JP7308161B2 - Method for producing asymmetric diarylamines - Google Patents

Description

Application of Article 30, Paragraph 2 of the Patent Act Published four times in total from March 1, 2019 to September 9, 2019 in the following publications. 1. Issued on March 1, 2019 / Proceedings of the 99th Annual Meeting of the Chemical Society of Japan, titled "C—H Arylation Reaction at the Arylamine Ortho Position Using a Nickel Catalyst" 2. Issued on June 24, 2019 / The 52nd Organometallic Wakamono Association Summer School Proceedings, titled "C-H Arylation Reaction at Arylamine Ortho-Position Using Ni Catalyst"3. Issued on August 29, 2019 / 66th Symposium on Organometallic Chemistry, Japan, ABSTRACT Title "Nickel-Catalyzed C-H Arylation of Arylamines" 4. Issued on September 9, 2019 / The 2nd JGP Chem & ChemEn International Workshop: Sustainability-Oriented Organic Synthesis, entitled "Nickel-Catalyzed C-H Arylation of Ary lamines"

TECHNICAL FIELD The present invention relates to a method for producing an asymmetric diarylamine, which is a partial skeleton useful as a hole transport material for organic EL.

Diarylamines are industrially useful because they are important partial skeletons as hole-transporting materials for organic EL.

For example, a carbon-nitrogen (C—N) coupling reaction utilizing the active nitrogen atom of diarylamines enables the production of π-conjugated extended organic compounds with linked π-conjugated systems.

Among diarylamines, asymmetric compounds (asymmetric diarylamines) have high amorphous properties, making it easy to form a uniform thin film. Establishment of a method for producing amines is industrially important.

As a method for producing asymmetric diarylamines, there is a method of reacting an aniline with chlorobenzene in the presence of a base. However, this reaction requires an excessive amount of anilines and bases and is poor in efficient productivity. In addition, it is not suitable for late-synthetic diversification strategies that are necessary to produce electronic materials with a wide variety of substituents.

On the other hand, Non-Patent Document 2 is also cited as a method for producing asymmetric diarylamines. This document requires the starting material to be the anilide substrate and requires a multi-step process to obtain the unsymmetrical diarylamines. In addition, it uses an expensive rhodium catalyst and is not economically viable.

Olafs Daugulis, Organic Letters 14, 2012, pp. 5964-5967 Chien-Hong Cheng, Advanced Synthesis & Catalysis 357, 2015, pp. 366-370

The asymmetric diarylamines of the present invention are used as precursors or introduced as partial skeletons of compounds useful as hole-transporting materials for organic EL. Accordingly, an object of the present invention is to provide a method for producing asymmetric diarylamines.

As a result of intensive studies on the above problems, the present inventors prepared magnesium amides by reacting diarylamines with a Grignard reagent, and reacted them with haloaryls in the presence of a nickel catalyst to synthesize asymmetric diarylamines. I found that it can be done, and came to complete the present invention.

That is, the present invention provides the following general formula (1)

[In formula (1),
Ar ₁ represents a phenyl group, biphenyl group, naphthyl group, terphenyl group, anthracenyl group or phenanthrenyl group, and a linear, branched or cyclic alkyl group, alkoxy group and perfluoroalkyl group having 3 to 6 carbon atoms; , a methyl group, an ethyl group, and a nitrile group, preferably a phenyl group,
Ar ² represents a divalent aromatic hydrocarbon group having 6 to 22 carbon atoms, such as a phenyl group, a biphenyl group, a naphthyl group, a terphenyl group, an anthracenyl group or a phenanthrenyl group, and a straight chain having 3 to 6 carbon atoms; may have one or more substituents selected from the group consisting of linear, branched or cyclic alkyl groups, alkoxy groups, perfluoroalkyl groups, methyl groups, ethyl groups and nitrile groups; However, a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted or fused is preferred,
Ar ₃ represents a phenyl group, a biphenyl group, a naphthyl group, a terphenyl group, anthracenyl group, a phenanthrenyl group, a pyrenyl group, a thiophenyl group, a pyrenyl group or a furanyl group, having 3 to 6 carbon atoms, linear or branched or may have one or more substituents selected from the group consisting of cyclic alkyl groups, alkoxy groups and perfluoroalkyl groups, methyl groups, ethyl groups and nitrile groups; Phenyl or naphthyl groups are preferred. ]
A method for producing an asymmetric diarylamine represented by

General formula (2) below

[In Formula (2), Ar ₁ and Ar ₂ are the same as in Formula (1) above. ]
Obtained by reacting a diarylamine and a Grignard reagent represented by

General formula (3) below

[In Formula (3), Ar ₁ and Ar ₂ are the same as in Formula (1) above, and X ₁ represents a chlorine atom, a bromine atom, or an iodine atom. ], the following general formula (4)

[In Formula (4), Ar ₃ is the same as in Formula (1) above, and X ₂ represents a chlorine atom, a bromine atom, or an iodine atom. ]
It relates to a method for producing an asymmetric diarylamine represented by the general formula (1), wherein an aryl halide represented by is reacted in the presence of a nickel catalyst.

The present invention also relates to the above process for producing asymmetric diarylamines, wherein Ar ₁ is a phenyl group and Ar ₂ is a phenyl group or a naphthyl group.

Industrially useful asymmetric diarylamines can be obtained in good yield according to the present invention.

DETAILED DESCRIPTION OF THE INVENTION Embodiments for carrying out the present invention will be described in detail below. In addition, the present invention is not limited to the following embodiments. The present invention can be modified appropriately within the scope of its gist.

In the method for producing an asymmetric diarylamine of the present invention, in the above formula (1), as a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms substituted by Ar ₁ , Ar ₂ and Ar ₃ is n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, i-propyl group, i-butyl group, s-butyl group, t-butyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1,2-dimethylpropyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4 -methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethyl butyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.

In the above formula (1), the linear, branched or cyclic alkoxy group having 3 to 6 carbon atoms substituted by Ar ₁ , Ar ₂ and Ar ₃ includes a methoxy group, an ethoxy group and an n-propoxy group. , i-propoxy group, n-butoxy group, s-butoxy group, t-butoxy group, 1-methylbutoxy group, 2-methylbutoxy group, 3-methylbutoxy group, 1,1-dimethylpropoxy group, 2,2 -dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-methylpentoxy group, 2-methylpentoxy group, 3-methylpentoxy group, 4-methylpentoxy group, 1,1-dimethylbutoxy group, 1 , 2-dimethylbutoxy group, 1,3-dimethylbutoxy group, 2,2-dimethylbutoxy group, 2,3-dimethylbutoxy group, 3,3-dimethylbutoxy group, 1,1,2-trimethylpropoxy group, 1 , 2,2-trimethylpropoxy group, cyclopropoxy group, cyclobutoxy group, cyclopentoxy group, cyclohexoxy group and the like.

In the above formula (1), the linear, branched or cyclic perfluoroalkyl group having 3 to 6 carbon atoms substituted by Ar ₁ , Ar ₂ and Ar ₃ includes trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, undecafluoropentyl group, tridecafluorohexyl group, pentafluorocyclopropyl group, heptafluorocyclobutyl group, nonafluorocyclopentyl group, undecafluorocyclohexyl group and the like. .

The Grignard reagent used in the present invention may be any aliphatic Grignard reagent. Chloride compounds such as magnesium chloride and butylmagnesium chloride, and iodide compounds such as methylmagnesium iodide, ethylmagnesium iodide, isopropylmagnesium iodide, and butylmagnesium iodide are used. is preferably 1.0 molar equivalents to 100.0 molar equivalents, more preferably 1.1 molar equivalents to 10.0 molar equivalents with respect to the magnesium amides represented by or the aryl halides represented by the above general formula (4). be.

The nickel catalyst used in the present invention may be a common one, such as nickel (II) chloride, nickel (II) chloride tetrahydrate, nickel (II) chloride hexahydrate, [1,4- bis(diphenylphosphino)butane]nickel(II) dichloride, bis(triphenylphosphine)nickel(II) dichloride, bis(cyclohexyldiphenylphosphine)nickel(II) dichloride, bis(tricyclohexylphosphine)nickel(II) dichloride, Bis(trianisoylphosphine)nickel(II) dichloride is preferred from a yield standpoint. [1,4-bis(diphenylphosphino)ethane]nickel(II) dichloride, [1,4-bis(diphenylphosphino)butane]nickel(II) dichloride, [1,4-bis(diphenylphosphino) )ferrocene]nickel(II) dichloride, the ligand may inhibit the reaction and reduce the yield.

The amount of the nickel catalyst added is preferably in the range of 0.01 mol% to 100 mol%, more preferably 0.05 mol% to 5.0 mol%, relative to the magnesium amide represented by the general formula (3). Range is preferred. Olafs Daugulis, Organic Letters 14, 2012, pp. 5964-5967 (Non-Patent Document 1) mentioned above has the problem that 300 mol % or more is necessary when using lithium tetramethylpiperidide. On the other hand, in the present invention, if 0.05 mol % of the nickel catalyst is used, the desired product can be obtained in good yield.

As the co-catalyst used in the present invention, any general co-catalyst may be used, and examples thereof include triphenylphosphine, trianisoylphosphine, cyclohexyldiphenylphosphine, tricyclohexylphosphine and the like. Also, depending on the type of nickel catalyst used, such as bis(triphenylphosphine)nickel(II) dichloride, the co-catalyst may not be used.
The amount of co-catalyst added is preferably in the range of 0.01 mol% to 100 mol%, more preferably in the range of 1.0 mol% to 20 mol%, relative to the magnesium amides represented by the general formula (3). .

Any general organic solvent may be used in the present invention, and from the viewpoint of yield, toluene, benzene, xylene, ethylbenzene, diethyl ether and the like are desirable. Moreover, a solvent may be used singly or in combination of two or more. Incidentally, tetrahydrofuran may coordinate with the magnesium atom of the magnesium amide represented by the general formula (3) to inhibit the reaction.
The amount of the solvent used is preferably 1 to 1000 parts by weight with respect to the magnesium amide represented by the general formula (3) or the aryl halide represented by the general formula (4).

In the production method of the present invention, asymmetric diarylamines can be synthesized by reacting diarylamines with a Grignard reagent to prepare magnesium amides and reacting them with haloaryls in the presence of a nickel catalyst. That is, asymmetric diarylamines can be synthesized by reacting the above diarylamines, aryl halides, Grignard reagents, nickel catalysts, and, if necessary, in the presence of co-catalysts.

Specifically, the nickel catalyst, the co-catalyst and the solvent may be added at the same time as the magnesium amides represented by the above general formula (3). may be sequentially added to the magnesium amides obtained by reacting with. Alternatively, the diarylamine represented by the general formula (2), the nickel catalyst, the co-catalyst and the solvent may be mixed in advance, and the Grignard reagent may be added, as in Examples described later.

In the present invention, the reaction is desirably carried out in an inert gas atmosphere such as nitrogen or argon, and can also be carried out under normal pressure or increased pressure.
The reaction temperature is desirably in the range of -50°C to 300°C, more desirably in the range of 0°C to 150°C.
The reaction time is not particularly limited because it varies depending on the type of substrate and the reaction temperature, but the reaction can usually be completed within the range of 1 hour to 48 hours.

After completion of the reaction, generally known purification techniques can be used. For example, water or dilute hydrochloric acid is added to the reaction solution, the salt produced is dissolved, and then the organic layer is separated by liquid separation and concentrated to obtain the target compound. Thereafter, it can be isolated and purified by column chromatography, crystallization, recycle preparative GPC, or the like, if necessary.

EXAMPLES The present invention will be described in more detail below using examples, but these examples only show the outline of the present invention and the present invention is not limited to these examples.

（式（５）中、Ａｒ_１、Ａｒ_２及びＡｒ_３はそれぞれ前記式（１）と同じ。）で示されるトリアリールアミン類（Ｃ－Ｎ体）が副生する。上記（背景）したようなπ共役系が連結されたπ共役系拡張有機化合物を製造するためには、窒素原子上に活性水素を有しないＣ－Ｎ体の生成割合は少ないことが望ましい。Ｃ－Ｈ体とＣ－Ｎ体の生成比（Ｈ／Ｎ）については、ＧＣ分析により得られたＣ－Ｈ体の収率（ａ）［％］、Ｃ－Ｎ体の収率（ｂ）［％］から、下式により算出した。
Ｈ／Ｎ ＝ ａ／ｂ
目的物の精製は、塩溶解、溶媒抽出及び濃縮により行い、必要に応じてリサイクル分取ＧＰＣを用いた。 Production of the target compound was confirmed by ¹ H NMR ( ¹ H nuclear magnetic resonance spectrum) analysis and GC analysis.
The yield of the target compound was determined by GC analysis using undecane as an internal standard substance.
In this production, for the target compound (C-H form),
General formula (5) below

(In formula (5), Ar ₁ , Ar ₂ and Ar ₃ are the same as in formula (1) above.) Triarylamines (C—N bodies) represented by the formula are by-produced. In order to produce a π-conjugated extended organic compound in which π-conjugated systems are linked as described above (background), it is desirable that the proportion of C—N isomers that do not have active hydrogen on nitrogen atoms is small. Regarding the production ratio (H/N) of the C—H body and the C—N body, the yield of the C—H body obtained by GC analysis (a) [%], the yield of the C—N body (b) It was calculated by the following formula from [%].
H/N = a/b
Purification of the target product was carried out by salt dissolution, solvent extraction and concentration, and recycled preparative GPC was used as necessary.

The measurement equipment, conditions and sample preparation method are as follows.
[NMR analysis]
Device: JEOL ECS-400NR
Preparation method of measurement sample: About 25 mg of the measurement sample and about 25 mg of 1,2-dibromomethane as an internal standard were weighed and dissolved in about 0.7 mL of deuterated chloroform.

[GC analysis]
Apparatus: Shimadzu GC-2010 (FID)
Column: ZB-1MS (10 m × 0.10 mm I.D.df: 0.1 μm) (manufactured by Phenomenex)
Column temperature: 50°C x 2 min → 20°C/min up to 200°C → 15°C/min up to 300°C Vaporization chamber temperature: 350°C
Detector: Hydrogen flame ionization detector Detector temperature: 350°C
Measurement sample preparation method: About 0.02 mL of undecane as an internal standard substance was added to the reaction solution in advance, and the organic layer extracted with ethyl acetate was measured.

[Recycling preparative GPC]
Instrument: Japan Analytical Industry LC-9204 instrument
Column: JAIGEL-1H-40/JAIGEL-2H-40

Example 1: Synthesis of N-phenyl-2-biphenylamine

Diphenylamine (60.92 mg, 0.360 mmol), bis(triphenylphosphine)nickel(II) dichloride (9.81 mg, 0.015 mmol), triphenyl Phosphine (7.87 mg, 0.030 mmol), bromobenzene (47.10 mg, 0.300 mmol) and 2.00 mL of toluene were added dropwise and stirred at room temperature for 10 minutes. Then, a diethyl ether solution (0.117 mL) of ethylmagnesium bromide was added dropwise, and the mixture was aged at a heat block temperature of 80° C. for 3 hours. After cooling to room temperature, 1N hydrochloric acid (1.00 mL) was added to stop the reaction. Extraction was performed using ethyl acetate (2.00 mL×4 times), and the resulting organic layer was concentrated to dryness to obtain the target compound as a brown oily liquid (yield: 69%, yield: 50.78 mg). , H/N=88/12).

The formation of the desired product was confirmed by the peak at 11.00 min obtained by ¹ H NMR analysis and GC analysis.
¹ H NMR (CDCl ₃ , 392 MHz) δ 5.60 (s, 1H), 6.92 (t, J=7.8 Hz, 1H), 7.23-7.27 (m, 4H), 7.34 -7.45 (m, 6H)

Example 2: Synthesis of 1,N-diphenyl-2-naphthylamine

N-phenyl-2-naphthylamine (78.94 mg, 0.360 mmol), bis(triphenylphosphine)nickel(II) dichloride (9.81 mg, 0 .015 mmol), triphenylphosphine (7.87 mg, 0.030 mmol), bromobenzene (47.10 mg, 0.300 mmol) and 2.00 mL of toluene were added dropwise and stirred at room temperature for 10 minutes. Then, a diethyl ether solution (0.117 mL) of ethylmagnesium bromide was added dropwise, and the mixture was aged at a heat block temperature of 80° C. for 3 hours. After cooling to room temperature, 1N hydrochloric acid (1.00 mL) was added to stop the reaction. Extraction was performed using ethyl acetate (2.00 mL×4 times), and the resulting organic layer was concentrated to dryness to obtain the target compound as a brown oily liquid (yield: 85%, yield: 75.32 mg). , H/N=99/1). The formation of the desired product was confirmed by the peak at 13.65 min obtained by GC analysis.

Example 3: Synthesis of N-phenyl-2-(1-(4-methyl)phenyl)naphthylamine

N-phenyl-2-naphthylamine (78.94 mg, 0.360 mmol), bis(triphenylphosphine)nickel(II) dichloride (9.81 mg, 0 .015 mmol), triphenylphosphine (7.87 mg, 0.030 mmol), 4-bromotoluene (51.31 mg, 0.300 mmol), and 2.00 mL of toluene were added dropwise and stirred at room temperature for 10 minutes. Then, a diethyl ether solution (0.117 mL) of ethylmagnesium bromide was added dropwise, and the mixture was aged at a heat block temperature of 80° C. for 3 hours. After cooling to room temperature, 1N hydrochloric acid (1.00 mL) was added to stop the reaction. Extraction was performed using ethyl acetate (2.00 mL×4 times), and the obtained organic layer was concentrated to dryness to obtain the target compound as a brown oily liquid (yield: 81%, yield: 74.88 mg). , H/N=97/3). The formation of the desired product was confirmed by the peak at 14.10 min obtained by GC analysis.

Example 4: Synthesis of N-phenyl-2-(1-(4-methoxy)phenyl)naphthylamine

N-phenyl-2-naphthylamine (78.94 mg, 0.360 mmol), bis(triphenylphosphine)nickel(II) dichloride (9.81 mg, 0 .015 mmol), triphenylphosphine (7.87 mg, 0.030 mmol), 4-bromoanisole (56.11 mg, 0.300 mmol) and 2.00 mL of toluene were added dropwise and stirred at room temperature for 10 minutes. Then, a diethyl ether solution (0.117 mL) of ethylmagnesium bromide was added dropwise, and the mixture was aged at a heat block temperature of 80° C. for 3 hours. After cooling to room temperature, 1N hydrochloric acid (1.00 mL) was added to stop the reaction. Extraction was performed using ethyl acetate (2.00 mL×4 times), and the resulting organic layer was concentrated to dryness to obtain the target compound as a brown oily liquid (yield: 67%, yield: 65.73 mg). , H/N=>99/1). The formation of the desired product was confirmed by the peak at 14.84 min obtained by GC analysis.

Example 5: Synthesis of N-phenyl-2-(1-(4-trifluoromethyl)phenyl)naphthylamine

N-phenyl-2-naphthylamine (78.94 mg, 0.360 mmol), bis(triphenylphosphine)nickel(II) dichloride (9.81 mg, 0 .015 mmol), triphenylphosphine (7.87 mg, 0.030 mmol), 4-bromobenzotrifluoride (64.23 mg, 0.300 mmol), and 2.00 mL of toluene were added dropwise and stirred at room temperature for 10 minutes. Then, a diethyl ether solution (0.117 mL) of ethylmagnesium bromide was added dropwise, and the mixture was aged at a heat block temperature of 80° C. for 3 hours. After cooling to room temperature, 1N hydrochloric acid (1.00 mL) was added to stop the reaction. Extraction was performed using ethyl acetate (2.00 mL x 4 times), and the resulting organic layer was concentrated to dryness and purified by preparative recycling GPC to obtain the target compound as a white solid (yield: 62%, Yield: 71.98 mg, H/N=>99/1).

The formation of the desired product was confirmed by the peak at 13.24 min obtained by ¹ H NMR analysis and GC analysis.
¹ H NMR (CDCl ₃ , 392 MHz) δ 5.38 (s, 1H), 6.96 (tt, J=0.8, 7.8 Hz, 1H), 7.02 (dd, J=0.8, 7.8 Hz, 2H), 7.24-7.28 (m, 2H), 7.31-7.35 (m, 2H), 7.53 (d, J = 7.8 Hz, 2H), 7. 59 (d, J = 9.0Hz, 1H), 7.81 (d, J = 8.6Hz, 4H)

Example 6: Synthesis of N-phenyl-2-(1,1'-binaphthyl)amine

N-phenyl-2-naphthylamine (78.94 mg, 0.360 mmol), bis(triphenylphosphine)nickel(II) dichloride (9.81 mg, 0 .015 mmol), triphenylphosphine (7.87 mg, 0.030 mmol), 1-bromonaphthalene (62.12 mg, 0.300 mmol) and 2.00 mL of toluene were added dropwise and stirred at room temperature for 10 minutes. Then, a diethyl ether solution (0.117 mL) of ethylmagnesium bromide was added dropwise, and the mixture was aged at a heat block temperature of 80° C. for 3 hours. After cooling to room temperature, 1N hydrochloric acid (1.00 mL) was added to stop the reaction. Extraction was performed using ethyl acetate (2.00 mL x 4 times), and the resulting organic layer was concentrated to dryness to obtain a brown oily liquid (yield: 60%, yield: 65.98 mg, H/ N=93/7). The formation of the desired product was confirmed by the peak at 15.61 min obtained by GC analysis.

Example 7: Synthesis of N-phenyl-2-(1-(3-methyl)phenyl)naphthylamine

N-phenyl-2-naphthylamine (78.94 mg, 0.360 mmol), bis(triphenylphosphine)nickel(II) dichloride (9.81 mg, 0 .015 mmol), triphenylphosphine (7.87 mg, 0.030 mmol), 3-bromotoluene (51.31 mg, 0.300 mmol) and 2.00 mL of toluene were added dropwise and stirred at room temperature for 10 minutes. Then, a diethyl ether solution (0.117 mL) of ethylmagnesium bromide was added dropwise, and the mixture was aged at a heat block temperature of 80° C. for 3 hours. After cooling to room temperature, 1N hydrochloric acid (1.00 mL) was added to stop the reaction. Extraction was performed using ethyl acetate (2.00 mL x 4 times), and the resulting organic layer was concentrated to dryness to obtain the target compound as a brown oily liquid (yield: 80%, yield: 73.02 mg). , H/N=97/3). The formation of the desired product was confirmed by the peak at 13.94 min obtained by GC analysis.

Comparative example 1

Diphenylamine (60.92 mg, 0.360 mmol) and diethyl ether (1.000 mL) were charged in a screw-type Teflon (registered trademark) stoppered test tube (20 mL), and then diethyl magnesium bromide was added at an internal temperature of 0°C. An ether solution (0.117 mL) was added dropwise. Then, the mixture was stirred at room temperature for 1 hour, and the solvent was distilled off to obtain magnesium diphenylamide. Then, iron (III) fluoride trihydrate (1.50 mg, 0.030 mmol), bromobenzene (47.10 mg, 0.300 mmol), and 2.00 mL of xylene were added dropwise, and the heat block temperature was 160°C for 24 hours. Time aged. After cooling to room temperature, 1N hydrochloric acid (1.00 mL) was added to stop the reaction. Extraction was performed using ethyl acetate (2.00 mL×4 times), and the resulting organic layer was concentrated to dryness to obtain a brown oily liquid. When GC analysis was performed, a peak at 11.00 min derived from the target compound could not be confirmed, and a peak at 10.38 min derived from the CN form was confirmed (yield: 95%, yield: 73.60 mg, H/N=1/>99).

The above Examples 1 to 7 and Comparative Example 1 are summarized in Table 1.

By using the method of the present invention, asymmetric diarylamines, which are useful partial skeletons for organic EL hole-transporting materials, can be produced in high yields, and are industrially extremely useful.

Claims (2)

General formula (1) below

[Ar ₁ represents a phenyl group, a naphthyl group, an anthracenyl group or a phenanthrenyl group; It may have one or more substituents selected from the group consisting of an ethyl group and a nitrile group,
Ar ² represents a divalent aromatic hydrocarbon group having 6 to 22 carbon atoms, a linear or branched or cyclic alkyl group, alkoxy group and perfluoroalkyl group having 3 to 6 carbon atoms, a methyl group, It may have one or more substituents selected from the group consisting of an ethyl group and a nitrile group,
Ar ₃ represents a phenyl group, a biphenyl group, a naphthyl group, a terphenyl group, anthracenyl group, a phenanthrenyl group, a pyrenyl group, a thiophenyl group, a pyrenyl group or a furanyl group, having 3 to 6 carbon atoms, linear or branched or It may have one or more substituents selected from the group consisting of cyclic alkyl groups, alkoxy groups, perfluoroalkyl groups, methyl groups, ethyl groups and nitrile groups. ]
A method for producing an asymmetric diarylamine represented by
General formula (2) below

[In Formula (2), Ar ₁ and Ar ₂ are the same as in Formula (1) above. ]
Obtained by reacting a diarylamine and a Grignard reagent represented by
General formula (3) below

[In Formula (3), Ar ₁ and Ar ₂ are the same as in Formula (1) above, and X ₁ represents a chlorine atom, a bromine atom, or an iodine atom. ], the following general formula (4)

[In Formula (4), Ar ₃ is the same as in Formula (1) above, and X ₂ represents a chlorine atom, a bromine atom, or an iodine atom. ]
A method for producing an asymmetric diarylamine represented by the general formula (1), wherein an aryl halide represented by is reacted in the presence of a nickel catalyst. The production method according to claim ₁ , wherein Ar 1 is a phenyl group and Ar ₂ is a phenyl group or a naphthyl group.