JP2010120875A - Method for producing arylamine compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an arylamine compound in good yield. <P>SOLUTION: The method for producing the arylamine compound uses a complex of bidentate phosphines and a nickel-based compound as a catalyst in the amination reaction of an aromatic halide by an amine compound in the presence of a base. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to an element for electronic materials such as an organic electroluminescent element and an electrophotographic photosensitive member, and a method for producing an arylamine compound useful as an intermediate thereof in a high yield.

As a method for synthesizing an arylamine compound, Ullmann-Goldberg reaction in which an aromatic amine compound and an aromatic halide are reacted in the presence of a base and a copper catalyst is known. (For example, see Non-Patent Document 1)
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, it is characterized by requiring a high temperature, and the reaction product is remarkably colored, and a large amount of by-products are produced, so that the yield of arylamines is generally low.

In addition, a method using a palladium compound as a catalyst and trialkylphosphine as a ligand has been reported. (For example, see Patent Document 1)
Although this condition has an advantage that inexpensive aryl chloride can be used as a raw material, in order to maintain the activity of the palladium-phosphine complex, it is necessary to carry out the reaction under a strict inert gas atmosphere. In addition, since the trialkylphosphine itself as a ligand is unstable in the air, it is necessary to carry out storage and weighing in an inert gas atmosphere, which is not practical. In addition, using an expensive palladium compound is not suitable for practical use.

Further, a nickel compound is used as a catalyst, and bis (triphenylphosphino) ferrocene (see Non-Patent Document 2) and 1,2-bis (dicyclohexylphosphino) ethane or 1,3-bis (dicyclohexylphosphino) propane are used. A method has been reported. (For example, see Patent Document 2)
However, these production methods are not necessarily satisfactory in reaction yield, and improvements have been demanded.

JP 10-139742 A JP 2003-201268 A Tetrahedron, 40, 1433 (1984) J. et al. Am. Chem. Soc. 119, 6054 (1997)

The present invention provides a method for producing an arylamine compound that can be reacted under practical conditions that can be accommodated industrially and that can be easily purified after the reaction.

As a result of intensive studies to solve these problems, the present inventor, in the presence of a base, in the amination reaction of an aromatic halide with an amine compound, a bidentate phosphine having a specific structure and a nickel-based compound By using the complex as a catalyst, a production method with high production efficiency and industrial response was completed.

That is, the present invention has the following configuration.

[1] Amination of an aromatic halide represented by the following general formula (2) using an amine compound represented by the following general formula (1) in the presence of a bidentate phosphine, a nickel-based compound and a base A process for producing an arylamine compound represented by the following general formula (3), wherein the reaction is performed.

(In the formula, A is methyl group, ethyl group, n-propyl group, n-butyl group, cyclopentyl group, cyclohexyl group, methoxymethyl group, 2-methoxyethyl group, phenyl group, benzyl group, or methyl group, ethyl group. Represents a phenyl group having a propyl group, a tert-butyl group or a methoxy group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group or a fluorenyl group, and B represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, n -Represents a butyl group, a phenyl group or a benzyl group.)

(In the formula, C represents a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group or a pyrenyl group, and these groups further have an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenoxy group. X represents fluorine, chlorine, bromine or iodine.)

(In the formula, A, B and C are the same as defined in the general formulas (1) and (2).)

[2] The method for producing an arylamine compound according to [1], wherein the bidentate phosphine and the nickel-based compound act as a catalyst in the amination reaction.

[3] The arylamine compound according to [1] or [2], wherein the bidentate phosphine and the nickel compound form a complex in the amination reaction and act as a catalyst. Production method.

[4] The arylamine compound according to any one of [1] to [3], wherein the bidentate phosphine is a bidentate phosphine having a coordination angle of 95 ° to 115 °. Production method.

[5] The bidentate phosphines are 1,4-bis (diphenylphosphino) butane, 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene, bis [2- (diphenylphosphino) phenyl. ] Ether, (4R, 5R)-(−)-4,5-bis (diphenylphosphinomethyl) -2,2-dimethyl-1,3-dioxolane, (4S, 5S)-(+)-4,5 -One or more selected from bis (diphenylphosphinomethyl) -2,2-dimethyl-1,3-dioxolane and 1,4-bis (dicyclohexylphosphino) butane, The method for producing an arylamine compound according to any one of [1] to [4].

[6] The nickel compound is nickel chloride (II), nickel bromide (II), nickel iodide (II), nickel nitrate (II), nickel acetate (II), nickel acetylacetonate (II), stearin Nickel (II) acid, nickel (II) 2-ethylhexanoate, nickel (II) citrate, nickel (II) naphthenate, bis (η-cyclopentadienyl) nickel (II), bis (1,5- The arylamine compound according to any one of [1] to [5] above, which is one or more selected from cyclooctadiene) nickel (0) and nickelcarbonyl (0) Production method.

[7] The method for producing an arylamine compound according to [6], wherein a reducing agent is further added during the amination reaction when the nickel valence of the nickel compound is divalent.

[8] Any one of [1] to [7] above, wherein X of the aromatic halide represented by the general formula (2) is one selected from chlorine, bromine and iodine The manufacturing method of the arylamine compound as described in above.

By using the production method of the present invention, it is possible to produce an industrially useful arylamine compound with good yield and cost.

Hereinafter, the present invention will be described in detail.
The aromatic halide used in the present invention is not particularly limited as long as at least one halogen atom is substituted on the aromatic hydrocarbon ring, and is not particularly limited, but halogenated benzene, halogenated naphthalene, halogenated anthracene. , Halogenated phenanthrene, halogenated pyrene and the like. In the present invention, the halogen atom of the aromatic halide is not particularly limited, but chlorine, bromine or iodine is preferable. Furthermore, in the present invention, the aromatic halide used may have a substituent on the aromatic ring in addition to the halogen atom. Examples of the substituent include an alkyl group, an alkoxy group, and a phenoxy group.

Examples of the amine compound used in the present invention include primary amines and secondary amines. Specific examples include methylamine, cyclohexylamine, benzylamine, aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, m-anisidine, p-anisidine, 1-naphthylamine, 2-naphthylamine, 4-methoxy. Examples include 2-methylaniline, 4-tert-butylaniline, N-methylaniline, N-ethylaniline, dibenzylamine, morpholine, pyrrolidine, and piperidine.

The bidentate phosphines used in the present invention are preferably bidentate phosphines having a coordination angle of 95 ° to 115 °. The coordination angle here refers to a bit angle in complex chemistry. (Ryoji Noyori et al., Graduate Course Organic Chemistry I, Tokyo Chemical Co., Ltd., 1999, p404-405)

The bidentate phosphine forms a complex with a nickel-based compound described later in the method for producing an arylamine compound of the present invention, and the aromatic halogen compound and amine compound as raw materials are coordinated and eliminated from the nickel atom of the complex. It is thought to function as a catalyst that promotes the amination reaction.

At this time, in a complex using bidentate phosphines having a coordination angle of more than 115 °, each phosphorus atom and a group (atomic group) bonded to the phosphorus atom are bulky around the nickel atom due to the wide angle of the angle. As a result, it is considered that the aromatic halogen compound and amine compound, which are raw materials, are physically inhibited from coordinating to the nickel atom of the complex, and the reaction is unlikely to proceed.
In addition, in the complex using bidentate phosphines whose coordination angle is less than 95 °, the above physical inhibition is unlikely to occur, but conversely, the coordination of the starting material aromatic halogen compound and amine compound to the nickel atom It is considered that the stability becomes so high that these raw materials are not easily desorbed from the nickel atoms, and the amination reaction occurring simultaneously with the desorption is difficult to proceed.

Specific examples of the bidentate phosphine having a coordination angle of 95 ° to 115 ° include 1,4-bis (diphenylphosphino) butane and 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene. Bis [2- (diphenylphosphino) phenyl] ether, (4R, 5R)-(−)-4,5-bis (diphenylphosphinomethyl) -2,2-dimethyl-1,3-dioxolane, (4S , 5S)-(+)-4,5-bis (diphenylphosphinomethyl) -2,2-dimethyl-1,3-dioxolane, 1,4-bis (dicyclohexylphosphino) butane and the like.

In this invention, the usage-amount of bidentate phosphine is 0.1-4 equivalent normally with respect to a nickel atom, Preferably it is 0.5-2.5 equivalent.

Examples of nickel compounds include nickel chloride (II), nickel bromide (II), nickel iodide (II), nickel nitrate (II), nickel acetate (II), nickel acetylacetonate (II), nickel stearate. Bivalent nickel compounds such as (II), nickel 2-ethylhexanoate (II), nickel citrate (II), nickel naphthenate (II), bis (η-cyclopentadienyl) nickel (II), bis Zero-valent nickel compounds such as (1,5-cyclooctadiene) nickel (0) and nickel carbonyl (0) can be mentioned. The form of the nickel compound may be an anhydrous body or a hydrated body.

In the case where a nickel valence is used, it is preferable to use a reducing agent for the reaction. The reducing agent is not particularly limited, but preferably sodium hydride, lithium aluminum hydride, sodium borohydride, diisobutylaluminum hydride, alkyl Grignard reagent, alkyl lithium, polymethylhydrosilane, phenylsilane, tripentyloxysilane, hexamethyltrimethyl. Examples thereof include siloxane, octamethyltetrasiloxane, polymethylhydrosiloxane, and metallic zinc.

In this case, in preparing the catalyst, a divalent nickel-based compound, a bidentate phosphine, a reducing agent, and an appropriate solvent as required are used, but the order of addition is not particularly limited. The nickel-based compound may be dissolved in the reaction mixture or suspended.

The nickel-based compound may be used as it is, or may be used by being supported on a substance that does not dissolve in the solvent used in such a reaction, such as carbon, silica, or alumina. In this reaction, the amount of nickel compound used is usually 0.0001 to 1 equivalent, preferably 0.001 to 0.1 equivalent, relative to the aromatic halide.

In the present invention, the base used in the reaction is not particularly limited as long as it is selected from inorganic bases or organic bases, but preferably sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, lithium. Alkali metal alkoxides such as -tert-butoxide, sodium-tert-butoxide, potassium-tert-butoxide and the like can be mentioned. The base may be added directly to the reaction solution, but an in-situ preparation prepared from an alkali metal, alkali metal hydride, alkali metal hydroxide or the like may be added to the reaction solution.

In the present invention, the amount of the base used in the reaction is preferably 0.5 equivalents or more, particularly preferably in the range of 1 to 3 equivalents, relative to the hydrogen halide generated in the reaction. If the amount of the base used in the reaction is less than 0.5 equivalent, the yield of the resulting arylamines may be lowered, which is not preferable. In addition, when the base used in the reaction is added in a large excess, the yield of the resulting arylamines is not affected, but the post-treatment operation after completion of the reaction becomes complicated, which is not preferable.

The solvent used in the present invention is not particularly limited as long as it is an inert solvent for the reaction, but is an aromatic hydrocarbon solvent such as toluene or xylene, tetrahydrofuran, 1,2-dimethoxyethane, cyclopentylmethyl. And ether solvents such as ether, aliphatic hydrocarbon solvents such as heptane and octane, and aprotic polar solvents such as acetonitrile, dimethylformamide and dimethyl sulfoxide. The amine compound, aromatic halide, bidentate phosphine, nickel-based compound, and solvent that dissolves the base are preferable.

In the present invention, the reaction can be carried out under normal pressure or under pressure, and can be carried out under normal air conditions. However, due to the flammability problem of the organic solvent used, it can be carried out under an inert gas atmosphere such as nitrogen or argon. It is preferable to do so.

In the present invention, the reaction temperature is not particularly limited as long as it is in the range of 20 ° C. to 300 ° C., but a temperature at which the reaction can proceed in a homogeneous system is preferred. A preferred temperature range is 50 ° C to 200 ° C, and a particularly preferred temperature range is 80 ° C to 150 ° C.

In the present invention, the reaction time varies depending on the amine compound, aromatic halide, bidentate phosphine, nickel compound, base type, amount and reaction temperature used in the reaction, but is usually in the range of several minutes to 72 hours. Is preferred.

In the present invention, the treatment after completion of the reaction is not particularly limited, but may be carried out by conventional methods such as solvent extraction, filtration, and washing, and the target arylamine compound can be obtained simply and efficiently.

EXAMPLES Hereinafter, although an Example demonstrates this invention, these do not limit this invention at all. In the examples, “parts” are all “parts by mass”, and the conversion is the sum of the area values of the gas chromatography of the amination target and unreacted amine compound by analyzing the reaction mixture by gas chromatography. Represents a value obtained by converting a product into a percentage.
In all examples and comparative examples, the conversion rate was measured by the following apparatus and conditions. Gas chromatography; GC-14A (manufactured by Shimadzu Corporation)
Column: TC-1 (inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm)
Conditions: After flowing at 70 ° C. for 5 minutes, the temperature is raised at a rate of 15 ° C./min, and flowing at 250 ° C. for 55 minutes.

To a 50 ml three-necked flask equipped with a stirrer, a condenser, a thermometer and a gas introduction tube, 1.38 g (1 mmol) of a 25 wt% toluene solution of nickel 2-ethylhexanoate, 1,4-bis (diphenylphosphino) ) 853 mg (2 mmol) of butane, 2.0 ml (2 mmol) of 1M toluene solution of diisobutylaluminum hydride and 25 ml of toluene were added, and the temperature of the oil bath was adjusted to 60 to 65 ° C. under an argon stream, followed by stirring for 90 minutes. After cooling the reaction solution to room temperature, 5.0 ml (49 mmol) of chlorobenzene, 1.86 g (20 mmol) of aniline and 2.5 g (26 mmol) of sodium tert-butoxide were added. The temperature of the oil bath was 130 ° C., and the reaction was stirred for 7 hours under reflux conditions. Since the conversion rate of the target product diphenylamine was 99.4%, the reaction solution was cooled to room temperature, and then 50 ml of toluene was added. The toluene layer was washed twice with water. After dehydrating and drying with 5 g of anhydrous sodium sulfate, the solvent was distilled off to obtain 3.4 g of a residue. The residue was recrystallized from ethanol to obtain 2.6 g (yield 77%) of diphenylamine.

In a 50 ml three-necked flask equipped with a stirrer, a condenser, a thermometer and a gas introduction tube, 110 mg (0.4 mmol) of bis (1,5-cyclooctadiene) nickel, bis [2- (diphenylphosphino) Phenyl] ether 431 mg (0.8 mmol), sodium tert-butoxide 865 mg (9 mmol), chlorobenzene 788 mg (7 mmol), aniline 466 mg (5 mmol), toluene 15 ml were added at room temperature under an argon stream, The temperature was controlled at 130 ° C. and reacted for 7 hours under reflux conditions. The conversion rate of the target product diphenylamine was 100%.

In a 50 ml three-necked flask equipped with a stirrer, a condenser, a thermometer and a gas inlet tube, 110 mg (0.4 mmol) of bis (1,5-cyclooctadiene) nickel, 4,5-bis (diphenylphosphino) ) -9,9-dimethylxanthene 463 mg (0.8 mmol), sodium tert-butoxide 865 mg (9 mmol), chlorobenzene 788 mg (7 mmol), aniline 466 mg (5 mmol), toluene 15 ml at room temperature under an argon stream. In addition, the temperature of the oil bath was controlled at 130 ° C., and the mixture was reacted for 7 hours under reflux conditions. The conversion rate of the target product diphenylamine was 100%.

To a 100 ml three-necked flask equipped with a stirrer, a condenser, a thermometer, and a gas introduction tube was added 4.42 g (3.2 mmol) of a 25 wt% toluene solution of nickel 2-ethylhexanoate and 1,4-bis (diphenyl). 2.73 g (6.4 mmol) of phosphino) butane, 6.4 ml (6.4 mmol) of 1M toluene solution of diisobutylaluminum hydride and 50 ml of toluene were added, and the temperature of the oil bath was adjusted to 60 to 65 ° C. under an argon stream. Stir for minutes. After cooling the reaction solution to room temperature, 9.84 g (77.7 mmol) of p-chlorotoluene, 4.28 g (40 mmol) of p-toluidine, and 5.0 g (52 mmol) of sodium-tert-butoxide were added. The temperature of the oil bath was 130 ° C., and the reaction was stirred for 24 hours under reflux conditions. The conversion rate of the desired product 4,4′-dimethyldiphenylamine was 97.4%.

To a 100 ml three-necked flask equipped with a stirrer, a condenser, a thermometer, and a gas introduction tube, 2.76 g (2 mmol) of a 25 wt% toluene solution of nickel 2-ethylhexanoate, (4S, 5S)-(+) -4,5-bis (diphenylphosphinomethyl) -2,2-dimethyl-1,3-dioxolane 1.99 g (4 mmol), polymethylhydrosiloxane (FW1900) 1.17 g (0.6 mmol), toluene 50 ml was added, the temperature of the oil bath was 130 ° C. under an argon stream, and the mixture was stirred for 90 minutes. After cooling the reaction solution to room temperature, 9.79 g (48 mmol) of iodobenzene, 3.73 g (40 mmol) of aniline, and 5.0 g (52 mmol) of sodium tert-butoxide were added. The temperature of the oil bath was 130 ° C., and the reaction was stirred for 24 hours under reflux conditions. The conversion rate of the desired product diphenylamine was 95.6%.

To a 100 ml four-necked flask equipped with a stirrer, a condenser, a thermometer, and a gas introduction tube, 2.21 g (1.6 mmol) of a 25 wt% toluene solution of nickel 2-ethylhexanoate and 1,4-bis (diphenyl) 1.36 mg (3.2 mmol) of phosphino) butane, polymethylhydrosiloxane {molecular weight 1900} (0.5 mmol) and 50 ml of toluene were added, and the temperature of the oil bath was adjusted to 130 ° C. under an argon stream. Stir for 90 minutes. After cooling the reaction solution to room temperature, 10 ml (98 mmol) of chlorobenzene, 3.73 g (40 mmol) of aniline, and 5.0 g (52 mmol) of sodium-tert-butoxide were added. The temperature of the oil bath was 130 ° C., and the reaction was stirred for 7 hours under reflux conditions. The conversion rate from the desired product diphenylamine was 97.3%.

[Comparative Example 1]
In a 50 ml three-necked flask equipped with a stirrer, a condenser, a thermometer and a gas introduction tube, 140 mg (0.5 mmol) of bis (1,5-cyclooctadiene) nickel, 1,3-bis (dicyclohexylphosphino) ) Propane 440 mg (1 mmol), sodium-tert-butoxide 1.25 g (13 mmol), chlorobenzene 1.44 g (12.8 mmol), aniline 466 mg (5 mmol), toluene 15 ml were added at room temperature under a stream of argon, The temperature of the oil bath was controlled at 130 ° C., and the reaction was carried out for 7 hours under reflux conditions. The conversion rate of the desired product diphenylamine was 55.3%.

By using the production method of the present invention, an industrially useful arylamine compound can be produced with good yield and cost.

Claims (8)

Amination reaction of an aromatic halide represented by the following general formula (2) using an amine compound represented by the following general formula (1) in the presence of a bidentate phosphine, a nickel-based compound and a base; A process for producing an arylamine compound represented by the following general formula (3):

(In the formula, A is methyl group, ethyl group, n-propyl group, n-butyl group, cyclopentyl group, cyclohexyl group, methoxymethyl group, 2-methoxyethyl group, phenyl group, benzyl group, or methyl group, ethyl group. Represents a phenyl group having a propyl group, a tert-butyl group or a methoxy group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group or a fluorenyl group, and B represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, n -Represents a butyl group, a phenyl group or a benzyl group.)

(In the formula, C represents a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group or a pyrenyl group, and these groups further have an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenoxy group. X represents fluorine, chlorine, bromine or iodine.)

(In the formula, A, B and C are the same as defined in the general formulas (1) and (2).) 2. The method for producing an arylamine compound according to claim 1, wherein the bidentate phosphine and the nickel-based compound act as a catalyst in the amination reaction. 3. The method for producing an arylamine compound according to claim 1, wherein the bidentate phosphine and the nickel-based compound form a complex in the amination reaction and act as a catalyst. The method for producing an arylamine compound according to any one of claims 1 to 3, wherein the bidentate phosphine is a bidentate phosphine having a coordination angle of 95 ° to 115 °. The bidentate phosphines are 1,4-bis (diphenylphosphino) butane, 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene, bis [2- (diphenylphosphino) phenyl] ether; (4R, 5R)-(−)-4,5-bis (diphenylphosphinomethyl) -2,2-dimethyl-1,3-dioxolane, (4S, 5S)-(+)-4,5-bis ( 2. One or more selected from diphenylphosphinomethyl) -2,2-dimethyl-1,3-dioxolane and 1,4-bis (dicyclohexylphosphino) butane, The manufacturing method of the arylamine compound in any one of -4. The nickel compound is nickel chloride (II), nickel bromide (II), nickel iodide (II), nickel nitrate (II), nickel acetate (II), nickel acetylacetonate (II), nickel stearate ( II), nickel 2-ethylhexanoate (II), nickel citrate (II), nickel naphthenate (II), bis (η-cyclopentadienyl) nickel (II), bis (1,5-cyclooctadiene) The method for producing an arylamine compound according to any one of claims 1 to 5, wherein the arylamine compound is one or more selected from nickel (0) and nickel carbonyl (0). The method for producing an arylamine compound according to claim 6, wherein a reducing agent is further added in the amination reaction when the nickel valence of the nickel compound is divalent. The arylamine compound according to claim 1, wherein X of the aromatic halide represented by the general formula (2) is one selected from chlorine, bromine, and iodine. Manufacturing method.