JP5546872B2 - Method for producing N, N, N ', N'-tetraarylbenzidine derivative - Google Patents

Description

The present invention industrially efficiently produces N, N, N ′, N′-tetraarylbenzidine derivatives useful as organic electroluminescent elements, electrophotographic photosensitive members, element materials for electronic materials such as organic transistors, and intermediates thereof. It is about how to do.

As a method for synthesizing N, N, N ′, N′-tetraarylbenzidine derivatives, Ullmann-Goldberg reaction in which diphenylamines and dihalogenobiphenyls are reacted with a copper catalyst is known. (For example, see Patent Documents 1 and 2)
However, in this method, it is necessary to use a large amount of copper catalyst, and removing this becomes a heavy burden during the purification operation, which hinders practical use. In addition, high temperature and long reaction time are often required, the reaction product is markedly colored, and a large amount of by-products are produced, resulting in a low yield of N, N, N ′, N′-tetraarylbenzidine derivatives. In addition, there is a drawback that it takes time and effort for purification depending on the application.

For this reason, studies have been made to moderate the conditions of the Ullmann-Goldberg reaction. For example, Goodbrand has copper (I) chloride, potassium hydroxide, 1,10 at the reflux temperature of an aromatic hydrocarbon solvent (xylene). -N, N, N ', N'-tetraarylbenzidine derivatives are obtained using a phenanthroline ligand. (See Non-Patent Document 1)
However, this reaction system has an industrial problem that it is necessary to use an expensive ligand.

A method for dimerizing a triphenylamine derivative in acetonitrile in the presence of copper perchlorate to obtain an N, N, N ′, N′-tetraarylbenzidine derivative has also been reported. (See Non-Patent Document 2)
However, since the produced N, N, N ′, N′-tetraarylbenzidine derivative is dissolved in the acetonitrile solvent, an oligomer is produced by overreaction, and the N, N, N ′, N′-tetraarylbenzidine derivative There are problems in production efficiency and quality such that the yield is reduced and the oligomer as an impurity cannot be removed by recrystallization or the like.
Furthermore, a method of dimerization using iron chloride has been reported, but it still has the same problems. (Non Patent Literature 3)

Japanese Patent Publication No. 58-52983 JP-A-5-9159

J. et al. Org. Chem. 64,670-674 (1999) J. et al. Org. Chem. 73, 3245-3251 (2008) Chem. Lett. 1999, 79-80 (1999)

The present invention provides a method for producing an N, N, N ′, N′-tetraarylbenzidine derivative which can be reacted under practical conditions and can be easily purified after the reaction.

As a result of intensive studies to solve these problems, the present inventor used triarylamines, a solvent A in which the triarylamines are soluble, an oxidizing agent, and a solvent B in which the oxidizing agent is soluble. , The triarylamines are oxidized with the oxidizing agent in a co-solvent system, thereby improving production efficiency and suppressing the formation of by-products. N, N, A process for producing N ′, N′-tetraarylbenzidine derivatives has been completed.
That is, the present invention has the following configurations [1] to [11].

[1]
The triarylamines represented by the following general formula (1), the oxidizing agent, and at least two or more kinds of solvents are used for the oxidation reaction of the triarylamines. A method for producing an N, N, N ′, N′-tetraarylbenzidine derivative.

（式中、ＰおよびＱはそれぞれ独立に無置換または１ないし２以上の置換基を有する芳香族炭化水素基を表し、該置換基はそれぞれ独立にメチル基、エチル基、ｔｅｒｔ−ブチル基、メトキシ基、トリフルオロメチル基、フルオロ基、フェニル基から選ばれ、Ｒ_１〜Ｒ_４はそれぞれ独立に水素原子、メチル基またはフルオロ基を表し、またＲ_３とＲ_４は連環してベンゼン環を形成してもよく、その場合、該ベンゼン環はメチル基またはフルオロ基を置換基に有してもよい。）

(Wherein P and Q each independently represent an unsubstituted or aromatic hydrocarbon group having 1 to 2 or more substituents, and each of the substituents independently represents a methyl group, an ethyl group, a tert-butyl group, a methoxy group, Group, trifluoromethyl group, fluoro group and phenyl group, R _{1 to} R ₄ each independently represents a hydrogen atom, a methyl group or a fluoro group, and R ₃ and R ₄ are linked to form a benzene ring. In this case, the benzene ring may have a methyl group or a fluoro group as a substituent.)

(Wherein, P, Q and _R 1 to R ₄ are each identical P, a Q, and _R 1 to R ₄ in the general formula (1).)

[2]
The solvent is a co-solvent composed of a solvent A capable of dissolving the triarylamines and a solvent B capable of dissolving the oxidizing agent, and the triarylamines and the oxidizing agent are the cosolvent. The method for producing an N, N, N ′, N′-tetraarylbenzidine derivative as described in [1], wherein the oxidation reaction is carried out in a state dissolved in

[3]
N, N, N ′, N according to [1] or [2], wherein the oxidizing agent is one selected from copper perchlorate, iron perchlorate and copper tetrafluoroborate. A method for producing a '-tetraarylbenzidine derivative.

[4]
The solvent A has an SP value of 8 to 9, and is one or more selected from solvents having a weak radical quenching effect, according to any one of [1] to [3] Of N, N, N ′, N′-tetraarylbenzidine derivatives of

[5]
N, N, N ′, N ′ according to any one of [1] to [4], wherein the solvent A is one or more selected from toluene, xylenes, and cyclohexane -Method for producing tetraarylbenzidine derivatives.

[6]
The solvent B has an SP value of 10 to 18, and is one or more selected from solvents having a weak radical quenching effect, according to any one of [1] to [5] Of N, N, N ′, N′-tetraarylbenzidine derivatives of

[7]
The method for producing an N, N, N ′, N′-tetraarylbenzidine derivative according to any one of [1] to [6], wherein the solvent B is a nitrile solvent.

[8]
N, N, according to any one of [1] to [7], wherein the nitrile solvent is one or more selected from acetonitrile, propionitrile, butyronitrile, and benzonitrile. A method for producing an N ′, N′-tetraarylbenzidine derivative.

[9]
In the method for producing the N, N, N ′, N′-tetraarylbenzidine derivative, the produced N, N, N ′, N′-tetraarylbenzidine derivative is quenched with a base, an acid or water. [1] A method for producing an N, N, N ′, N′-tetraarylbenzidine derivative according to any one of [1] to [8].

[10]
In the method for producing the N, N, N ′, N′-tetraarylbenzidine derivative, when the oxidizing agent is one selected from copper perchlorate and copper tetrafluoroborate, quenching with ammonia water is provided. The method for producing an N, N, N ′, N′-tetraarylbenzidine derivative according to [9].

[11]
In the method for producing the N, N, N ′, N′-tetraarylbenzidine derivative, when the oxidizing agent is iron perchlorate, quenching with dilute hydrochloric acid is performed. , N ′, N′-Tetraarylbenzidine derivative production method.

Hereinafter, the present invention will be described in detail.
In the present invention, the triarylamine to be used is a compound in which three aromatic hydrocarbons are bonded to a nitrogen atom, and each aromatic hydrocarbon may be unsubstituted or substituted. If at least one of them is a benzene ring, they may be different or the same. Specific examples include triphenylamine, 4,4′-dimethyltriphenylamine, N-phenyl-bis (4-biphenylyl) amine, N- (3-methylphenyl) -bis (4-biphenylyl) amine, N, N-diphenyl (4-biphenylyl) amine, N- (3,5-dimethylphenyl) -bis (4-biphenylyl) amine, N-3-biphenylyl-bis (4-biphenylyl) amine, N-3-fluorophenyl- Bis (4-biphenylyl) amine, N, N-diphenyl (1-naphthyl) amine, N-1-naphthyl-bis (4-biphenylyl) amine and the like can be mentioned.

In the present invention, the solvent A is not particularly limited as long as it dissolves the triarylamines and does not inhibit the oxidation reaction of the triarylamines by the following oxidizing agent. As the solvent A, it is preferable to use one or two or more selected from solvents having an SP value of 8 to 9 and a weak radical quenching effect, and one or more selected from toluene, xylenes and cyclohexane. It is particularly preferable to use
Here, the SP value is a solubility parameter, which is a measure of the solubility of a two-component solution.

  In the present invention, the oxidizing agent used for the reaction is preferably one selected from copper perchlorate, iron perchlorate and copper tetrafluoroborate. The amount is preferably 1 equivalent or more, particularly preferably in the range of 1 to 3 equivalents relative to the triarylamine used. When the amount of the oxidizing agent used in the reaction is less than 1 equivalent, the yield of the obtained N, N, N ′, N′-tetraarylbenzidine derivative may be lowered, which is not preferable. In addition, when a large excess of the oxidizing agent used in the reaction is added, by-products increase, the post-treatment operation after the completion of the reaction becomes complicated, and the resulting N, N, N ′, N′-tetra The yield of the arylbenzidine derivative decreases, which is not preferable.

  In the present invention, the solvent B is not particularly limited as long as it dissolves the oxidizing agent and does not inhibit the oxidation reaction of the triarylamines by the oxidizing agent. As the solvent B, it is preferable to use one or more selected from solvents having an SP value of 10 to 18 and a weak radical quenching effect. Preferred solvents include nitrile solvents from the viewpoint of redox potential. As the nitrile solvent, it is particularly preferable to use one or more selected from acetonitrile, propionitrile, butyronitrile, and benzonitrile.

  In the present invention, the dissolution / mixing order of the triarylamines, the solvent A, the oxidizing agent and the solvent B is not particularly limited. The triarylamines are dissolved in the solvent A, and the oxidizing agent is dissolved in the solvent B. Thereafter, both solutions are mixed, and the triarylamines and the oxidizing agent are mixed with the solvent A and the solvent B in a cosolvent system. Alternatively, the solvent A and the solvent B may be mixed in advance to form a cosolvent, the triarylamines and the oxidizing agent are dissolved in the cosolvent, and then reacted in a cosolvent system. Also good.

  In the present invention, the reaction temperature is not particularly limited as long as it is in the range of -20 to 100 ° C.

  In the present invention, the reaction time varies depending on the triarylamines used in the reaction, the kind and amount of the oxidizing agent, and the reaction temperature, and may be appropriately selected, and is usually about 1 to 24 hours.

In the production method of the present invention, by using two or more kinds of solvents as described above, an N, N, N ′, N′-tetraarylbenzidine derivative is produced from the triarylamines by the action of the oxidizing agent. Then, the solubility of the N, N, N ′, N′-tetraarylbenzidine derivative in the solvent in which it was generated decreases, and it can no longer be dissolved and precipitates. Therefore, it is possible to suppress the production of oligomers and the like produced by further reaction of the produced derivative and increase the reaction efficiency. Further, since the produced derivative is precipitated, the target product can be easily recovered and purified.

  In the present invention, after completion of the oxidation reaction, the generated radical of the N, N, N ′, N′-tetraarylbenzidine derivative is quenched. The method for quenching radicals is not particularly limited as long as it has a quenching effect, but it is preferable to add a base such as triethylamine, dimethylformamide or aqueous ammonia, potassium carbonate, an acid such as dilute hydrochloric acid or water. In particular, when copper perchlorate or copper tetrafluoroborate is used as the oxidizing agent, it is more preferable to use aqueous ammonia from the viewpoint of preventing the precipitation of copper and facilitating the recovery of the target product by filtration or the like. When iron perchlorate is used as the agent, it is more preferable to use dilute hydrochloric acid from the viewpoint of preventing precipitation of iron and facilitating recovery of the target product by filtration or the like.

The treatment after quenching is not particularly limited, but may be performed by a conventional method such as filtration or washing, and the target N, N, N ′, N′-tetraarylbenzidine derivative can be obtained.

  According to the production method of the present invention, it is possible to produce an N, N, N ′, N′-tetraarylbenzidine derivative efficiently while suppressing the production of by-products.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, these do not limit this invention at all. The progress of the reaction was determined by HPLC analysis (column Inertsil ODS-3 (manufactured by GL Sciences) 4.6 × 150 mm, 3 μm; detector UV254 nm; column temperature 40 ° C .; flow rate 0.7 ml / min.). It was.

[Example 1]
To a 100 ml three-necked flask equipped with a thermometer, 1.74 g (3 mmol) of N-phenyl-bis (4-biphenylyl) amine and 40 ml of toluene were added and dissolved at room temperature. A solution prepared by dissolving 2.22 g (6 mmol) of copper perchlorate hexahydrate in 20 ml of acetonitrile was added thereto, and the mixture was stirred at room temperature for 9 hours and left overnight (15 hours). After adding 10 ml of 3% aqueous ammonia at room temperature and stirring for 30 minutes, insolubles were collected by filtration. After washing with 3% aqueous ammonia and then with water, it was dried at 40 ° C. under reduced pressure. In HPLC analysis, the raw material residue was 0.8%, and the oligomer was 0.2%. Recrystallization from 60 ml of o-dichlorobenzene gave 990 mg (yield 85%) of N, N, N ′, N′-tetra (4-biphenylyl) benzidine.

[Example 2]
To a 100 ml three-necked flask equipped with a thermometer, 1.74 g (3 mmol) of N-phenyl-bis (4-biphenylyl) amine and 40 ml of toluene were added and dissolved at room temperature. A solution prepared by dissolving 2.8 g (6 mmol) of iron perchlorate heptahydrate in 20 ml of acetonitrile was added thereto, and the mixture was stirred at room temperature for 9 hours and left overnight (15 hours). After adding 10 ml of 3% hydrochloric acid at room temperature and stirring for 30 minutes, insoluble matters were collected by filtration. After washing with 3% hydrochloric acid and then with water, it was dried under reduced pressure at 40 ° C. It was heated and dissolved in 60 ml of o-dichlorobenzene, and then filtered while hot. Crystals deposited by allowing the filtrate to cool to room temperature were collected by filtration and dried to obtain 950 mg (yield 81%) of N, N, N ′, N′-tetra (4-biphenylyl) benzidine.

[Example 3]
To a 100 ml three-necked flask equipped with a thermometer, 0.96 g (3 mmol) of N, N-diphenyl (4-biphenylyl) amine and 40 ml of cyclohexane were added and dissolved at room temperature. A solution prepared by dissolving 2.2 g (6 mmol) of copper perchlorate hexahydrate in 20 ml of acetonitrile was added thereto, and the mixture was stirred at room temperature for 8 hours and left overnight (16 hours). After adding 10 ml of 3% aqueous ammonia at room temperature and stirring for 30 minutes, insolubles were collected by filtration. After washing with 3% aqueous ammonia and then with water, it was dried at 40 ° C. under reduced pressure. Purification by column chromatography (carrier: NH silica gel 50 g, manufactured by Fuji Silysia Chemical Ltd., eluent: cyclohexane / chloroform = 10/1), N, N′-di (4-biphenylyl) -N, N′-diphenyl 830 mg of benzidine (yield 86.5%) was obtained.

[Example 4]
To a 100 ml three-necked flask equipped with a thermometer, 20 ml of toluene and 10 ml of acetonitrile were added and mixed. N-phenyl-bis (4-biphenylyl) amine (0.59 g, 1.5 mmol) and copper perchlorate hexahydrate (1.11 g, 3 mmol) were added thereto, and the mixture was stirred at room temperature for 9 hours. Left overnight (15 hours). After adding 10 ml of 3% aqueous ammonia at room temperature and stirring for 30 minutes, insolubles were collected by filtration. After washing with 3% aqueous ammonia and then with water, it was dried at 40 ° C. under reduced pressure. Recrystallization from 30 ml of o-dichlorobenzene gave 440 mg (yield 75%) of N, N, N ′, N′-tetra (4-biphenylyl) benzidine.

[Example 5]
To a 500 ml three-necked flask equipped with a thermometer, 6.17 g (15 mmol) of N- (3-methylphenyl) -bis (4-biphenylyl) amine and 200 ml of toluene were added and dissolved at 50 ° C. A solution obtained by dissolving 11.12 g (30 mmol) of copper perchlorate hexahydrate in 100 ml of acetonitrile was added thereto, and the mixture was stirred at 40 ° C. for 8 hours and left overnight (15 hours). After adding 100 ml of 3% aqueous ammonia at room temperature and stirring for 30 minutes, insoluble matters were collected by filtration. After washing with 3% aqueous ammonia and then with water, it was dried at 40 ° C. under reduced pressure. Recrystallized twice with 100 ml of o-dichlorobenzene to obtain 4.07 g (yield 66.1%) of 2,2′-dimethyl-N, N, N ′, N′-tetra (4-biphenylyl) benzidine. It was.

[Example 6]
To a 500 ml three-necked flask equipped with a thermometer, 6.38 g (15 mmol) of N- (3,5-dimethylphenyl) -bis (4-biphenylyl) amine and 200 ml of toluene were added and dissolved at 50 ° C. . A solution prepared by dissolving 9.26 g (25 mmol) of copper perchlorate hexahydrate in 100 ml of acetonitrile was added thereto, followed by stirring at 50 ° C. for 1 hour and cooling to room temperature. After adding 100 ml of 3% aqueous ammonia at room temperature and stirring for 30 minutes, insoluble matters were collected by filtration. After washing with 3% aqueous ammonia and then with water, it was dried at 40 ° C. under reduced pressure. Recrystallization from 75 ml of chlorobenzene gave 6.0 g (yield 94.2%) of 2,2 ′, 6,6′-tetramethyl-N, N, N ′, N′-tetra (4-biphenylyl) benzidine. Obtained.

[Example 7]
To a 50 ml three-necked flask equipped with a thermometer, 294 mg (0.75 mmol) of N-phenyl-bis (4-biphenylyl) amine and 10 ml of toluene were added and dissolved at room temperature. To this was added a solution of 556 mg (1.5 mmol) of copper perchlorate hexahydrate in 5 ml of butyronitrile, and the mixture was stirred at room temperature for 9 hours and left overnight (15 hours). After adding 10 ml of 3% aqueous ammonia at room temperature and stirring for 30 minutes, insolubles were collected by filtration. After washing with 3% aqueous ammonia, followed by water and methanol, drying under reduced pressure at 40 ° C. gave 264 mg (yield 90.3%) of N, N, N ′, N′-tetra (4-biphenylyl) benzidine. It was.

[Example 8]
To a 50 ml three-necked flask equipped with a thermometer, 294 mg (0.75 mmol) of N-phenyl-bis (4-biphenylyl) amine and 10 ml of toluene were added and dissolved at room temperature. To this was added a solution of 556 mg (1.5 mmol) of copper perchlorate hexahydrate in 5 ml of propionitrile, and the mixture was stirred at room temperature for 9 hours and left overnight (15 hours). After adding 10 ml of 3% aqueous ammonia at room temperature and stirring for 30 minutes, insolubles were collected by filtration. After washing with 3% aqueous ammonia, followed by water and methanol, drying under reduced pressure at 40 ° C. gave 271 mg (yield 92.5%) of N, N, N ′, N′-tetra (4-biphenylyl) benzidine. It was.

[Example 9]
To a 50 ml three-necked flask equipped with a thermometer, 294 mg (0.75 mmol) of N-phenyl-bis (4-biphenylyl) amine and 10 ml of toluene were added and dissolved at room temperature. When a solution of 556 mg (1.5 mmol) of copper perchlorate hexahydrate dissolved in 5 ml of benzonitrile was added thereto, it appeared to be gelled, but after stirring for 9 hours at room temperature, overnight (15 Time) After adding 10 ml of 3% aqueous ammonia at room temperature and stirring for 30 minutes, insolubles were collected by filtration. After washing with 3% aqueous ammonia, followed by water and methanol, drying under reduced pressure at 40 ° C. gave 263 mg of N, N, N ′, N′-tetra (4-biphenylyl) benzidine (yield 89.7%). It was.

[Example 10]
To a 200 ml three-necked flask equipped with a thermometer, 2.37 g (5 mmol) of N-3-biphenyl-bis (4-biphenylyl) amine and 80 ml of toluene were added and dissolved at 45 ° C. A solution prepared by dissolving 3.70 g (10 mmol) of copper perchlorate hexahydrate in 40 ml of acetonitrile was added thereto, and the mixture was stirred at 45 ° C. for 8 and a half hours, and then 80 ml of 3% aqueous ammonia was added at the same temperature. Stir for 30 minutes. After standing overnight (13 hours), insolubles were collected by filtration. After washing with 3% aqueous ammonia, followed by water and methanol, drying under reduced pressure at 40 ° C., 2.03 g of 2,2′-diphenyl-N, N, N ′, N′-tetra (4-biphenylyl) benzidine ( Yield 85.9%).

[Example 11]
To a 200 ml three-necked flask equipped with a thermometer, 2.91 g (7 mmol) of N-3-fluorophenyl-bis (4-biphenylyl) amine and 50 ml of toluene were added and dissolved at room temperature. A solution prepared by dissolving 5.19 g (14 mmol) of copper perchlorate hexahydrate in 20 ml of acetonitrile was added thereto, followed by stirring at room temperature for 8 and a half hours, and then 100 ml of 3% aqueous ammonia was added at the same temperature. Stir for minutes. After standing overnight (13 hours), insolubles were collected by filtration. After washing with 3% aqueous ammonia, followed by water and methanol, drying under reduced pressure at 40 ° C., 1.09 g of 2,2′-difluoro-N, N, N ′, N′-tetra (4-biphenylyl) benzidine ( Yield 37.6%).

[Example 12]
To a 50 ml three-necked flask equipped with a thermometer, 179 mg (0.4 mmol) of N-1-naphthyl-bis (4-biphenylyl) amine and 20 ml of toluene were added and dissolved at room temperature. A solution of 222 mg (0.6 mmol) of copper perchlorate hexahydrate dissolved in 10 ml of acetonitrile was added to this, and the mixture was stirred at room temperature for 8 hours, and then 20 ml of 3% aqueous ammonia was added at the same temperature for 30 minutes. After stirring, the insoluble material was collected by filtration. After washing with 3% aqueous ammonia, followed by water and methanol, it was dried under reduced pressure at 40 ° C. Purification by column chromatography (carrier: NH silica gel 100 g, manufactured by Fuji Silysia Chemical Ltd., eluent: cyclohexane / chloroform = 25/1), N, N, N ′, N′-tetra (4-biphenylyl) -1 , 1′-binaphthyl-4,4′-diamine (110 mg, yield 61.5%) was obtained.

[Comparative example]
To a 50 ml three-necked flask equipped with a thermometer, N-phenyl-bis (4-biphenylyl) amine 0.59 g (1.5 mmol) and 20 ml of acetonitrile were added and stirred at room temperature. To this was added a solution of 1.11 g (3 mmol) of copper perchlorate hexahydrate dissolved in 10 ml of acetonitrile, and the mixture was stirred at room temperature for 9 hours and left overnight (15 hours). After adding 10 ml of 3% aqueous ammonia at room temperature and stirring for 30 minutes, insolubles were collected by filtration. After washing with 3% aqueous ammonia and then with water, it was dried at 40 ° C. under reduced pressure. In the HPLC analysis, the raw material residue was 6.1%, and the oligomer was 11.5%.

N, N, N ', N'-tetraarylbenzidine derivatives useful as organic electroluminescent elements, electrophotographic photosensitive members, organic transistors, and other electronic materials, and intermediates thereof can be produced efficiently and by-products can be produced. It can be manufactured with suppression.

Claims (7)

Triarylamine compound represented by the following general formula (1), characterized in that the oxidation reaction of triarylamines using an oxidizing agent and at least two or more solvents, is represented by the following general formula (2) A method for producing an N, N, N ′, N′-tetraarylbenzidine derivative , wherein the solvent can dissolve the triarylamines, and the solvent can dissolve the oxidizing agent. N, N, N ′, a co-solvent comprising a nitrile solvent as B, wherein the triarylamines and the oxidizing agent are oxidized in a state of being dissolved in the co-solvent. A method for producing an N′-tetraarylbenzidine derivative.

(Wherein P and Q each independently represent an unsubstituted or aromatic hydrocarbon group having 1 to 2 or more substituents, and each of the substituents independently represents a methyl group, an ethyl group, a tert-butyl group, a methoxy group, Group, trifluoromethyl group, fluoro group and phenyl group, R _{1 to} R ₄ each independently represents a hydrogen atom, a methyl group or a fluoro group, and R ₃ and R ₄ are linked to form a benzene ring. In this case, the benzene ring may have a methyl group or a fluoro group as a substituent.)

(Wherein, P, Q and _R 1 to R ₄ are each identical P, a Q, and _R 1 to R ₄ in the general formula (1).) 2. The N, N, N ′, N′-tetraaryl according to claim 1, wherein the oxidizing agent is one selected from copper perchlorate, iron perchlorate, and copper tetrafluoroborate. A method for producing a benzidine derivative. The said solvent A is 1 type, or 2 or more types chosen from toluene, xylenes, and a cyclohexane, N, N, N ', as described in any one of Claim 1 or Claim 2 characterized by the above-mentioned. A method for producing an N′-tetraarylbenzidine derivative. The N, according to any one of claims 1 to 3, wherein the nitrile solvent is one or more selected from acetonitrile, propionitrile, butyronitrile, and benzonitrile. A method for producing an N, N ′, N′-tetraarylbenzidine derivative. The method for producing the N, N, N ′, N′-tetraarylbenzidine derivative includes a step of quenching the produced N, N, N ′, N′-tetraarylbenzidine derivative with a base, an acid or water. The manufacturing method of the N, N, N ', N'-tetraaryl benzidine derivative as described in any one of Claims 1-4 characterized by the above-mentioned. The N, N, N ', N'- method of manufacturing a tetra aryl benzidine derivatives, when the oxidizing agent is a copper perchlorate or copper tetrafluoroborate, claim, characterized in that quenching with aqueous ammonia 5 A method for producing an N, N, N ′, N′-tetraarylbenzidine derivative as described in 1. above. The N, N, N ', N'- method of manufacturing a tetra aryl benzidine derivatives, when the oxidizing agent is a perchlorate of iron, according to claim 5, characterized in that quenching with dilute hydrochloric acid N, N , N ′, N′-Tetraarylbenzidine derivative production method.