reaction system, the copper 8-quinolinol complex catalyst has a molar amount of 8-quinolinol relative to the molar amount of copper atoms constituting the catalyst, as described above, 8-quinolinol/copper atom = 0.6 to 2.1. and more preferably 8-quinolinol/copper atom=1.0 to 2.0. This 8-quinolinol/copper atom molar ratio (molar ratio) is, when the inorganic copper salt and 8-quinolinol are separately added to the reaction system, the copper constituting the inorganic copper salt It means that the copper 8-quinolinol complex catalyst is preferably formed with the molar amount of 8-quinolinol relative to the molar amount of atoms, 8-quinolinol/copper atom = 0.6 to 2.1, 8-quinolinol It means that it is more preferable to form a copper 8-quinolinol complex catalyst with /copper atom = 1.0 to 2.0.
For example, bis(8-quinolinolato)copper (commercial name: oxine copper) with 8-quinolinol/copper salt=2 is suitable as a copper 8-quinolinol complex catalyst.

The added amount of the copper 8-quinolinol complex catalyst that acts as a catalyst for the above reaction is such that the molar amount of copper atoms contained in the copper 8-quinolinol complex catalyst is equal to the molar amount of the copper atom/copper atom/ The amount is such that the dihalogenated aryl compound ≥ 0.01, the amount is preferably such that the copper atom/dihalogenated aryl compound = 0.01 to 0.3, and the copper atom/dihalogenated aryl compound = 0.05 to 0.2. is more preferable. By setting such a ratio, the reaction rate can be further accelerated, and the by-production of high-boiling substances can be further suppressed. When the inorganic copper salt and 8-quinolinol are separately added to the reaction system, the molar amount of copper atoms is the molar amount of copper atoms constituting the inorganic copper salt to be added.

Ammonia water used in the above reaction has a relatively low concentration and can sufficiently proceed with the desired reaction. The concentration of ammonia water is preferably 10 to 50% by weight, more preferably 20 to 35% by weight. Ammonia water with a high concentration of 28% or more is prepared by adding and mixing liquid ammonia to water or a commercially available 28% ammonia water in a closed vessel. In the present invention, since it is sufficient to use ammonia water of relatively low concentration, the reaction is not required to be performed under severe high-pressure conditions, so leakage of the reaction liquid during the reaction is unlikely to occur, and a reactor with high pressure resistance is not required. It is also advantageous in terms of equipment costs.

In the above reaction, the molar amount of ammonia in the aqueous ammonia with respect to the molar amount of the dihalogenated aryl compound as the raw material is preferably ammonia/dihalogenated aryl compound = 6 to 50, and ammonia/dihalogenated aryl compound = 6 to 30. More preferably, ammonia/aryl dihalogen compound=10 to 20, and particularly preferably ammonia/aryl dihalogen compound=8 to 20. Within this range, the production of high-boiling by-products such as dianodiphenylamine can be further suppressed, and the yield of the target aromatic diamine compound can be further increased. The concentration of the aromatic diamine compound can also be sufficiently increased.

In the above reaction, an inert organic solvent that does not participate in the reaction may be used. In this case, the organic solvent has the effect of uniformly dispersing the copper 8-quinolinol complex catalyst in the reaction solution and promoting the progress of the above reaction. Examples of the organic solvent include hydrocarbons such as toluene and xylene, and ethers such as THF (tetrahydrofuran) and cyclopentyl methyl ether.

The reaction temperature for the above reaction is preferably 150 to 230°C, more preferably 170 to 210°C. Although certain high temperatures are required for the desired reaction to proceed, the production process of the present invention can employ relatively mild high temperature conditions, thus avoiding high pressure conditions. Therefore, an expensive high-pressure-resistant reactor is not required, and the production of low-boiling-point by-products such as aniline and tar-like high-boiling-point by-products can be further suppressed.
In the above reaction, the desired aromatic diamine compound is produced from the dihalogenated aryl compound via, for example, chloroaniline as a precursor (intermediate). The temperature may be raised stepwise within the range of 170 to 210° C. to allow the reaction to proceed step by step.

The reaction pressure for the above reaction is appropriately determined according to the reaction temperature and the concentration of aqueous ammonia. From an economical point of view such as equipment costs, the pressure is preferably 2 to 9 MPa, more preferably 3 to 6 MPa. The reaction time varies depending on various conditions such as reaction temperature and catalyst concentration, but is usually 2 to 10 hours, for example.

The above reaction can be carried out either by batch operation using a pressure vessel such as an autoclave equipped with a stirrer, or continuous operation using a flow system reactor such as a static mixer. In the above reaction, the raw material p-dichlorobenzene or m-dichlorobenzene, aqueous ammonia and catalyst (copper 8-quinolinol complex) are dispersed in a heterogeneous system while the reaction proceeds. It is preferable that the raw materials are completely reacted while being mixed in a reactor or a continuous reactor such as a static mixer.

In the batchwise operation, an autoclave equipped with a stirrer is sealed with a dihalogenated aryl compound, a catalyst (copper 8-quinolinol complex) and aqueous ammonia, stirred at a predetermined temperature for a predetermined time, and then room temperature (eg, 25 ° C.). Cool to Subsequently, the reaction solution is taken out and neutralized with a caustic alkali such as sodium hydroxide, then ammonia and water are removed by distillation, and the reaction solution from which these have been removed is concentrated. Next, after extracting the target substance from the resulting concentrate using an organic solvent such as dichloromethane, the residue is filtered off. Subsequently, the extract of the filtrate is concentrated while removing the solvent to obtain a crude target product, which is further purified by distillation under reduced pressure. The filtration residue (filtrate) contains a catalyst (copper 8-quinolinol complex), an inorganic salt (eg sodium chloride), and the like. Inorganic salts can be removed by washing the residue with water. Also, the catalyst can be recovered by drying after the inorganic salts are removed by washing with water. That is, in the production method of the present invention, the copper 8-quinolinol complex, which is a catalyst, is less likely to be deactivated during the reaction, and can be recovered and reused as a catalyst for chemical reactions. In addition, if the production method of the present invention is applied to this chemical reaction, the catalyst can be reused in repeated reactions, and the amount of copper 8-quinolinol complex catalyst used can be greatly reduced in the overall reaction for repeatedly obtaining an aromatic diamine compound. be able to. As a result, the environmental load can be reduced, and it is advantageous in terms of cost. This is the same for the operation of the continuous flow type, which will be described later.
In the production method of the present invention, when bis(8-quinolinolato)copper is employed as the copper 8-quinolinol complex catalyst, the recovered catalyst is partially 8-quinolinol in bis(8-quinolinolato)copper. Although it is considered to include those with desorbed structures, if the molar ratio of 8-quinolinol to copper in this recovery catalyst is in the range of 0.6 to 2.1, there is sufficient catalytic activity, and it can be used as a catalyst for chemical reactions. It can be reused as it is.

In other words, according to the present invention, the following recycling reactions are provided in connection with the production method of the present invention.
A method for recycling a copper 8-quinolinol complex catalyst, comprising recovering the copper 8-quinolinol complex catalyst in the production method of the present invention after the reaction, and reusing the recovered copper 8-quinolinol complex catalyst in a chemical reaction.
The above recycling method, wherein the chemical reaction is a reaction of obtaining an aromatic diamine compound by reacting a dihalogenated aryl compound having a specific structure described later with aqueous ammonia.

In the continuous flow operation, for example, a reaction raw material (PDCB or MDCB) heated to a predetermined temperature and a slurry mixture of a catalyst (copper 8-quinolinol complex) are continuously supplied to a reactor such as a static mixer, and the predetermined After the elapse of the residence time of , the crude target product is obtained from the outflowing reaction solution by the same operation as the batchwise operation described above. Then, by distilling the resulting crude product, a highly pure target product can be obtained.

Next, preferred structures of the dihalogenated aryl compound and the target aromatic diamine compound used in the production method of the present invention will be described.

In the present invention, the dihalogenated aryl compound is a compound represented by the following formula (1).

In formula (1), each X independently represents a halogen atom. Examples of the halogen atom include fluorine atom, bromine atom, chlorine atom and iodine atom, with chlorine atom being preferred. Two X's in formula (1) are usually the same halogen atom. The two Xs may be substituted on the aromatic ring at any two positions, for example, the 2-position, the 3-position, the 4-position and the 5-position with the position substituted by the substituent R being the 1-position.
R represents a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom. Hydrocarbon groups that can be used as R include, for example, alkyl groups (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, more preferably 1 or 2 alkyl groups), alkenyl groups (preferably having 2 to 5, more preferably 2 to 4, more preferably 2 or 3 alkenyl groups), aryl groups (preferably 6 to 10 carbon atoms, more preferably phenyl groups), aralkyl groups (preferably 7 to 10 carbon atoms, more Benzyl group, p-tolyl group, m-tolyl group) and the like are preferred. Among them, an alkyl group is preferred, a methyl group or an ethyl group is preferred, and a methyl group is more preferred.
In formula (1), two Xs are preferably at the para-position or the meta-position with respect to each other. Among them, the dihalogenated aryl compound is preferably p-dichlorobenzene or m-dichlorobenzene, more preferably p-dichlorobenzene. In formula (1), 2,4-dichlorotoluene, 2,5-dichlorotoluene and 3,5-dichlorotoluene are readily available as dihalogenated aryl compounds having a substituent R other than a hydrogen atom, and are highly reactive. It is suitable because it is sufficient.

The aromatic diamine compound is a compound represented by the following formula (3) derived from the dihalogenated aryl compound of the above formula (1).

In formula (3), R has the same definition as R in formula (1), and preferred forms are also the same. The substitution positions of the two amino groups on the aromatic ring are the same as the substitution positions of the halogen group X of the starting dihalogenated aryl compound. The aromatic diamine compound represented by formula (3) above is preferably p-phenylenediamine or m-phenylenediamine.

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited to these.

[Example 1]
80.0 g (0.544 mol) of p-dichlorobenzene, 445.0 g of 28% aqueous ammonia (ammonia : 7.317 mol) and 19.2 g of oxine copper (copper atom: 0.054 mol, copper atom/p-dichlorobenzene = 0.1) were added, then sealed and heated while stirring. Next, after reacting at an internal temperature of 185° C. for 3 hours, the internal temperature was raised to 195° C., and the reaction was completed for an additional 4 hours. The internal pressure decreased from 4.6 MPa to 3.9 MPa during the reaction at an internal temperature of 185° C. for 3 hours. Further, the internal pressure decreased from 4.4 MPa to 4.1 MPa during the reaction for 4 hours at an internal temperature of 195°C.
After the reaction was completed, the autoclave was cooled to room temperature (25° C.), and the reaction solution was extracted. Subsequently, 51.6 g of sodium hydroxide is added to the reaction solution to neutralize the by-produced ammonium chloride and liberate ammonia and by-produced amines, and then the ammonia and moisture are removed from the reaction solution by distillation. The reaction solution from which these were removed was concentrated to dryness.

The reaction of neutralizing ammonium chloride with sodium hydroxide is represented by the following reaction formula (4). Ammonia (NH ₃ ) and water produced by this reaction are removed by distillation as described above and can be recovered.
_NH4Cl +NaOH→NaCl+ _NH3 + _H2O (4)

Subsequently, 500 g of dichloromethane was added to the concentrated dry matter to extract the reaction product, and the residue was filtered off. Next, the extract (organic phase) of the filtrate was concentrated by distillation and dried under reduced pressure to obtain 51.0 g of crude p-phenylenediamine.
Next, the residue obtained by the filtration was washed with warm water to remove the NaCl described above, and dried under reduced pressure to obtain 15.0 g of a recovered catalyst. Analysis of this recovered product revealed that the recovered product contained 0.049 mol of copper atoms and 0.073 mol of 8-quinolinol, and contained 8-quinolinol at a molar ratio of about 1.5 times that of copper atoms. was
Subsequently, the crude p-phenylenediamine was put into a vacuum distiller and distilled at a temperature of 145 to 150° C. under a reduced pressure of 6 to 10 mmHg to obtain 41.2 g of purified p-phenylenediamine (gas chromatograph A purity of 99.92%, where "%" is based on the peak area of the gas chromatograph) was obtained. The yield of the purified product was 70% with respect to p-dichlorobenzene as a starting material.

[Example 2]
In the same manner as in Example 1, except that 498.4 g of 25% ammonia water (ammonia: 7.317 mol) was used instead of 445.0 g of 28% ammonia water (ammonia: 7.317 mol) in Example 1. , to obtain 50.1 g of crude p-phenylenediamine. Subsequently, this crude product was put into a vacuum distiller and distilled at a temperature of 145 to 150° C. under a reduced pressure of 6 to 10 mmHg to obtain 40.2 g of purified p-phenylenediamine (gas chromatographic purity: 99.94). %) was obtained. The yield of the purified product was 68% with respect to p-dichlorobenzene as a starting material.

[Example 3]
After carrying out the reaction of Example 1 twice to obtain 29.5 g of the recovered catalyst, p- 51.6 g of crude phenylenediamine was obtained. Subsequently, this crude product is put into a vacuum distiller and distilled at a temperature of 145 to 150° C. under a reduced pressure of 6 to 10 mmHg to obtain 39.6 g of purified p-phenylenediamine (gas chromatographic purity 99.94). %) was obtained. The yield of the purified product relative to p-dichlorobenzene as a starting material was 71%.

[Example 4]
61.5 g of crude m-phenylenediamine was obtained in the same manner as in Example 1, except that m-dichlorobenzene was used instead of p-dichlorobenzene. Subsequently, this crude product was put into a vacuum distiller and distilled at a temperature of 148 to 153° C. under a reduced pressure of 6 to 10 mmHg to obtain 58.9 g of purified m-phenylenediamine (gas chromatographic purity: 99.95). %) was obtained. The yield of the purified product relative to m-dichlorobenzene as a starting material was 75%.

[Comparative example]
80.0 g (0.544 mol) of p-dichlorobenzene, 445.0 g of 28% aqueous ammonia (ammonia : 7.317 mol) and 0.34 g of oxine copper (copper atom: 0.001 mol, copper atom/p-dichlorobenzene = 0.002) were added, then the flask was sealed and heated while stirring. Next, after reacting at an internal temperature of 185° C. for 3 hours, the internal temperature is raised to 195° C., the reaction is further completed for 4 hours, the autoclave is cooled to room temperature (25° C.), and the reaction solution is extracted. rice field. Subsequently, 5.1 g of sodium hydroxide was added to the reaction solution to neutralize the by-produced ammonium chloride, and the composition of the reaction solution was analyzed by gas chromatography. About 90% remained, and only about 4% of the intermediate p-chloroaniline was formed. In other words, practically no p-phenylenediamine was produced.

As is clear from the above, in the production method of the comparative example, only a small amount of intermediate was produced, and it was difficult to obtain the desired product.
In contrast, both the production method using p-dichlorobenzene as a starting material in Examples 1 and 2 and the production method using m-dichlorobenzene as a starting material in Example 4 produced by-products such as aniline and aminophenol. It was found that the target product can be obtained in high yield and high purity without producing Moreover, as in Example 3, it was found that even if the recovered catalyst was used, the desired product could be obtained with high yield and high purity.

Claims (10)

In the presence of a copper 8-quinolinol complex catalyst in an amount such that the molar amount of copper atoms is at least 0.01 times the molar amount of the dihalogenated aryl compound represented by the following formula (1), the dihalogenated aryl compound and ammonia water to obtain an aromatic diamine compound.

In Formula (1), X represents a halogen atom. R represents a hydrogen atom or a hydrocarbon group. 2. The method for producing an aromatic diamine compound according to claim 1, wherein the copper 8-quinolinol complex catalyst has a molar amount of 8-quinolinol that is 0.6 to 2.1 times the molar amount of copper atoms. 3. The method for producing an aromatic diamine compound according to claim 1, wherein the copper 8-quinolinol complex catalyst has a molar amount of 8-quinolinol that is 1.0 to 2.0 times the molar amount of copper atoms. . The method for producing an aromatic diamine compound according to any one of claims 1 to 3, wherein the copper 8-quinolinol complex catalyst contains bis(8-quinolinolato)copper. In the presence of a copper 8-quinolinol complex catalyst in an amount such that the molar amount of copper atoms is 0.01 to 0.3 times the molar amount of the halogenated aryl compound, the dihalogenated aryl compound and aqueous ammonia are mixed. The method for producing an aromatic diamine compound according to any one of claims 1 to 4, wherein the reaction is performed. The method for producing an aromatic diamine compound according to any one of claims 1 to 5, wherein the dihalogenated aryl compound is p-dichlorobenzene and/or m-dichlorobenzene. The method for producing an aromatic diamine compound according to any one of claims 1 to 6, wherein the aromatic diamine compound is p-phenylenediamine and/or m-phenylenediamine. The copper 8-quinolinol complex catalyst in the method for producing an aromatic diamine compound according to any one of claims 1 to 7 is recovered after the reaction, and the recovered copper 8-quinolinol complex catalyst is reused in chemical reactions. A method of recycling a copper 8-quinolinol complex catalyst comprising: 9. The recycling method according to claim 8, wherein the chemical reaction is a reaction of reacting the dihalogenated aryl compound represented by the formula (1) with aqueous ammonia to obtain an aromatic diamine compound. A method for producing an aromatic diamine compound, comprising obtaining the aromatic diamine compound through the recycling method according to claim 8 or 9.