JPH10310561A - Production of tertiary arylamines - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a tertiary arylamine, enabling to synthesize the tertiary arylamine from a primary amine in one pot in high activity and in high selectivity. SOLUTION: This method for producing a tertiary arylamine comprises reacting a primary amine of formula I: R(NH2 )n [R is an alkyl group or a substituted or unsubstituted aryl group; (n) is 1 or 2] with two different kinds of arylamines of formula II: Ar1(X1)m1 [Ar1 is a substituted or unsubstituted aryl group; X1 is F, Cl, Br or I; (m1) is an integer of 1-3] and formula III: Ar2(X2)m2 [Ar2 is a substituted or unsubstituted aryl group different from Ar1; X2 is F, Cl, Br or I; (m2) is an integer of 1-3] in the presence of a base and a catalyst comprising a trialkylphosphine and a palladium compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing tertiary arylamines. Arylamines are compounds useful as intermediates for medicines and agricultural chemicals, hole transport materials for organic electroluminescence (organic EL) devices, or organic photosensitive materials.

[0002]

2. Description of the Related Art Arylamines have conventionally been synthesized using amines and iodide benzenes.
n) by reaction. For example, Chem. Le
tt. Pp. 1145 to 1148, 1989, U.S. Pat. No. 4,764,625, JP-A-8-4897.
No. 4 gazette discloses that a corresponding arylbenzene iodide is reacted with a diarylamine in an inert hydrocarbon solvent such as decalin at 150 ° C. or higher in the presence of 1 equivalent or more of copper powder and a base represented by potassium hydroxide. The preparation of triarylamines is described.

[0003] Recently, an example of the reaction between a secondary amine and an aryl halide is described in Stephen L. et al. Buch
Wald et al. reported a method for synthesizing arylamines from aryl halides and amine compounds (Ang).
ew. Chem. Int. Ed. Engl. , 34, N
o. 12, 1348 (1995)). In this method, an aryl bromide is used as a raw material, and sodium-t is used as a base.
Using ert-butoxide as a base, bis (dibenzylideneacetone) -bis (tri-o-tolylphosphine) palladium or dichloro-bis (tri-o-tolylphosphine) palladium, that is, tri-o-tolylphosphine as a ligand An arylamine is synthesized using a palladium compound as a catalyst. A similar method is J
ohnF. Hartwig et al. (Tetrahedron Letters, Vol.
36, no. 21, 3609 (1995)).

[0004]

However, in the method based on the Ullmann reaction, an expensive iodide must be used as a reactant, so that not only the applicability is poor, but also the reaction yield is not sufficient. . Further, a high temperature of 150 ° C. or more and a long reaction time are required, and a large amount of copper powder is used, so that a waste liquid containing a large amount of copper is generated, and there is also an environmental problem.

In a method using a palladium compound having tri-o-tolylphosphine as a ligand as a catalyst,
When a primary amine is reacted with an aryl halide, the reaction activity decreases and not only takes a long time, but also
Subsequently, when the obtained secondary amine is reacted with an aryl halide, there is a problem that steric repulsion between the ligand and tri-o-tolylphosphine increases, and the reaction hardly proceeds.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for producing a tertiary arylamine from a primary amine in one pot with high activity and high selectivity. It is.

[0007]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, surprisingly, in the presence of a catalyst comprising a trialkylphosphine and a palladium compound and a base, 1 The inventors have found that tertiary arylamines can be synthesized with high activity and high selectivity by reacting a tertiary amine with two kinds of different aryl halides, thereby completing the present invention.

That is, the present invention relates to a compound represented by the following general formula (1) R (NH ₂ ) _n (1) wherein R is an alkyl group or a substituted or unsubstituted trialkylphosphine and a palladium compound. And a primary amine represented by the following general formula (2): Ar1 (X1) _m1 (2) (wherein, Ar1 is a substituted or unsubstituted group) Represents an aryl group,
X1 represents F, Cl, Br or I, and m1 represents an integer of 1 to 3. ) And the following general formula (3): Ar2 (X2) _m2 (3) (wherein, Ar2 represents a substituted or unsubstituted aryl group different from Ar1, X2 represents F, Cl, Br or I,
m2 represents an integer of 1 to 3. 3) reacting with two different aryl halides represented by
This is a method for producing secondary arylamines.

Hereinafter, the present invention will be described in detail.

The following general formula (1) R (NH ₂ ) _n (1) wherein R represents an alkyl group or a substituted or unsubstituted aryl group, and n represents 1 or 2 Is not particularly limited, and R is usually an alkyl group having 1 to 18 carbon atoms or 6 to 2 carbon atoms.
Two substituted or unsubstituted aryl groups are used.

The primary amine used in the present invention includes:
Specifically, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-amylamine, isoamylamine, t
ert-amylamine, cyclohexylamine, n-hexylamine, heptylamine, 2-aminoheptane,
3-aminoheptane, octylamine, nonylamine,
Primary alkylamines such as decylamine, undecylamine, dodecylamine, tridecylamine, 1-tetradecylamine, pentadecylamine, 1-hexadecylamine and octadecylamine; ethylenediamine, 1,
2-diaminopropane, 1,3-diaminopropane,
Primary alkyl diamines such as 1,4-diaminobutane;
Aniline, o-fluoroaniline, m-fluoroaniline, p-fluoroaniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, m-anisidine, p-anisidine, 1-naphthylamine, 2-naphthylamine, 1 -Aminoanthracene, 2-aminoanthracene, 2-aminobiphenyl, 4-aminobiphenyl, 9-aminophenanthrene, 2-trifluoromethyltoluidine, 3-trifluoromethyltoluidine,
Arylamines such as trifluoromethyltoluidine; o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, fluorenediamine,
And aryldiamines such as 1,8-naphthalenediamine.

The following general formula (2) used in the present invention: Ar1 (X1) _m1 (2) (wherein, Ar1 represents a substituted or unsubstituted aryl group;
X1 represents F, Cl, Br or I, and m1 represents an integer of 1 to 3. ) And the following general formula (3): Ar2 (X2) _m2 (3) (wherein, Ar2 represents a substituted or unsubstituted aryl group different from Ar1, X2 represents F, Cl, Br or I,
m2 represents an integer of 1 to 3. ) Is not particularly limited, but as Ar1 and Ar2, an alkyl group having 1 to 18 carbon atoms or a substituted or unsubstituted aryl group having 6 to 22 carbon atoms is usually used. The aromatic ring may have a substituent. In the present invention, the aryl group includes a condensed cyclic hydrocarbon.

The aryl halide used in the present invention is, specifically, bromobenzene, o-bromoanisole, m-bromoanisole, p-bromoanisole,
o-bromotoluene, m-bromotoluene, p-bromotoluene, o-bromophenol, m-bromophenol, p-bromophenol, 2-bromobenzotrifluoride, 3-bromobenzotrilolide, 4-bromobenzotrif Chloride, 1-bromo-2,4-dimethoxybenzene, 1-bromo-2,5-dimethoxybenzene, 2-
Bromophenethyl alcohol, 3-bromophenethyl alcohol, 4-bromophenethyl alcohol, 5-bromo-1,2,4-trimethylbenzene, 2-bromo-m
-Xylene, 2-bromo-p-xylene, 3-bromo-
o-xylene, 4-bromo-o-xylene, 4-bromo-m-xylene, 5-bromo-m-xylene, 1-bromo-3- (trifluoromethoxy) benzene, 1-bromo-4- (trifluoro Methoxy) benzene, 2-bromobiphenyl, 3-bromobiphenyl, 4-bromobiphenyl, 4-bromo-1,2- (methylenedioxy) benzene, 1-bromonaphthalene, 2-bromonaphthalene, 1-bromo-2- Methylnaphthalene, 1-bromo-
Aryl bromides such as 4-methylnaphthalene; chlorobenzene, o-chloroanisole, m-chloroanisole, p-chloroanisole, o-chlorotoluene, m-
Chlorotoluene, p-chlorotoluene, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2-chlorobenzotrifluoride, 3-chlorobenzotrifluoride, 4-chlorobenzotrifluoride, 1-chloro -2,4-dimethoxybenzene, 1-chloro-2,
5-dimethoxybenzene, 2-chlorophenethyl alcohol, 3-chlorophenethyl alcohol, 4-chlorophenethyl alcohol, 5-chloro-1,2,4-trimethylbenzene, 2-chloro-m-xylene, 2-chloro-p- Xylene, 3-chloro-o-xylene, 4-chloro-o-xylene, 4-chloro-m-xylene, 5-chloro-m-xylene, 1-chloro-3- (trifluoromethoxy) benzene, 1-chloro -4- (trifluoromethoxy) benzene, 2-chlorobiphenyl, 3-chlorobiphenyl, 4-chlorobiphenyl, 1-chloronaphthalene, 2-chloronaphthalene, 1-chloro-2-methylnaphthalene, 1-chloro-4- Aryl chlorides such as methylnaphthalene; iodobenzene, o-iodoanisole, m-io Anisole, p-iodoanisole, o-iodotoluene, m-iodotoluene, p-iodotoluene, o-iodophenol, m-iodophenol, p-iodophenol, 2-iodobenzotrifluoride, 3-iodobenzotrif Chloride, 4-iodobenzotrifluoride, 1-iodo-2,4-dimethoxybenzene, 1-iodo-2,5-dimethoxybenzene,
2-iodophenethyl alcohol, 3-iodophenethyl alcohol, 4-iodophenethyl alcohol, 5-
Iodo-1,2,4-trimethylbenzene, 2-iodo-m-xylene, 2-iodo-p-xylene, 3-iodo-o-xylene, 4-iodo-o-xylene, 4-iodo-m-xylene , 5-iodo-m-xylene, 1-
Iodo-3- (trifluoromethoxy) benzene, 1-
Iodo-4- (trifluoromethoxy) benzene, 2-
Aryl iodides such as iodobiphenyl, 3-iodobiphenyl, 4-iodobiphenyl, 1-iodonaphthalene, 2-iodonaphthalene, 1-iodo-2-methylnaphthalene, 1-iodo-4-methylnaphthalene;
Fluorobenzene, o-fluoroanisole, m-fluoroanisole, p-fluoroanisole, o-fluorotoluene, m-fluorotoluene, p-fluorotoluene, o-fluorophenol, m-fluorophenol, p-fluorophenol, 2- Fluorobenzotrifluoride, 3-fluorobenzotrifluoride, 4-fluorobenzotrifluoride, 1-fluoro-2,4-dimethoxybenzene, 1-fluoro-2,5-dimethoxybenzene, 2-fluorophenethyl alcohol, 3-fluorophenethyl alcohol, 4-fluorophenethyl alcohol, 5-fluoro-1,2,4-trimethylbenzene, 2-fluoro-m-xylene, 2-fluoro-p
-Xylene, 3-fluoro-o-xylene, 4-fluoro-o-xylene, 4-fluoro-m-xylene, 5-
Fluoro-m-xylene, 1-fluoro-3- (trifluoromethoxy) benzene, 1-fluoro-4- (trifluoromethoxy) benzene, 2-fluorobiphenyl, 3-fluorobiphenyl, 4-fluorobiphenyl, 4-fluoro And arylfluorides such as -1,2- (methylenedioxy) benzene, 1-fluoronaphthalene, 2-fluoronaphthalene, 1-fluoro-2-methylnaphthalene, 1-fluoro-4-methylnaphthalene, and the like. .

In addition, unless departing from the object of the present invention, 1,2-dibromobenzene, 1,3-dibromobenzene, 1,4-dibromobenzene, 9,10-dibromoanthracene, 9,10-dichloroanthracene,
4,4'-dibromobiphenyl, 4,4'-dichlorodiphenyl, 4,4'-diiodobiphenyl, 1-bromo-2-fluorobenzene, 1-bromo-3-fluorobenzene, 1-bromo-4-fluoro Benzene, 2-bromochlorobenzene, 3-bromochlorobenzene, 4-bromochlorobenzene, 2-bromo-5-chlorotoluene, 3-bromo-4-chlorobenzotrifluoride, 5-
Bromo-2-chlorobenzotrifluoride, 1-bromo-
2,3-dichlorobenzene, 1-bromo-2,6-dichlorobenzene, 1-bromo-3,5-dichlorobenzene, 2-bromo-4-fluorotoluene, 2-bromo-
5-fluorotoluene, 3-bromo-4-fluorotoluene, 4-bromo-2-fluorotoluene, 4-bromo-3-fluorotoluene, tris (4-bromophenyl) amine, and 1,3,5-tribromo An aryl halide having two or more, preferably two to three halogen atoms such as benzene can also be used.

The aryl halide having two or more halogen atoms is preferably added after the production of the secondary amine.

In the present invention, the method of adding the aryl halide is not particularly limited. For example, before starting the reaction, two different aryl halides may be added simultaneously with the primary amine, and these may be reacted. After reacting the primary amine with one of the aryl halides, the resulting 2
The other aryl halide may be added to the primary amine and reacted. Since the tertiary arylamine can be produced more selectively, the latter method of sequentially adding different aryl halides is preferable.

In the present invention, the addition amount of the aryl halide is not particularly limited, but when two different aryl halides are added simultaneously with the primary amine,
0.5 mole times to 1 mole of 1 mole of primary amine.
A range of 0 mole times is appropriate, and in order to simplify the post-treatment such as economy and separation of unreacted aryl halide, it is preferably 0.7 to 5 mole times with respect to 1 mole of primary amine. It is. When different aryl halides are sequentially added, the first added aryl halide is 0.5 to 1 to 1 amino group of the primary amine.
It may be added to the reaction system in an amount of 5 moles, but from the viewpoint of improving the selectivity of the intended tertiary arylamine, more preferably 0.1 to 1 amino group of the primary amine. What is necessary is just to add to a reaction system in the range of 9 mol-1.1 times mol.

The aryl halide added after the production of the secondary amine may be added in an amount of 0.1 to 10 times the amount of one amino group of the primary amine used as a raw material. Since the operation of separating the aryl halide and the unreacted secondary amine becomes complicated, it is preferable to add 0.9 to 5 moles per one amino group of the primary amine.

The palladium compound used as a catalyst component in the present invention is not particularly limited as long as it is a palladium compound. Examples thereof include sodium hexachloropalladium (IV) tetrahydrate, potassium hexachloropalladium (IV), and the like. Tetravalent palladium compounds;
Palladium (II) chloride, palladium (II) bromide, palladium (II) acetate, palladium acetylacetonate (II), dichlorobis (benzonitrile) palladium (II), dichlorobis (acetonitrile) palladium (II), dichlorobis (triphenyl) Phosphine)
Divalent palladium compounds such as palladium (II), dichlorotetraamminepalladium (II), dichloro (cycloocta-1,5-diene) palladium (II), palladium trifluoroacetate (II); tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium chloroform complex (0), tetrakis (triphenylphosphine)
Zero-valent palladium compounds such as palladium (0) can be mentioned.

In the present invention, the use amount of the palladium compound is not particularly limited, but it is 0.00001 to 20.0 mol% in terms of palladium based on 1 mol of the primary amine. When palladium is within the above range, a tertiary arylamine can be synthesized with a high selectivity. However, since an expensive palladium compound is used, the tertiary arylamine is more preferably used.
0.001 to palladium conversion per mole of primary amine
5.0 mol%.

The trialkylphosphine used as a catalyst component in the present invention is not particularly limited. For example, triethylphosphine, tricyclohexylphosphine, triisopropylphosphine, tri-n
-Butylphosphine, triisobutylphosphine, tri-sec-butylphosphine, tri-tert-butylphosphine and the like. Tri-tert-butylphosphine is preferred because it has high reaction activity.

The amount of the trialkylphosphine used may be 0.01 to 10000 times the molar amount of the palladium compound. There is no change in the selectivity of the arylamine as long as the trialkylphosphine is in the above-mentioned usage amount, but since an expensive trialkylphosphine is used, it is more preferably 0.1 to 10 moles relative to the palladium compound. is there.

In the present invention, a palladium compound and a trialkylphosphine are indispensable as catalyst components, and both are combined and added as a catalyst to a reaction system. Regarding the method of addition, they may be added individually to the reaction system, or may be prepared in advance and added in the form of a complex.

The base that can be used in this reaction may be selected from inorganic bases such as sodium and potassium carbonates and alkali metal alkoxides, and organic bases such as tertiary amines. Is
For example, sodium methoxide, sodium ethoxide,
Potassium methoxide, potassium ethoxide, lithium-
alkali metal alkoxides such as tert-butoxide, sodium-tert-butoxide, potassium-tert-butoxide, etc., which can be added to the reaction field as they are, or can be added to alkali metals, alkali metal hydrides and alkali metal hydroxides. It may be prepared in situ from alcohol and provided to the reaction site.

The amount of the base to be used is not particularly limited, but it is preferable to use the base in an amount of 0.5 times or more the halogen atom of two different aryl halides to be added to the reaction. If the amount of the base is less than 0.5 mol, the reaction activity is decreased, and the yield of the arylamine is decreased, which is not preferable. Although the yield of the arylamine does not change even if the amount of the base is added in a large excess, the post-treatment operation after the completion of the reaction becomes complicated, and therefore, the amount of the base is more preferably 1.0 to 1.0.
It is not more than 5 times mol.

The reaction in the present invention is usually carried out in an inert solvent, and any inert solvent may be used as long as it does not significantly inhibit the reaction. For example, aromatic solvents such as benzene, toluene and xylene Hydrocarbon solvents; ether solvents such as diethyl ether, tetrahydrofuran and dioxane; acetonitrile, dimethylformamide,
Dimethyl sulfoxide, hexamethyl phosphotriamide and the like can be exemplified. More preferred are aromatic hydrocarbon solvents such as benzene, toluene and xylene.

The present invention is preferably carried out under normal pressure and in an atmosphere of an inert gas such as nitrogen or argon, but can be carried out even under pressurized conditions.

In the present invention, the reaction temperature may be selected from the range of 20 ° C. to 300 ° C., more preferably 50 ° C. to 200 ° C., and the reaction time may be selected from the range of several minutes to 72 hours.

[0029]

According to the present invention, a tertiary arylamine useful as an electronic material or the like can be converted into a primary amine and a secondary amine in the presence of a catalyst comprising a trialkylphosphine and a palladium compound and a base.
From different types of aryl halides, synthesis with high activity and high selectivity has become possible.

[0030]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited to these examples. The yields shown below were calculated based on the charged primary amine.

Preparation Example 1 Tris (dibenzylideneacetone) dipalladium (manufactured by Aldrich) and o-xylene (5 ml) were added to a 20 ml eggplant-shaped flask at room temperature in nitrogen. Under stirring, tri-te
rt-butylphosphine (Kanto Chemical) was added (tri-t
ert-butylphosphine / Pd molar ratio = 4/1), 8
The mixture was heated and stirred on a hot water bath at 0 ° C. for 10 minutes to obtain a catalyst.

Preparation Example 2 Tris (dibenzylideneacetone) was used as a palladium compound.
A catalyst was obtained by performing the same operation as in Example 1 except that palladium acetate was converted from the dipalladium chloroform complex.

Preparation Example 3 A known method (J. Organomet. Chem., 6
5,253 (1974)), a tris (dibenzylideneacetone) dipalladium chloroform complex was synthesized. 51.8 mg of the synthesized complex was prepared in the same manner as in Preparation Example 1 in nitrogen at room temperature.

Example 1 An o-tube containing a cooling tube, a thermometer and the catalyst prepared in Preparation Example 1
A dropping funnel containing about 5 ml of xylene solution (palladium atom / aryl halide = 0.25 mol%) was attached.
In a 00 ml four-necked flask, at room temperature, 4.14 g of 1-naphthyl bromide as an aryl halide, 2.22 g of p-fluoroaniline as a primary amine, and 4.61 g of sodium tert-butoxide as a base (hereinafter referred to as tert-butoxide).
(Abbreviated as BuONa) (t-BuONa / primary amine =
2.4 / 1) were each poured with 20 ml of o-xylene. After stirring and flowing nitrogen for about 20 minutes, the mixture was heated to 80 ° C.
The catalyst solution was added. Subsequently, the mixture was heated to 120 ° C. and stirred for 3 hours. After 3 hours, o- containing 3.74 g of p-bromoanisole as a different aryl halide
The xylene solution was added to the reactor under a nitrogen atmosphere. After the addition, heating and stirring was continued at 120 ° C. for 12 hours. After the completion of the reaction, GC analysis revealed that the peak of the aryl halide used had completely disappeared. After completion of the reaction, the mixture was allowed to cool to 80 ° C., and 80 ml of water was added. The reaction solution was transferred to a separating funnel, and the organic phase was separated. After o-xylene was removed from the organic phase under reduced pressure, column purification was performed to obtain 6.5 g of a pale yellow solid. The product was analyzed by GC-MASS. As a result, it was found that the target compound, N- (1-naphthyl) -N- (4-methoxyphenyl) -4-fluoroaniline had a molecular weight of 34.
Matched 3 The purity of the product was 98% by weight as a result of GC analysis, and the yield was 92.4% by mole.

Example 2 The primary amine was changed from p-fluoroaniline to 2.14 g of m-toluidine, the different aryl halide was changed from p-anisole to 3.50 g of p-fluorobromobenzene, and the reaction time was 12 hours. The operation was performed in the same manner as in Example 1 except that the time was changed to 8 hours. Column purification 6.2
3 g of a yellow solid were obtained. The product was analyzed by GC-MASS, and as a result, N- (1-naphthyl)
This corresponds to a molecular weight of 327 of -N- (3-methylphenyl) -4-fluoroaniline. The purity of the product was 96% by weight as a result of GC analysis, and the yield was 89.2 mol%.

Example 3 The procedure was performed except that the aryl halide was changed from 1-naphthyl bromide to 3.14 g of bromobenzene, and a different aryl halide was changed from p-fluorobromobenzene to 9.64 g of tris (4-bromophenyl) amine. The reaction operation was carried out in the same manner as in Example 2. The product was isolated by recrystallization in THF / methanol to give 14.3 g of a white solid. As a result of MASS analysis, the product was the target compound, 4, 4 ',
This corresponds to a molecular weight of 4 ″ -tris (3-methylphenylphenylamino) triphenylamine of 788. The yield was 90.5 mol%.

Example 4 The same operation as in Example 3 was carried out except that the aryl halide was changed from tris (4-bromophenyl) amine to 6.4 g of 4,4'-dibromobiphenyl. By recrystallization, 9.0 g of a white solid was obtained. As a result of MASS analysis, the product was N, N'-diphenyl-N, N'-
(3-methylphenyl)-[1,1′-biphenyl]-
This corresponds to a molecular weight of 516 of 4,4′-diamine. Also,
The yield was 87.0 mol%.

Example 5 The same operation as in Example 3 was carried out except that the aryl halide was changed from tris (4-bromophenyl) amine to 8,4 g of 4,4'-diiodobiphenyl. As a result of recrystallization, 9.0 g of a white solid was obtained. The product was N, N'-diphenyl-N, N'-
(3-methylphenyl)-[1,1′-biphenyl]-
This corresponds to a molecular weight of 516 of 4,4′-diamine. Also,
The yield was 86.8 mol%.

Example 6 The same operation as in Example 3 was carried out except that the aryl halide was changed from tris (4-bromophenyl) amine to 6.30 g of 1,3,5-tribromobenzene. As a result of recrystallization, 11.1 g of a white solid was obtained. The product was found to have a molecular weight of 621 of 1,3,5-tris (3-methylphenylphenylamino) benzene as a result of MASS analysis. The yield was 89.5 mol%.

Example 7 The same operation as in Example 3 was performed except that the aryl halide was changed from tris (4-bromophenyl) amine to 9,10-dibromoanthracene. 9.7 as a result of recrystallization
g of a white solid were obtained. As a result of MASS analysis, the product was found to have a molecular weight of 540 of 9,10-di (3-methylphenylphenylamino) anthracene, which was the intended product. The yield was 89.5 mol%.

Example 8 The primary amine was changed from p-fluoroaniline to N, N-diphenylphenylenediamine 5.20 g, and the aryl halide was obtained from 1-naphthyl bromide and p-bromoanisole with 3.14 g of bromobenzene and 1 The same operation as in Example 1 was performed, except that the amount was changed to 6.30 g of 3,5-tribromobenzene. As a result of recrystallization, a white solid 18.9 was obtained.
g was obtained. The product was found to have a molecular weight of 1,3,5-tris [N-phenyl-N- (diphenylaminophenyl) amino] benzene of 1080 by MASS analysis. The yield was 87.3 mol%.

Example 9 The primary amine was changed from p-fluoroaniline to 1.2 g of ethylenediamine, and the aryl halide was converted from 1-naphthyl bromide and p-bromoanisole to 3.14 g of bromobenzene and 3.42 g of o-bromotoluene. Operations were performed in the same manner as in Example 1, except that As a result of recrystallization, 7.1 g of a white solid was obtained. As a result of MASS analysis, the product was found to have a molecular weight of 392 of N, N′-diphenyl-N, N′-di (2-methylphenyl) ethylenediamine, which was the target substance. The yield was 89.9 mol%.

Example 10 o- containing a cooling tube, a thermometer and the catalyst prepared in Preparation Example 1
About 5 ml of xylene solution (palladium atom / primary amine =
200 m with a dropping funnel containing 0.05 mol%)
1 In a four-necked flask, add 1
-Naphthyl bromide 4.14 g, p- as primary amine
2.22 g of fluoroaniline and sodium ter
4.61 g of t-butoxide (hereinafter abbreviated as t-BuONa) (t-BuONa / primary amine = 2.4 / liter) was poured with 20 ml of o-xylene. After stirring and flowing nitrogen for about 20 minutes, the mixture was heated and the catalyst solution was added at 80 ° C. Subsequently, the mixture was heated to 120 ° C. and stirred for 3 hours. After 3 hours, p-bromoanisole 3.74
g-containing o-xylene solution was added to the reactor under a nitrogen atmosphere. After the addition, heating and stirring was continued at 120 ° C. for 20 hours. After the completion of the reaction, GC analysis revealed that the peak of the aryl halide used had completely disappeared. After completion of the reaction, the mixture was allowed to cool to 80 ° C., and 80 ml of water was added. The reaction solution was transferred to a separating funnel, and the organic phase was separated. After o-xylene was removed from the organic phase under reduced pressure, column purification was performed to obtain 5.9 g of a pale yellow solid. The purity of the product was determined by GC analysis as 98
% By weight, and the yield was 83.9 mol%.

Example 11 4.61 g of t-BuONa of Example 10 was replaced with t-BuOK
The same operation as in Example 10 was performed except that the amount was changed to 5.4 g. After column purification, 6.3 g of a pale yellow solid was obtained. As a result of GC analysis, the purity of the product was 98% by weight, and the yield was 8%.
It was 9.1 mol%.

Example 12 The same operation as in Example 1 was carried out except that the catalyst prepared in Preparation Example 2 was used (palladium atom / primary amine = 0.25). After column purification, 5.6 g of a pale yellow solid was obtained. G
As a result of C analysis, the purity of the product was 98% by weight, and the yield was 80.0 mol%.

Comparative Example 1 The same operation as in Example 1 was carried out except that the phosphine ligand was changed from tri-tert-butylphosphine to tri-o-tolylphosphine. As a result of GC analysis, the yield of the target product was 5.0 mol%. Comparative Example 2 Same as Example 2 except that the phosphine ligand was changed from tri-tert-butylphosphine to tri-o-tolylphosphine. The operation was performed. As a result of GC analysis, the yield of the target product was 3.2 mol%.

Comparative Example 3 A reaction was carried out in the same manner as in Example 2 except that the phosphine ligand was changed from tri-tert-butylphosphine to triphenylphosphine.

After the completion of the reaction, the product was subjected to a GC analysis to find that the yield of the desired product was 7.9%.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 211/58 C07C 211/58 211/59 211/59 211/61 211/61 213/02 213/02 217/84 217/84 // C07B 61/00 300 C07B 61/00 300

Claims (7)

[Claims] 1. In the presence of a catalyst comprising a trialkylphosphine and a palladium compound and a base, a compound represented by the following general formula (1): R (NH ₂ ) _n (1) wherein R is an alkyl group or a substituted or unsubstituted And a primary amine represented by the following general formula (2): Ar1 (X1) _m1 (2) (wherein, Ar1 represents a substituted or unsubstituted aryl group) Represent
X1 represents F, Cl, Br or I, and m1 represents an integer of 1 to 3. ) And the following general formula (3): Ar2 (X2) _m2 (3) (wherein, Ar2 represents a substituted or unsubstituted aryl group different from Ar1, X2 represents F, Cl, Br or I,
m2 represents an integer of 1 to 3. 3) reacting with two different aryl halides represented by
Production method of secondary arylamines. 2. The method according to claim 1, wherein the primary amine represented by the general formula (1) and the aryl halide represented by the general formulas (2) and (3) are simultaneously reacted. A method for producing tertiary arylamines, characterized by the following. 3. The method according to claim 1, wherein the primary amine represented by the general formula (1) is reacted with the aryl halide represented by the general formula (2) to obtain a secondary amine. A method for producing a tertiary arylamine, comprising reacting a tertiary amine with an aryl halide represented by the general formula (3). 4. The method according to claim 1, wherein m1 in the general formula (2) is 1, and m2 in the general formula (3) is 1. the following general formula (4) R [n (Ar1 ) (Ar2)] n (4) ( wherein the, R represents an alkyl group or a substituted or unsubstituted aryl group, Ar @ 1 is a substituted or unsubstituted aryl group And Ar2 represents a substituted or unsubstituted aryl different from Ar1, and n represents 1 or 2.) A method for producing a tertiary arylamine represented by the formula: 5. The method according to claim 1, wherein n in the general formula (1) is 1,
Wherein m1 in the general formula (2) is 1. Ar2 [N (Ar1) (R)] _m2 (5) wherein R is an alkyl group or a substituted or unsubstituted Represents an aryl group, Ar1 represents a substituted or unsubstituted aryl group, Ar2 represents a substituted or unsubstituted aryl group different from Ar1, and m2 represents an integer of 1 to 3.) Method for producing amines. 6. The method for producing a tertiary arylamine having three different substituents according to claim 1, wherein R, Ar1 and Ar2 are different from each other. Method 7. The method of claim 1, wherein the trialkylphosphine is tri-te
The method for producing a tertiary arylamine according to any one of claims 1 to 6, wherein the method is rt-butylphosphine.