KR20190103173A - Process for producing aromatic diamine compound precursor - Google Patents

Abstract

[Ar 은 아릴렌기 또는 헤테로아릴렌기 ; X 는 할로겐 ; R 은 C₁ ∼ C₆ 알킬]Provided are a method for producing a dinitro compound, which is a precursor of a diamine compound as a raw material for producing polyamic acid and / or polyimide, with little by-products and with high purity and high yield.
N- (nitrophenyl) represented by Formula (3) by reacting the aromatic dihalogen compound represented by Formula (1) and the N-alkylnitroaniline derivative represented by Formula (2) in presence of a metal complex solvent and a base. Method for producing an aromatic amine compound.

[Ar is an arylene group or a hetero arylene group; X is halogen; R is C ₁ -C ₆ alkyl]

Description

Process for producing aromatic diamine compound precursor

The present invention relates to a novel method for producing a dinitro compound, which is a precursor of a specific diamine compound, which is a raw material for producing a polyimide for use in a liquid crystal aligning agent or the like, with few by-products and having high purity and high yield.

Currently, the polyimide film is used for the liquid crystal aligning film used for a liquid crystal display element in many cases. The liquid crystal aligning film of this polyimide film is manufactured by the method of apply | coating the solution of the polyamic acid which is a precursor of a polyimide, or the solution of the solvent-soluble polyimide to a board | substrate, and carrying out the orientation processing of a film obtained by baking, such as a rubbing process. See Documents 1 and 2). Generally this polyamic acid and solvent-soluble polyimide are manufactured by the polycondensation reaction of tetracarboxylic-acid derivatives, such as tetracarboxylic dianhydride, and a diamine compound.

Since diamine compounds which are raw materials, such as a polyamic acid and a polyimide, are important because they affect the characteristic of the liquid crystal aligning film obtained from this, and also the characteristic of a liquid crystal display element, various diamine compounds are conventionally used and are proposed.

Japanese Laid-Open Patent Publication No. 7-120769 Japanese Patent Laid-Open No. 9-146100

As a diamine compound excellent in various characteristics, what has a structure which the aromatic ring couple | bonded is proposed. Such a diamine compound is generally produced by reduction of a dinitro compound as a precursor, but some types of these dinitro compounds require a multi-step process, low yield, or There is a problem that the manufacturing cost is high. In addition, the coupling reaction between the aromatic dihalogen compound and the N-alkylnitroaniline derivative was low in reactivity, and thus, it was difficult to apply to the production of the dinitro compound.

The present invention solves the above problems in the case of producing a dinitro compound using a coupling reaction between an aromatic dihalogen compound and an N-alkylnitroaniline derivative, and has a high reaction rate, few by-products, and high purity. Moreover, it aims at providing the method of obtaining a target object in high yield.

As a result of earnestly researching in order to achieve the above object, the present invention has reached a novel production method having the following points.

1. Represented by the following formula (3) by reacting the aromatic dihalogen compound represented by the following formula (1) and the N-alkylnitroaniline derivative represented by the following formula (2) in the presence of a metal complex catalyst and a base: Process for producing N- (nitrophenyl) aromatic amine compound.

[Formula 1]

[Wherein Ar represents an arylene group or a heteroarylene group, and X represents a halogen.]

[Formula 2]

[Wherein, R represents C ₁ to C ₆ alkyl.]

[Formula 3]

[Wherein Ar, X, and R are the same as defined above.]

2. The manufacturing method of said 1 whose metal complex catalyst is a palladium complex or a copper complex.

3. Manufacturing method of said 1 or 2 whose base is hydroxide, carbonate, hydrogencarbonate, phosphate, hydrogen phosphate, or carboxylate of alkali metal or alkaline earth metal.

4. The manufacturing method in any one of said 1-3 made to react in presence of a solvent.

5. The manufacturing method in any one of said 1-4 whose said aromatic dihalogen compound is a compound represented by either of following formula (X1)-(X6).

6. The manufacturing method in any one of said 1-4 whose aromatic dihalogen compound is a compound represented by either of following formula (X1)-(X3).

7. The manufacturing method in any one of said 1-6 whose X in Formula (1) or Formula (X1)-(X6) is Cl or Br.

8. The manufacturing method in any one of said 1-7 whose N-alkyl nitroaniline derivative is N-methyl-p-nitroaniline.

9. Said 4-8 whose solvent is toluene, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylformamide, dimethylacetamide, or N-methyl- 2-pyrrolidone. The manufacturing method in any one of Claims.

10. The manufacturing method in any one of said 1-9 whose base is cesium carbonate or tripotassium phosphate.

11. The palladium in the palladium _{complex, Pd 2 (dba) 3 (} dba) n (dba is dibenzylideneacetone represents dipalladium, n represents an integer of 0 to 2) which is indicated, any of the above 2-10 as The manufacturing method of one term | claim.

12. The ligands in the palladium complex or the copper complex are 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl and 2-dicyclohexylphosphino-2 ', 6'- The manufacturing method in any one of said 2-11 which is at least 1 sort (s) chosen from the group which consists of diisopropoxy biphenyl.

13. Of N- (aminophenyl) aromatic amine compound by reducing the nitro group which the N- (nitrophenyl) aromatic amine compound represented by Formula (3) obtained by the manufacturing method in any one of said 1-12 has. Manufacturing method.

ADVANTAGE OF THE INVENTION According to this invention, the dinitro compound which is a precursor of a diamine compound can be manufactured in high yield by the coupling reaction of the generally low reactivity aromatic dihalogen compound and N-alkylnitroaniline derivative. Moreover, since the dinitro compound obtained by this invention can reduce the usage-amount of a metal catalyst, the content of the residual metal which becomes a problem in the electronic material field can be reduced to the minimum, and reaction which is difficult to separate from a target object There is little content of the monocoupling body which is an intermediate, and complicated purification, such as column treatment, is not needed.

The dinitro compound obtained by this invention is used as a precursor of the diamine compound which is a raw material of polyamic acid and / or polyimide, etc.

EMBODIMENT OF THE INVENTION Below, this invention is demonstrated in detail.

In the present specification, "n" represents a normal, "s" represents a secondary, "t" represents a tertiary, "o" represents an ortho, "m" represents a meta, and "p" represents a para. .

Reaction in the manufacturing method of this invention is shown by the following scheme (A). That is, N- (nitrophenyl) aromatic represented by Formula (3) by making the aromatic dihalogen compound represented by Formula (1) and N-alkylnitroaniline represented by Formula (2) react in presence of a metal complex catalyst and a base. It is to prepare an amine compound.

[Formula 4]

In said formula (1), Ar and X are as having described in said 1 above.

The arylene group represented by Ar is a divalent group produced by removing one hydrogen atom each of two ring carbon atoms from the arene. Moreover, a heteroarylene group is a bivalent group produced | generated by removing each hydrogen atom of two ring carbon atoms from heteroarene.

Moreover, Cl, Br or I is preferable, and, as for the halogen represented by X, Cl or Br is more preferable.

As an aromatic dihalogen compound represented by said Formula (1), what is represented by any of the following (X1)-(X6) is preferable, and what is represented by either of (X1)-(X3) is more preferable.

[Formula 5]

In the formulas (3) and (X1) to (X6), X represents a halogen. As the halogen, Cl, Br or I is preferable, and Cl or Br is more preferable.

The formula (3) R is C ₁ ~ C ₆ alkyl represented by in the carbon atom number is 1 atom hydrogen lost from 1-6 aliphatic hydrocarbon group of linear or branched consisting of monovalent produced. R is preferably C ₁ to C ₃ alkyl, and more preferably methyl or ethyl.

Examples of R include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, 1,1-dimethyl Propyl, n-hexyl, or isohexyl is preferred, and methyl is more preferred.

Any of the aromatic dihalogen compounds used herein are known compounds and can be synthesized according to the known methods described in the literature. For example, 2,5-bis (4-bromophenyl) -1-methyl-1H-pyrrole is described in J. Med. Chem. The compound can be obtained by reacting according to the method described in 1977, Volume 20, pages 531-536.

The position to the amino group of the nitro group in N-alkylnitroaniline may be any of o position, m position, or p position, but the p position is more preferable.

As for the usage-amount of N-alkyl nitroaniline at the time of making an aromatic dihalogen compound and N-alkyl nitroaniline react, 1.0-1.5 mol is preferable and 1.05-1.2 mol is especially preferable per mol of halogen atoms of an aromatic dihalogen compound.

In the present invention, the reaction of the scheme (A) is carried out in the presence of a metal complex catalyst and a base. The metal complex catalyst is formed using a metal complex and a ligand.

As a metal complex catalyst, although the thing of various structures can be used, the palladium complex or copper complex of a low atom is especially preferable. In particular, as the palladium complex, a zero-valent metal complex catalyst having tertiary phosphine or tertiary phosphite as a ligand is preferable.

In the present invention, it is also possible to use a precursor which is easily converted into a zero-valent metal complex catalyst in the reaction system. Furthermore, in the reaction system, a metal complex which does not contain tertiary phosphine or tertiary phosphite as a ligand and tertiary phosphine or tertiary phosphite which is a ligand are mixed, and tertiary phosphine or tertiary phosphite is mixed. Low atoms as ligands can also be used to produce metal complex catalysts.

As tertiary phosphine or tertiary phosphite which is a ligand, for example, triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2-bis (diphenyl Phosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1'-bis (diphenylphosphino) ferrocene, trimethylphosphite, tri Ethylphosphite, triphenylphosphite, 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl, 2-di-t-butylphosphino-2 ', 4', 6 ' -Triisopropylbiphenyl, 2-dicyclohexylphosphino-2 ', 6'-diisopropoxybiphenyl, 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl, (2- Biphenyl) di-t-butylphosphine, (2-biphenyl) dicyclohexylphosphine, 2-dicyclohexylphosphino-2'-methylbiphenyl, 2-dicyclohexylphosphino-2 '-( N, N-dimethylamino) biphenyl, 2- (dicyclohexylphosphino) -3,6-dimethoxy-2 ', 4', 6'-triisopropyl- 1,1'-biphenyl, 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene, (oxydi-2,1-phenylene) bis (diphenylphosphine), etc. are mentioned. have. Metal complex catalysts containing two or more kinds of these ligands in admixture are also preferably used.

Among them, preferred ligands include 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane and 2-dish Clohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl, 2-di-t-butylphosphino-2 ', 4', 6'-triisopropylbiphenyl, 2-dicyclohexyl Phosphino-2 ', 6'-diisopropoxybiphenyl, 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl, (2-biphenyl) di-t-butylphosphine, ( 2-biphenyl) dicyclohexyl phosphine and 2-dicyclohexyl phosphino-2'-methylbiphenyl are mentioned, A more preferable ligand is 2-dicyclohexyl phosphino-2 ', 4', 6'-triisopropylbiphenyl, 2-dicyclohexyl phosphino-2 ', 6'- diisopropoxy biphenyl, 2-dicyclohexyl phosphino-2', 6'- dimethoxy biphenyl Can be.

As a metal complex catalyst, it is also preferable to use combining the palladium complex which does not contain a tertiary phosphine or tertiary phosphite, and the metal complex containing a tertiary phosphine or tertiary phosphite. In this case, you may further combine the said ligand. Examples of palladium complexes containing no tertiary phosphine or tertiary phosphite include bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, bis (acetonitrile) dichloropalladium and bis (benzonitrile) Dichloro palladium, palladium acetate, palladium chloride, palladium-activated carbon, and the like. Examples of palladium complexes containing tertiary phosphine or tertiary phosphite as ligands include (ethylene) bis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) dichloropalladium Etc. can be mentioned.

Preferred metal complex catalysts in the present invention include bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, palladium acetate, or palladium-activated carbon. Especially, bis (dibenzylidene acetone) palladium or tris (dibenzylidene acetone) dipalladium is mentioned.

When the metal complex catalyst in the present invention is a copper complex, the copper complex is preferably monovalent, and for example, copper chloride (I), copper bromide (I), copper iodide (I), and copper acetate (I) Etc. can be mentioned. Especially, copper chloride (I), copper bromide (I), or copper iodide (I) is preferable.

When using a copper complex as a metal complex catalyst, you may use it, mixing a copper complex and a ligand in a reaction system. As the ligand to be mixed with the copper complex in the reaction system, L-proline, 1,2-trans-cyclohexanediamine, ethylenediamine, tetramethylethylenediamine (TMEDA), N, N'-dimethylethylenediamine (DMEDA), 1, 10-phenanthroline, 2,2'-bipyridyl, 2-picolylamine, 18-crown-6 are preferred, L-proline, trans-cyclohexanedicarboxylic acid, tetramethylethylenediamine (TMEDA) This is more preferable.

The amount of the metal complex catalyst in the present invention may be a so-called catalyst amount, and in the case of using a palladium catalyst, it is preferably 20 mol% or less, more preferably 10 mol% or less with respect to the aromatic dihalogen compound. . When using a copper catalyst, it is 100 mol% or less with respect to an aromatic dihalogen compound, More preferably, it is 50 mol% or less. The amount of the metal complex catalyst used is preferably as small as possible, but is usually 0.001 mol% or more, particularly 0.01 mol% or more, based on the aromatic dihalogen compound.

As a base used by this invention, it is hydroxide; Carbonates; Hydrogen carbonate; Phosphate; Hydrogen phosphate; Carboxylates; Alkoxides; Amines; Ammonia etc. are mentioned. The hydroxide, the carbonate, the hydrogen carbonate, the phosphate, the hydrogen phosphate, and the carboxylate are preferably salts of alkali metals or alkaline earth metals. The base may be a hydrate or may not be a hydrate.

As said hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, etc. are mentioned, for example. As a carbonate, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate, barium carbonate, potassium carbonate, etc. are mentioned, for example. Examples of the hydrogen carbonate include lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate and the like. As phosphate, sodium orthophosphate, tripotassium phosphate, tricalcium phosphate, triammonium phosphate, etc. are mentioned, for example. Examples of the hydrogen phosphate include disodium hydrogen phosphate, dipotassium hydrogen phosphate, calcium hydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, calcium dihydrogen phosphate and ammonium dihydrogen phosphate. Examples of the carboxylate salts of alkali metals and alkaline earth metals include sodium acetate, potassium acetate, calcium acetate, and the like. As an alkoxide, lithium methoxide, sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium t-butoxide, etc. are mentioned, for example. As the amines, for example, triethylamine, tri-n-butylamine, diisopropylethylamine, N-methylpiperidine, 4-methylmorpholine, 4-ethylmorpholine, pyridine, 4- (N, N-dimethylamino) pyridine, 4-pyrrolidinopyridine, 4-pyrrolidinopyridine, 2,6-di (t-butyl) -4-methylpyridine, quinoline, N, N-dimethylaniline, N, N- Diethylaniline, 1,5-diazabicyclo [4.3.0] nonane-5-ene (DBN), 1,8-diazabicyclo [5.4.0] undecane-7-ene (DBU), 1,4 -Diazabicyclo [2.2.2] octane (DABCO), etc. are mentioned.

Preferable bases include potassium hydroxide, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, tripotassium phosphate, dipotassium hydrogen phosphate, sodium t-butoxide, potassium t-butoxide or triethylamine. As a more preferable base, cesium carbonate or tripotassium phosphate is mentioned. These bases can also be used 1 type or in combination or 2 or more types.

It is preferable that reaction in the manufacturing method of this invention is performed in presence of a solvent. It is preferable that it does not inhibit the progress of reaction as a reaction solvent. For example, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, dichloromethane and chloroform Aliphatic halogenated hydrocarbons such as carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, trichloroethylene and tetrachloroethylene, diethyl ether, isopropyl ether, 1,2-dimethoxyethane, Tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1-methoxy-2- (2-methoxyethoxy) ethane, TBME (t-butylmethylether), CPME (cyclopentylmethylether Ethers such as), esters such as ethyl acetate and ethyl propionate, amides such as dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone, triethylamine, tributylamine, N, N- Amines such as dimethylaniline, Pyridines such as pyridine and picoline, alcohols such as methanol, ethanol, n-propanol and ethylene glycol, acetonitrile, dimethyl sulfoxide, sulfolane, 1,3-dimethyl-2-imidazolidinone, acetone and water Etc. can be mentioned.

Preferable solvents include toluene, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylformamide, dimethylacetamide, or N-methyl-2-pyrrolidone. As a more preferable solvent, 1,2-dimethoxyethane or tetrahydrofuran is mentioned. Solvent may be independent and may use 2 or more types.

Although reaction temperature can select the range from -100 degreeC or more to the temperature of the boiling point of the reaction solvent used, Preferably it is -50-150 degreeC, More preferably, it is 0-100 degreeC. The reaction time is 0.1 to 1000 hours, preferably 0.5 to 100 hours.

The reaction may be atmospheric pressure or may be pressurized, or may be continuous or batchwise.

The dinitro compound represented by Formula (3) produced by the above scheme (A) may be purified by column chromatography such as distillation, recrystallization or silica gel.

The N- (nitrophenyl) aromatic amine compound obtained in this way can be manufactured easily by reducing a nitro group to an amino group by the conventionally well-known conventional method.

Example

Hereinafter, although an Example demonstrates this invention further more concretely, the interpretation of this invention is not limited by these Examples. In addition, the analysis apparatus and analysis conditions used in the Example are as follows.

¹ H-NMR;

Device: ECX-300 (300 MHz), manufactured by Nihon Electronics Co., Ltd.

Measurement solvent: CDCl ₃ , DMSO-d ₆ , Reference substance: Tetramethylsilane (TMS) (The δ value of ¹ H in TMS is 0.0 ppm.)

HPLC;

Equipment: HPLC, LC-20AD (manufactured by Shimadzu Corporation)

Column: Inertsil ODS-3 (GL Science), Average particle diameter of a packing material: 5 micrometers, Internal diameter: 4.6 mm, Length: 250 mm Column temperature: 40 degreeC

Eluent: acetonitrile / water = 80/20 (v / v), flow rate: 1.0 ml / min

Detection method: UV (254 nm), data collection time: 40 min

Synthesis Example 1 Preparation of 2,5-bis (N- (4-aminophenyl) -N-methyl-4-aminophenyl) -N-methylpyrrole (Compound DA-1)

(Step a); Preparation of 2,5-bis (N- (4-nitrophenyl) -N-methyl-4-aminophenyl) -N-methylpyrrole (Compound DN-1)

[Formula 6]

Synthesis Example 1-a-01

In a 50 mL four-necked flask, 2,5-bis (4-bromophenyl) -1-methyl-1H-pyrrole (1.5 g, 3.84 mmol), tris (dibenzylideneacetone) dipalladium (70.2 mg, 0.08 mmol ), 2-dicyclohexylphosphino-2 ', 6'-diisopropoxybiphenyl (71.6 mg, 0.15 mmol), and cesium carbonate (2.5 g, 7.68 mmol) are added, and the inside of the reaction vessel is nitrogen After replacement with gas, tetrahydrofuran (9.0 g) was injected and stirred under reflux for 30 minutes.

Subsequently, tetrahydrofuran solution (10.5 g) of N-methyl-4-nitroaniline (1.28 g, 8.45 mmol) prepared separately was dripped over 30 minutes, and it stirred for 42 hours under reflux. After completion of the stirring, the area percentage (hereinafter referred to as LC face white) of the target product was confirmed by HPLC, and the result was 99.6%. The reaction mixture was cooled to 20 degreeC-25 degreeC, water (15.0g) was added, and it stirred for 30 minutes. The precipitated crystals were filtered under reduced pressure, the crystals were washed with a mixed solvent of tetrahydrofuran and water (volume ratio 1: 1, 7.5 g), and then dried to obtain powder crystals (DN-1) having the following NMR analysis results ( Yield 1.91 g, yield 96%).

(Synthesis example 1-a-02-1-a-12)

The reaction was carried out in accordance with the method described in Synthesis Example 1-a-01 except that the ligand, base, and solvent were changed.

Table 1 shows the ligands, bases, solvents, reaction temperatures, reaction times, and LC cotton bags in Synthesis Examples 1-a-01 to 1-a-12.

"XPhos" in Table 1 represents 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl, and "RuPhos" represents 2-dicyclohexylphosphino-2 ', 6 Represents "-diisopropoxybiphenyl," DMF "represents dimethylformamide," THF "represents tetrahydrofuran," NMP "represents N-methyl-2-pyrrolidone, and" DMAc " Represents dimethylacetamide, "MeTHF" represents 2-methyltetrahydrofuran, and "DME" represents 1,2-dimethoxyethane. In addition, LC face white represents the ratio (%) of the target object in reaction liquid, when the reaction was tracked by LC. However, the solvent, N-methyl-4-nitroaniline and dba are the numerical values excluded.

Synthesis Example 1-a-13

In a 500 mL four-necked flask, 2,5-bis (4-bromophenyl) -1-methyl-1H-pyrrole (25.0 g, 63.9 mmol), N-methyl-4-nitroaniline (21.4 g, 140.58 mmol) , Copper (I) iodide (4.87 g, 25.6 mmol), L-proline (5.89 g, 51.12 mmol), and tripotassium phosphate (54.27 g, 255.6 mmol) were added, and the inside of the reaction vessel was replaced with nitrogen gas. Then, NMP (125.0g) was injected and stirred at 120 degreeC for 27 hours. After completion of the stirring, LC cotton white of the target product was confirmed by HPLC and found to be 48.2%.

(Step b); Preparation of 2,5-bis (N- (4-aminophenyl) -N-methyl-4-aminophenyl) -N-methylpyrrole (Compound DA-1)

[Formula 7]

A mixture of compound (DN-1) (12.0 g, 22.5 mmol), 5 mass% Pd / C (41.3% hydrous, 1.45 g), activated carbon (1.2 g), and THF (120 g) was prepared at a gauge pressure of 0.3 MPa. It stirred at 50 degreeC under hydrogen atmosphere for 4 hours. After completion of the reaction, the catalyst and the activated carbon were separated by filtration, and then the filtrate was washed twice with THF (24.0 g), and the filtrate was concentrated under reduced pressure until the contents were 48 g at 50 ° C, and methanol (84.0 g) was added, it cooled to 5 degreeC and stirred for 1 hour. The precipitated crystals were filtered off, washed twice with methanol (24.0 g), dried under reduced pressure at 50 ° C. to obtain powder crystals, thereby obtaining powder crystals (DA-1) having the following NMR analysis results (amount 8.93 g) , Yield 84%).

According to the present invention, the diamine compound useful as a raw material of the liquid crystal aligning agent can be produced with few by-products, high purity and high yield. Moreover, the manufacturing method of this invention is implementable on a large scale, and is industrially useful.

In addition, all the content of the JP Patent application 2017-004140, a claim, drawing, and the abstract for which it applied on January 13, 2017 is referred here, and it takes in as an indication of the specification of this invention.

Claims (13)

N- represented by the following formula (3) by reacting the aromatic dihalogen compound represented by the following formula (1) and the N-alkylnitroaniline derivative represented by the following formula (2) in the presence of a metal complex catalyst and a base: Method for producing a (nitrophenyl) aromatic amine compound.

[Wherein Ar represents an arylene group or a heteroarylene group, and X represents a halogen.]

[Wherein, R represents C ₁ to C ₆ alkyl.]

[Wherein Ar, X, and R are the same as defined above.] The method of claim 1,
The metal complex catalyst is a palladium complex or a copper complex. The method according to claim 1 or 2,
The base is a hydroxide, carbonate, hydrogencarbonate, phosphate, hydrogen phosphate or carboxylate of an alkali metal or alkaline earth metal. The method according to any one of claims 1 to 3,
The reaction is carried out in the presence of a solvent. The method according to any one of claims 1 to 4,
The aromatic dihalogen compound is a compound represented by any one of the following formulas (X1) to (X6).

[Wherein X represents halogen.] The method according to any one of claims 1 to 4,
The aromatic dihalogen compound is a compound represented by any of the following formulas (X1) to (X3).

[Wherein X represents a halogen.] The method according to any one of claims 1 to 6,
The manufacturing method in which X in Formula (1) or Formula (X1)-(X6) is Cl or Br. The method according to any one of claims 1 to 7,
The N-alkylnitroaniline derivative is N-methyl-p-nitroaniline. The method according to any one of claims 4 to 8,
The solvent is toluene, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylformamide, dimethylacetamide, or N-methyl-2-pyrrolidone. The method according to any one of claims 1 to 9,
The base is cesium carbonate or tripotassium phosphate. The method according to any one of claims 2 to 10,
The palladium in the palladium complex, Pd ₂ (dba) ₃ (dba) _n represented by (dba represents dibenzylideneacetone, n represents an integer of 0 to 2) The manufacturing method. The method according to any one of claims 2 to 11,
The ligands in the palladium complex or the copper complex are 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl and 2-dicyclohexylphosphino-2 ', 6'-diiso The manufacturing method which is at least 1 sort (s) chosen from the group which consists of propoxybiphenyl. N- (aminophenyl) aromatic amine compound by reducing the nitro group which the N- (nitrophenyl) aromatic amine compound represented by Formula (3) obtained by the manufacturing method in any one of Claims 1-12 has. Method of preparation.