CN110167916B - Method for producing aromatic diamine compound precursor - Google Patents
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- CN110167916B CN110167916B CN201880006675.3A CN201880006675A CN110167916B CN 110167916 B CN110167916 B CN 110167916B CN 201880006675 A CN201880006675 A CN 201880006675A CN 110167916 B CN110167916 B CN 110167916B
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- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
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Abstract
The present invention provides a method for producing a dinitro compound which is a precursor of a diamine compound as a raw material for producing a polyamic acid and/or a polyimide with a high purity and a high yield with a small amount of by-products. A process for producing an N- (nitrophenyl) aromatic amine compound represented by the formula (3) by reacting an aromatic dihalogen compound represented by the formula (1) with an N-alkylnitroaniline derivative represented by the formula (2) in the presence of a metal complex solvent and a base. [ Ar represents an arylene or heteroarylene group; x represents a halogen; r represents C 1 ～C 6 Alkyl radical]。
Description
Technical Field
The present invention relates to a novel method for producing a dinitro compound, which is a precursor of a specific diamine compound as a raw material for producing polyimide used for a liquid crystal aligning agent or the like, with a high purity and a high yield with little by-product.
Background
Currently, polyimide films are often used as liquid crystal alignment films used in liquid crystal display devices. The liquid crystal alignment film of the polyimide film is prepared by the following method: a solution of polyamic acid or a solution of solvent-soluble polyimide as a polyimide precursor is applied to a substrate and baked, and the resulting film is subjected to an alignment treatment such as a brushing treatment (see patent documents 1 and 2). The polyamic acid and the solvent-soluble polyimide are generally produced by a polycondensation reaction between a tetracarboxylic acid derivative such as tetracarboxylic dianhydride and a diamine compound.
Diamine compounds as raw materials of such polyamic acids, polyimides, and the like are important because they affect the characteristics of liquid crystal alignment films obtained therefrom and the characteristics of liquid crystal display elements, and various diamine compounds have been used and proposed.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 7-120769
Patent document 2: japanese patent laid-open publication No. 9-146100
Disclosure of Invention
Problems to be solved by the invention
As a diamine compound having excellent properties, a diamine compound having a structure in which aromatic rings are bonded to each other has been proposed. The diamine compound is generally produced by reduction of a dinitro compound as a precursor, but a production method of some dinitro compounds is not yet established, and there are problems that a multi-stage process is required, the yield is low, and the production cost is high. In addition, the coupling reaction between an aromatic dihalogen compound and an N-alkylnitroaniline derivative is difficult to apply to the production of a dinitro compound because of its low reactivity.
The present invention has an object to provide a process for producing a dinitro compound by a coupling reaction between an aromatic dihalogen compound and an N-alkylnitroaniline derivative, which solves the above-mentioned problems and can produce the target substance with high purity and high yield at a high reaction rate and with less by-products.
Means for solving the problems
The present invention has been made in an effort to achieve the above object, and as a result, a novel production method which is as follows has been found.
1. A process for producing an N- (nitrophenyl) aromatic amine compound represented by the following formula (3), which comprises reacting an aromatic dihalogen compound represented by the following formula (1) with an N-alkylnitroaniline derivative represented by the following formula (2) in the presence of a metal complex catalyst and a base.
[ in the formula, ar represents an arylene group or a heteroarylene group (heteroarylene), and X represents a halogen. ]
[ wherein R represents C 1 ～C 6 An alkyl group.]
[ wherein Ar, X and R are as defined above. ]
2. The production method according to the above 1, wherein the metal complex catalyst is a palladium complex or a copper complex.
3. The production process according to the above 1 or 2, wherein the base is a hydroxide, carbonate, bicarbonate, phosphate, hydrogenphosphate or carboxylate of an alkali metal or an alkaline earth metal.
4. The production process according to any one of the above 1 to 3, wherein the reaction is carried out in the presence of a solvent.
5. The production process according to any one of the above 1 to 4, wherein the aromatic dihalogen compound is a compound represented by any one of the following formulae (X1) to (X6).
6. The production process according to any one of the above 1 to 4, wherein the aromatic dihalogen compound is a compound represented by any one of the following formulae (X1) to (X3).
7. The production method according to any one of the above 1 to 6, wherein X in the formula (1) or the formulae (X1) to (X6) is Cl or Br.
8. The production process according to any one of the above 1 to 7, wherein the N-alkylnitroaniline derivative is N-methyl-p-nitroaniline.
9. The production process according to any one of the above 4 to 8, wherein the solvent is toluene, 1, 2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylformamide, dimethylacetamide or N-methyl-2-pyrrolidone.
10. The production method according to any one of the above 1 to 9, wherein the base is cesium carbonate or tripotassium phosphate.
11. The production method according to any one of the above 2 to 10, wherein the palladium in the palladium complex is composed of Pd 2 (dba) 3 (dba) n (dba represents dibenzylidene acetone, and n represents an integer of 0 to 2).
12. The production process according to any one of the above 2 to 11, wherein the ligand in the palladium complex or the copper complex is at least 1 selected from the group consisting of 2-dicyclohexylphosphino-2 ',4',6' -triisopropylbiphenyl and 2-dicyclohexylphosphino-2 ',6' -diisopropoxybiphenyl.
13. A method for producing an N- (aminophenyl) aromatic amine compound, which comprises reducing the nitro group of an N- (nitrophenyl) aromatic amine compound represented by formula (3) obtained by the production method described in any one of the above 1 to 12.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a dinitro compound which is a precursor of a diamine compound can be produced in high yield by a coupling reaction between an aromatic dihalogen compound having a generally low reactivity and an N-alkylnitroaniline derivative. In addition, since the dinitro compound obtained in the present invention is used in a small amount of the metal catalyst, the content of residual metals which are problematic in the field of electronic materials can be minimized, and the content of a mono-coupler which is a reaction intermediate that is difficult to separate from a target substance is substantially 0, and complicated purification such as column treatment is not necessary.
The dinitro compound obtained in the present invention can be used as a precursor of a diamine compound, which is a raw material for producing polyamic acid and/or polyimide.
Detailed Description
The present invention will be described in more detail below.
In the present specification, "n" represents normal (normal), "s" represents secondary (secondary), "t" represents tertiary (tertiary), "o" represents ortho (ortho), "m" represents meta (meta), and "p" represents para (para).
The reaction in the production method of the present invention is represented by the following scheme (a). That is, an aromatic dihalogen compound represented by the formula (1) and an N-alkylnitroaniline represented by the formula (2) are reacted in the presence of a metal complex catalyst and a base to produce an N- (nitrophenyl) aromatic amine compound represented by the formula (3).
In the above formula (1), ar and X are as described in the above formula 1.
The arylene group represented by Ar is a 2-valent group formed by removing 1 hydrogen atom from each of 2 ring carbon atoms of an aromatic hydrocarbon. The heteroarylene group is a 2-valent group formed by removing 1 hydrogen atom from each of 2 ring carbon atoms of a heteroaromatic hydrocarbon.
The halogen represented by X is preferably Cl, br or I, more preferably Cl or Br.
The aromatic dihalogen compound represented by the above formula (1) is preferably a compound represented by any of the following (X1) to (X6), and more preferably a compound represented by any of (X1) to (X3).
In the above formulae (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.
C represented by R in the above formula (3) 1 ～C 6 The alkyl group represents a 1-valent group formed by losing 1 hydrogen atom from a linear or branched aliphatic hydrocarbon having 1 to 6 carbon atoms. R is preferably C 1 ～C 3 Alkyl, more preferably methyl or ethyl.
As examples of R, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1-dimethylpropyl, n-hexyl or isohexyl groups are preferred, and methyl is more preferred.
Some of the aromatic dihalogen compounds used herein are known compounds, and can be synthesized by known methods described in the literature. For example, 2, 5-bis (4-bromophenyl) -1-methyl-1H-pyrrole was reacted according to the method described in J.Med.chem.1977, vol.20, pp.531-536 to obtain a compound.
The position of the nitro group relative to the amino group in the N-alkylnitroaniline may be any of the ortho-, meta-or para-positions, with the para-position being more preferred.
The amount of the N-alkylnitroaniline used in the reaction of the aromatic dihalogen compound and the N-alkylnitroaniline is preferably 1.0 to 1.5 mol, and particularly preferably 1.05 to 1.2 mol, based on 1 mol of the halogen atom of the aromatic dihalogen compound.
In the present invention, the reaction of the above-mentioned 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 the metal complex catalyst, catalysts of various structures can be used, and among them, a palladium complex or a copper complex having a low valence is preferable. In particular, as the palladium complex, a zero-valent metal complex catalyst in which a tertiary phosphine or a triester phosphite is used as a ligand is preferable.
In the present invention, a precursor which can be easily converted into a zero-valent metal complex catalyst can also be used in the reaction system. In addition, in the reaction system, a metal complex not containing a tertiary phosphine or a phosphite triester as a ligand may be mixed with a tertiary phosphine or a phosphite triester as a ligand to form a low-valence metal complex catalyst having the tertiary phosphine or the phosphite triester as a ligand.
Examples of the tertiary phosphine or the triester phosphite as the ligand include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane, 1' -bis (diphenylphosphino) ferrocene, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, 2-dicyclohexylphosphino-2 ',4',6' -triisopropylbiphenyl, 2-di-tert-butylphosphino-2 ',4',6' -triisopropylbiphenyl, 2-dicyclohexylphosphino-2 ',6' -diisopropoxybiphenyl, 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl, (2-biphenyl) di-tert-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-di (diphenylphosphine) anthracene, and the like. It is also preferable to use a metal complex catalyst containing 2 or more of these ligands in a mixed state.
Among these, preferable ligands include 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane, 2-dicyclohexylphosphino-2 ',4',6 '-triisopropylbiphenyl, 2-di-tert-butylphosphino-2', 4',6' -triisopropylbiphenyl, 2-dicyclohexylphosphino-2 ',6' -diisopropoxybiphenyl, 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl, (2-biphenyl) di-tert-butylphosphine, (2-biphenyl) dicyclohexylphosphine, and 2-dicyclohexylphosphino-2 '-methylbiphenyl, and more preferable ligands include 2-dicyclohexylphosphino-2', 4',6' -triisopropylbiphenyl, 2-dicyclohexylphosphino-2 ',6' -diisopropoxybiphenyl, and 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl.
As the metal complex catalyst, it is also preferable to use a palladium complex not containing a tertiary phosphine, a triester phosphite in combination with a metal complex containing a tertiary phosphine or a triester phosphite. In this case, the above ligands may be further combined. Examples of the palladium complex not containing a tertiary phosphine or a phosphite triester include bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, bis (acetonitrile) dichloropalladium, bis (benzonitrile) dichloropalladium, palladium acetate, palladium chloride, palladium-activated carbon, and the like. Examples of the palladium complex containing a tertiary phosphine or a phosphite triester as a ligand include (ethylene) bis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) dichloropalladium, and the like.
Examples of the metal complex catalyst preferable in the present invention include bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, palladium acetate, and palladium-activated carbon. Among them, bis (dibenzylideneacetone) palladium or tris (dibenzylideneacetone) dipalladium may be mentioned.
When the metal complex catalyst in the present invention is a copper complex, the copper complex is preferably a 1-valent complex, and examples thereof include copper (I) chloride, copper (I) bromide, copper (I) iodide, and copper (I) acetate. Among them, copper (I) chloride, copper (I) bromide or copper (I) iodide is preferable.
When a copper complex is used as the metal complex catalyst, the copper complex and the ligand may be mixed in the reaction system and used. The ligand to be mixed with the copper complex in the reaction system is preferably L-proline, 1, 2-trans-cyclohexanediamine, ethylenediamine, tetramethylethylenediamine (TMEDA), N '-dimethylethylenediamine (DMEDA), 1, 10-phenanthroline, 2' -bipyridine, 2-aminomethylpyridine, 18-crown-6, and more preferably L-proline, trans-cyclohexanedicarboxylic acid, or Tetramethylethylenediamine (TMEDA).
The amount of the metal complex catalyst used in the present invention, that is, the so-called catalyst amount, is preferably 20 mol% or less, more preferably 10 mol% or less, based on the aromatic dihalogen compound, when a palladium catalyst is used. When the copper catalyst is used, the amount is preferably 100 mol% or less, more preferably 50 mol% or less, based on the aromatic dihalogen compound. The amount of the metal complex catalyst used is preferably as small as possible within an effective range, and is usually 0.001 mol% or more, particularly 0.01 mol% or more, based on the aromatic dihalogen compound.
Examples of the base used in the present invention include hydroxides, carbonates, bicarbonates, phosphates, hydrogenphosphates, carboxylates, alkoxides, amines, and ammonia. The hydroxides, carbonates, bicarbonates, phosphates, hydrogenphosphates and carboxylates are preferably salts of alkali metals or alkaline earth metals. The base may or may not be a hydrate.
Examples of the hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide. Examples of the carbonate include lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate, barium carbonate, sodium potassium carbonate, and the like. Examples of the bicarbonate include lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, and ammonium bicarbonate. Examples of the phosphate include sodium orthophosphate, tripotassium phosphate, tricalcium phosphate, and triammonium phosphate. 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 alkali metal and alkaline earth metal carboxylates include sodium acetate, potassium acetate, and calcium acetate. Examples of the alkoxide include lithium methoxide, sodium ethoxide, sodium tert-butoxide, and potassium tert-butoxide. Examples of the amines include triethylamine, tri-N-butylamine, diisopropylethylamine, N-methylpiperidine, 4-methylmorpholine, 4-ethylmorpholine, pyridine, 4- (N, N-dimethylamino) pyridine, 4-pyrrolidinylpyridine, 2, 6-di (t-butyl) -4-methylpyridine, quinoline, N-dimethylaniline, N-diethylaniline, 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN), 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1, 4-diazabicyclo [2.2.2] octane (DABCO), and the like.
Preferred bases include potassium hydroxide, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, tripotassium phosphate, dipotassium hydrogen phosphate, sodium tert-butoxide, potassium tert-butoxide and triethylamine. More preferred bases include cesium carbonate and tripotassium phosphate. These bases may be used in combination of 1 kind or 2 or more kinds.
The reaction in the production method of the present invention is preferably carried out in the presence of a solvent. The reaction solvent is preferably a solvent which does not inhibit the reaction. For example, aromatic hydrocarbons such as benzene, toluene, xylene, etc.; aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane; aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; aliphatic halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, 1, 2-dichloroethane, 1-trichloroethane, trichloroethylene, and tetrachloroethylene; ethers such as diethyl ether, isopropyl ether, 1, 2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane, 1-methoxy-2- (2-methoxyethoxy) ethane, TBME (tert-butyl methyl ether), and CPME (cyclopentyl methyl ether); esters such as ethyl acetate and ethyl propionate; amides such as dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone; amines such as triethylamine, tributylamine, and N, N-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, water and the like.
Preferred solvents include toluene, 1, 2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone. More preferred examples of the solvent include 1, 2-dimethoxyethane and tetrahydrofuran. The solvent may be used alone, or 2 or more kinds thereof may be used.
The reaction temperature may be selected from the range of from-100 ℃ or higher to the boiling point temperature of the reaction solvent used, but is preferably from-50 to 150 ℃, more preferably from 0 to 100 ℃. The reaction time is from 0.1 to 1000 hours, preferably from 0.5 to 100 hours.
The reaction may be carried out under normal pressure or under pressure, and may be a continuous or batch type.
The dinitro compound represented by the formula (3) produced by the above-mentioned means (A) can be purified by distillation, recrystallization, column chromatography using silica sol or the like, or the like.
The N- (nitrophenyl) aromatic amine compound thus obtained can be easily produced by reducing the nitro group to an amino group by a known method.
Examples
The present invention is further specifically illustrated by the following examples, but the present invention is not to be construed as being limited thereto. The analytical devices and analytical conditions used in the examples are as follows. 1 H-NMR；
The device comprises the following steps: ECX-300 (300 MHz) manufactured by Nippon electronic official,
Measurement of solvent: CDCl 3 ,DMSO-d 6 And a reference substance: tetramethylsilane (TMS) (in TMS 1 The value of H.delta.was set to 0.0ppm. )
HPLC；
The device comprises the following steps: HPLC, LC-20AD (manufactured by Shimadzu corporation)
Column: inertsil ODS-3 (GL Science), average particle diameter of filler: 5 μm, inner diameter: phi 4.6mm, length: column temperature of 250 mm: 40 deg.C
Eluent: acetonitrile/water =80/20 (v/v), flow rate: 1.0 mL/min
Detection method: UV (254 nm), data acquisition time: 40 minutes
Synthesis example 1: production 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)
(Synthesis example 1-a-01)
In a 50mL four-necked flask, 2, 5-bis (4-bromophenyl) -1-methyl-1H-pyrrole (1.5g, 3.84mmol), tris (dibenzylideneacetone) dipalladium (70.2mg, 0.08mmol), 2-dicyclohexylphosphino-2 ',6' -diisopropoxybiphenyl (71.6 mg, 0.15mmol), and cesium carbonate (2.5g, 7.68mmol) were charged, and after the inside of the reaction vessel was replaced with nitrogen, tetrahydrofuran (9.0 g) was charged and stirred under reflux for 30 minutes.
Subsequently, a tetrahydrofuran solution (10.5 g) of N-methyl-4-nitroaniline (1.28g, 8.45mmol) prepared separately was added dropwise over 30 minutes, and the mixture was stirred at reflux for 42 hours. After completion of the stirring, the area percentage of the target substance (hereinafter referred to as LC area percentage) was confirmed by HPLC, and the result was 99.6%. The reaction mixture was cooled to 20 ℃ to 25 ℃, water (15.0 g) was added, and stirred for 30 minutes. The precipitated crystals were filtered under reduced pressure, washed with a mixed solvent of tetrahydrofuran and water (volume ratio 1,7.5g), and dried to obtain powdery crystals (DN-1) (yield 1.91g, 96%) having the following NMR analysis results.
1 H-NMR(DMSO-d 6 )：δ8.11-8.08(m、4H、Ar)，7.64(d、J＝2.0Hz、4H、Ar)，7.42(d、J＝2.0Hz、4H、Ar)，6.89-6.85(m、4H、Ar),6.38(s、2H、Ar)，3.69(3H，s、Me),3.44(s，6H、Me).
(Synthesis examples 1-a-02 to 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.
The ligand, base, solvent, reaction temperature, reaction time and LC surface percentage in Synthesis examples 1-a-01 to 1-a-12 are shown in Table 1.
"XPhos" in Table 1 means 2-dicyclohexylphosphino-2 ',4',6' -triisopropylbiphenyl, "RuPhos" means 2-dicyclohexylphosphino-2 ',6' -diisopropylbiphenyl, "DMF" means dimethylformamide, "THF" means tetrahydrofuran, "NMP" means N-methyl-2-pyrrolidone, "DMAc" means dimethylacetamide, "MeTHF" means 2-methyltetrahydrofuran, "DME" means 1, 2-dimethoxyethane. LC area hundred represents the ratio (%) of the target substance in the reaction solution when the reaction is followed by LC. Wherein, it is the values of the subtractive solvent, N-methyl-4-nitroaniline and dba.
[ Table 1 ]
(Synthesis examples 1-a-13)
2, 5-bis (4-bromophenyl) -1-methyl-1H-pyrrole (25.0g, 63.9mmol), N-methyl-4-nitroaniline (21.4g, 140.58mmol), copper (I) iodide (4.87g, 25.6mmol), L-proline (5.89g, 51.12mmol) and tripotassium phosphate (54.27g, 255.6mmol) were charged into a 500mL four-necked flask, and after the interior of the reaction vessel was replaced with nitrogen gas, NMP (125.0 g) was charged and stirred at 120 ℃ for 27 hours. After completion of the stirring, the LC abundance of the target substance was confirmed by HPLC, and the result was 48.2%.
(step b); production of 2, 5-bis (N- (4-aminophenyl) -N-methyl-4-aminophenyl) -N-methylpyrrole (Compound DA-1)
A mixture of compound (DN-1) (12.0 g, 22.5 mmol), 5 mass% Pd/C (41.3% aqueous form, 1.45 g), activated carbon (1.2 g) and THF (120 g) was stirred under a hydrogen atmosphere at a gauge pressure of 0.3MPa at 50 ℃ for 4 hours. After completion of the reaction, the catalyst and activated carbon were separated by filtration, and the filtrate was washed with THF (24.0 g) 2 times, concentrated under reduced pressure at 50 ℃ until the internal volume became 48g, added with methanol (84.0 g), cooled to 5 ℃ and stirred for 1 hour. The precipitated crystals were filtered, washed 2 times with methanol (24.0 g), and then dried under reduced pressure at 50 ℃ to obtain powdery crystals (DA-1) having the following NMR analysis results (yield 8.93g, 84%).
1 H-NMR(DMSO-d 6 )：δ7.21-7.18(m、4H、Ar)，6.89-6.85(m、4H、Ar)，6.66-6.58(m、8H、Ar)，6.02(s、2H、Ar)，5.03(4H，s、NH 2 ),3.45(s，3H、Me)，3.16(s、6H、Me).
Industrial applicability
According to the present invention, a diamine compound used as a raw material for a liquid crystal aligning agent can be produced with high purity and high yield with few by-products. In addition, the production method of the present invention can be carried out in a large scale, and is industrially useful.
The entire contents of the specification, claims, drawings and abstract of japanese patent application No. 2017-004140 filed on 1/13/2017 are incorporated herein as the disclosure of the present specification.
Claims (12)
1. A process for producing an N- (nitrophenyl) aromatic amine compound represented by the following formula (3), which comprises reacting an aromatic dihalogen compound with an N-alkylnitroaniline derivative represented by the following formula (2) in the presence of a metal complex catalyst and a base,
in the formula (2), R represents C 1 ～C 6 An alkyl group, a carboxyl group,
in the formula (3), ar represents a group obtained by removing X from any of the following formulas (X1) to (X5), and R represents C 1 ～C 6 An alkyl group, which is a radical of an alkyl group,
wherein the aromatic dihalogen compound is a compound represented by any one of the following formulae (X1) to (X5),
wherein X represents a halogen.
2. The production method according to claim 1, wherein the metal complex catalyst is a palladium complex or a copper complex.
3. The production process according to claim 1 or 2, wherein the base is a hydroxide, carbonate, bicarbonate, phosphate, hydrogenphosphate or carboxylate of an alkali metal or an alkaline earth metal.
4. The production process according to claim 1 or 2, wherein the reaction is carried out in the presence of a solvent.
5. The production process according to claim 1 or 2, wherein the aromatic dihalogen compound is a compound represented by any one of the following formulae (X1) to (X3),
wherein X represents a halogen.
6. The production process according to claim 1 or 2, wherein X in the formulae (X1) to (X5) is Cl or Br.
7. The production process according to claim 1 or 2, wherein the N-alkylnitroaniline derivative is N-methyl-p-nitroaniline.
8. The production process according to claim 4, wherein the solvent is toluene, 1, 2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylformamide, dimethylacetamide or N-methyl-2-pyrrolidone.
9. The production method according to claim 1 or 2, wherein the base is cesium carbonate or tripotassium phosphate.
10. The production method according to claim 2, wherein the palladium in the palladium complex is composed of Pd 2 (dba) 3 (dba) n Dba represents dibenzylidene acetone, and n represents an integer of 0 to 2.
11. The production process according to claim 2, wherein the ligand in the palladium complex or the copper complex is at least 1 selected from the group consisting of 2-dicyclohexylphosphino-2 ',4',6' -triisopropylbiphenyl and 2-dicyclohexylphosphino-2 ',6' -diisopropoxybiphenyl.
12. A method for producing an N- (aminophenyl) aromatic amine compound, which comprises reducing a nitro group contained in an N- (nitrophenyl) aromatic amine compound represented by formula (3) obtained by the production method according to any one of claims 1 to 11.
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| PCT/JP2018/000504 WO2018131657A1 (en) | 2017-01-13 | 2018-01-11 | Method for producing aromatic diamine compound precursor |
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| JPWO2018131657A1 (en) | 2019-11-07 |
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| JP7103232B2 (en) | 2022-07-20 |
| KR20190103173A (en) | 2019-09-04 |
| KR102544307B1 (en) | 2023-06-15 |
| TW201831438A (en) | 2018-09-01 |
| WO2018131657A1 (en) | 2018-07-19 |
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