JP6536848B2 - Method for producing aromatic compound and organic electronic material - Google Patents

Description

  The present invention relates to a method for producing an aromatic compound and an organic electronic material containing the aromatic compound obtained by the method.

  Aromatic halogen compounds are useful as raw materials for cross coupling reactions, and are used as synthetic raw materials for pharmaceuticals and functional materials.

  However, there are many aromatic halides that adversely affect the environment and the human body, and some are prohibited by law. In addition, when pharmaceuticals and functional materials are produced by a reaction using an aromatic halogen compound as a raw material, another aromatic halogen compound produced as a by-product or an unreacted raw material aromatic halogen compound remains in the product. There is concern that it may cause adverse effects on the human body and a significant decrease in device performance.

  For example, organic electroluminescent devices (hereinafter also referred to as organic EL devices) are widely used in the field of thin film display devices, backlights of liquid crystal displays, flat light sources, and the like. If a large amount of impurities from a halogenated organic compound material as a raw material remains in the organic EL element, the light emission efficiency and the light emission luminance are affected. Therefore, it has been proposed that the luminance deterioration of the organic EL element can be suppressed by controlling the halogen impurity concentration of the organic compound material (for example, aromatic compound) constituting the organic compound layer in the organic EL element to less than 1,000 mass ppm. (See, for example, Patent Document 1). As a method of controlling the above-mentioned organic compound material to a desired halogen impurity concentration, appropriately combining purification techniques such as sublimation purification, recrystallization, and high performance liquid chromatography is disclosed in the above-mentioned patent documents.

Patent No. 3290432

  However, separation by the purification method is effective only when there is a large difference in physical properties between the target substance and the halogen-containing impurity, and in particular, the aromatic halogen compound remains in a part of the polymer material such as oligomer and polymer. In the case of separation, it was difficult to separate by the purification method because there is almost no difference in physical properties. In addition, it is extremely difficult to apply purification methods such as sublimation purification to high molecular weight materials such as oligomers and polymers because the molecular weight is large and thermal decomposition proceeds.

  The present invention has been made in view of the above-mentioned circumstances, and a method for producing an aromatic compound capable of effectively reducing the content of halogen element contained in an aromatic compound used for an organic electronic material, and the method produced by this method It is an object of the present invention to provide an aromatic compound with reduced halogen content. Furthermore, it aims at providing the organic electronics material containing the said aromatic compound, and the organic electronics element manufactured using this organic electronics material.

  As a result of intensive studies to solve the above problems, the inventors of the present invention reacted dehalogenation hydrogenation by reacting an aromatic halogen compound in the presence of a palladium (Pd) catalyst, a base and a solvent, and thus dehalogenation. It has been found that halogen-hydrogenated aromatic compounds can be obtained in high yield, and the present invention has been completed.

  That is, the present invention relates to the following manufacturing method.

(1) A process for producing an aromatic compound comprising the step of dehalogenating an aromatic halogen compound in the presence of a palladium catalyst, a base and a solvent.

(2) The method for producing an aromatic compound according to the above (1), wherein the palladium catalyst is a palladium complex and the ligand is a phosphine compound.

(3) The method for producing an aromatic compound according to the above (1) or (2), wherein the palladium catalyst is a palladium complex in which the ligand is tri-tert-butylphosphine.

(4) The manufacturing method of the aromatic compound in any one of said (1)-(3) whose said base is an organic base.

(5) The manufacturing method of the aromatic compound in any one of said (1)-(4) whose halogen atom of the said aromatic halogen compound is a bromine or an iodine.

(6) The method for producing an aromatic compound according to any one of the above (1) to (5), wherein the aromatic halogen compound is a product produced using another aromatic halogen compound as a raw material.

(7) The method for producing an aromatic compound according to (6), wherein the aromatic halogen compound which is the product is an oligomer or a polymer.

  Moreover, this invention relates to the aromatic compound manufactured by the manufacturing method of the aromatic compound in any one of (8) said (1)-(7).

  The present invention also relates to (9) an organic electronic material comprising the aromatic compound according to (8).

  Moreover, this invention relates to the organic electronics element produced using the organic electronics material as described in (10) said (9).

  According to the present invention, an aromatic compound containing no halogen atom can be obtained from the aromatic halogen compound in a high yield. Moreover, the aromatic compound whose halogen atom content was reduced rather than the aromatic halogen compound which is a raw material can be obtained efficiently as a reaction product. In particular, even when the aromatic halogen compound remains in part of a polymer material such as an oligomer or a polymer, the halogen atom content can be easily reduced. The aromatic compound whose halogen atom content is reduced by the production method of the present invention is useful as an organic electronic material.

It is a ¹ H-NMR spectrum of N, N'-bis (4-bromophenyl) -N, N'-bis (4-tolyl) benzidine which is a raw material of Example 1 of the present invention. N, N'-bis (4-bromophenyl) -N, N'-bis (4-tolyl) benzidine, a dehalogenated hydride N, N'-diphenyl-N, N'-bis (4-tolyl ¹ ) ¹ H-NMR spectrum of benzidine.

  The aromatic halogen compound in the present invention is not particularly limited as long as it is a compound having a structure in which a halogen atom is directly chemically bonded to an atom constituting the ring of the aromatic compound. Examples of the above-mentioned "atom which constitutes a ring of an aromatic compound" include a carbon atom which constitutes a benzene ring. The number of benzene rings may be one or two or more, and the benzene ring may be a fused cyclic structure like a naphthalene ring. Moreover, as long as it has aromaticity, a ring structure is not limited to a benzene ring, A heterocyclic type may be sufficient, 5 membered rings other than a 6-membered ring, 7 membered ring, etc. may be sufficient. Furthermore, only one aromatic halogen compound may be used, or two or more different aromatic halogen compounds may be used in combination.

  The aromatic halogen compound may be a derivative, for example, having a nitrogen atom or an oxygen atom as in an aromatic amine, or being substituted by an organic group such as an aliphatic hydrocarbon group or the like It is also good.

  The aromatic halogen compound may be a polymer or a monomer, or may be a product such as a polymer produced using another aromatic halogen compound as a raw material. In the case of a polymer, it may be a low molecular weight compound such as an oligomer or a high molecular weight compound (polymer). In the case of a polymer, the aromatic halogen compound may be all or part of the monomers constituting the polymer. In particular, when the aromatic halogen compound remains in part of the polymer-based material, it is difficult to separate and reduce the halogen atoms by the conventional purification method, so the method of the present invention is useful. Thereby, the halogen atom content of the polymer compound can be reduced.

  In the present invention, "dehalogenation hydrogenation" refers to reacting at least a part of an organic compound containing a halogen atom to obtain an organic compound not containing a halogen atom. As an organic compound which does not contain a halogen atom, the compound which the halogen atom in the organic compound containing the said halogen atom substituted by the hydrogen atom is mentioned.

  As the aromatic halogen compound, for example, (1) a raw material for preparing the target aromatic compound, (2) a halogen atom is substituted to the aromatic compound in the course of preparing the target aromatic compound Examples include intermediates that are structures, or (3) intermediates that remain in the target aromatic compound.

  In the case of (3), the remaining intermediate may be used together with the target aromatic compound in the production method of the present invention, or only the intermediate may be taken out and used.

  From the above, as specific aromatic halogen compounds, for example, halides of aromatic hydrocarbons such as aromatic amines and derivatives thereof; halides of condensed ring aromatic compounds such as naphthalene, anthracene and pyrene; carbazole, pyridine And halides of heterocyclic compounds such as thiophene and imidazole; derivatives thereof, and oligomers or polymers containing these in a part of the structure.

  The halogen atom contained in the aromatic halogen compound is preferably bromine or iodine in terms of high activity for the coupling reaction, and more preferably bromine in terms of abundant species as a raw material compound. A single molecule may have a plurality of the same or different halogen atoms.

  As a palladium catalyst used for this invention, a palladium (0) complex or palladium (II) salt is preferable, More preferably, it is a palladium (0) complex. The palladium catalyst may be used in the process of the present invention in the form of a solution in a solvent.

  When the palladium catalyst is a solution, a solvent common to the solvent used for the dehalogenation hydrogenation reaction may be used. Furthermore, if the solution after preparation of the palladium catalyst contains a sufficient amount of a solvent for the dehalogenation hydrogenation reaction, it is not necessary to add a separate solvent in the dehalogenation hydrogenation reaction using this palladium catalyst solution.

Preferred specific palladium complexes include, for example, tetrakis (triphenylphosphine) palladium (0), tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium (0) chloroform adduct, acetic acid Palladium (II) or palladium (II) chloride, (bicyclo [2.2.1] hepta-2,5-diene) dichloropalladium (II), (2,2'-bipyridyl) dichloropalladium (II), bis ( Acetate) Bis (triphenylphosphine) palladium (II), bis (acetonitrile) chloronitropalladium (II), bis (benzonitrile) dichloropalladium (II), bis (acetonitrile) dichloropalladium (II), bis [1,2] -Bis (diphenylphosphino) ethane] palladium (0 [1,2-bis (diphenylphosphino) ethane] dichloropalladium (II), trans-dibromobis (triphenylphosphine) palladium (II), dichloro (1,5-cyclooctadiene) palladium (II), dichloro ( Ethylenediamine) palladium (II), dichloro (N, N, N ′, N′-tetramethylenediamine) palladium (II), dichloro (1,10-phenanthroline) palladium (II), cis-dichlorobis (dimethylphenylphosphine) palladium (II), dichlorobis (methyldiphenylphosphine) palladium (II), dichlorobis (tricyclohexylphosphine) palladium (II), dichlorobis (triethylphosphine) palladium (II), dichlorobis (triphenylphosphine) palladium (II), dichloro Lobis (tri-ortho-toluylphosphine) palladium (II), palladium (II) acetylacetonate, palladium (II) bromide, palladium (II) hexafluoroacetylacetonate, palladium (II) iodide, palladium nitrate (II) ), Palladium sulfate, trifluoroacetate palladium (II), potassium palladium chloride (IV), potassium palladium bromide (II), potassium palladium chloride (II), sodium chloride palladium (II), tetraammine palladium nitrate (II), tetrakis (Acetonitrile) palladium (II) tetrafluoroborate, tetrakis (methyl diphenyl phosphine) palladium (0) and the like.
These may be used alone or in combination of two or more.

  It is more preferable that the ligand of the palladium complex contains a phosphine compound from the viewpoint of steric hindrance which affects the catalytic activity of the coupling reaction and the high extensibility of molecular design, and the ligand of the palladium complex is phosphine It is more preferable that it is a compound.

The phosphine compound used for the ligand is particularly a compound represented by the general formula R ¹ R ² R ³ P (wherein R ¹ , R ² and R ³ are each independently a hydrogen atom or an organic group). There is no limitation, and for example, triphenyl phosphine, tri-ortho-tolyl phosphine, tri-meta-tolyl phosphine, tri-para-tolyl phosphine, tris (pentafluorophenyl) phosphine, tris (para-fluorophenyl) phosphine, tris ( Ortho-methoxyphenyl) phosphine, tris (meth-methoxyphenyl) phosphine, tris (para-methoxyphenyl) phosphine, tris (2,4,6-trimethoxyphenyl) phosphine, tri (meth-chlorophenyl) phosphine, tri (para) -Chlorophenyl) phosphine, tricyclo Xyl phosphine, tri-tert-butyl phosphine, tri-n-butyl phosphine, tri-2-furyl phosphine, 2- (dicyclohexylphosphino) biphenyl, 2- (di-tert-butylphosphino) biphenyl, 2-di- tert-Butylphosphino-2'-methylbiphenyl, 2- (dicyclohexylphosphino-2 ', 6'-dimethoxy-1,1'-biphenyl, 2- (dicyclohexylphosphino) -2'-(N, N-) Dimethylamino) biphenyl, 2-dicyclohexylphosphino-2'-methyl-biphenyl, and 2- (dicyclohexylphosphino) -2 ', 4', 6'-tri-isopropyl-1,1'-biphenyl etc. may be mentioned. These may be used alone or in combination of two or more. Various phosphine compounds listed as "supporting ligands" in the publication 3366 can also be used.

  Among the phosphine compounds, those which are bulky and have a high electron donating property are more preferable, and in particular, tri-ortho-tolyl phosphine, tris (2,4,6-trimethoxyphenyl) phosphine, tri from the viewpoint of high activity of dehalogenation reaction. Cyclohexyl phosphine and tri-tert-butyl phosphine are preferred, and among these, tri-tert-butyl phosphine is particularly preferred.

  In the case where the ligand of the palladium complex does not contain phosphine, as the compound to be a ligand (hereinafter referred to as a compound for a ligand), at least one of the phosphine compounds is not contained in the ligand It is preferable to use in combination with a palladium complex. In this case, the phosphine compound may be the above-mentioned phosphine compound, and the preferable phosphine compound is also the same as the above-mentioned preferable phosphine compound.

  Thereby, the palladium complex not containing phosphine can be used as a catalyst palladium source to catalyze the dehalogenation hydrogenation reaction similarly to a complex in which the compound for ligand is a ligand. Specifically, a palladium complex containing no phosphine in a ligand and a compound for a ligand may be mixed in advance, or both may be added into the dehalogenation hydrogenation reaction system.

Preferred examples of the palladium complex (or palladium source) when the ligand does not contain phosphine include tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium (0) chloroform adduct, And palladium (II) acetate and the like. Also, palladium complexes having a heterocyclic carbene ligand may be used.
More preferably, tris (dibenzylideneacetone) dipalladium (0) is mentioned. These palladium complexes may be used alone or in combination of two or more.

As a usage-amount of a palladium catalyst, 1 x 10 < ^-6 > mol-0.5 mol etc. of palladium catalysts can be mentioned, for example with respect to 1 mol of aromatic halogen compounds. More preferably, it is 1 × 10 ⁻⁵ moles to 1 × 10 ⁻² moles of the palladium catalyst with respect to 1 mole of the aromatic halogen compound. If it is 1 * 10 < ^-6 > mol or more, reaction will be enough, and if it is 0.5 mol or less, it can be made to react efficiently.

  As a usage-amount of the palladium catalyst in the case of using the compound for ligands together, 0.1 mol-10 mol etc. of compounds for ligands can be mentioned, for example with respect to 1 mol of palladium catalysts. More preferably, it is 1 mol to 8 mol of a compound for a ligand per 1 mol of a palladium catalyst.

  The base used in the present invention includes a substance to be a hydroxide ion source and a Lewis base which produces a substance to be a hydroxide ion source in combination with water.

  Among the bases, as the inorganic base, an aqueous solution of an inorganic acid salt of an alkali metal, for example, an aqueous solution of an alkali metal carbonate such as sodium carbonate and potassium carbonate; an alkali metal water such as sodium hydroxide, potassium hydroxide and lithium hydroxide An aqueous solution of oxide is exemplified. Examples of organic bases include aqueous solutions of quaternary ammonium hydroxides such as tetramethyl ammonium hydride and tetraethyl ammonium hydride.

  Preferably, it is an aqueous solution of alkali metal hydroxide or an aqueous solution of quaternary ammonium hydroxide. From the viewpoint of reactivity, organic bases such as quaternary ammonium hydroxides are more preferred. The base may be a single one or a mixture of different types of bases.

  The amount of the base used is at least the equivalent, preferably 1 to 10 equivalents of the base relative to the number of moles of the aromatic halide. The higher the base concentration, the easier the dehalogenation hydrogenation reaction proceeds. Preferably it is 0.01 M or more, More preferably, it is 0.1 M or more, More preferably, it is 0.5 M or more.

  In the production method of the present invention, a phase transfer catalyst may be used in combination with a palladium catalyst. Examples of phase transfer catalysts include quaternary ammonium and its salts, phosphonium salts, crown ethers, and cryptands. Preferred phase transfer catalysts include, for example, ammonium tetraalkyl halides, ammonium tetraalkyl hydrogen sulfate, and tetraalkyl ammonium hydroxide.

  The amount of the phase transfer catalyst used is, for example, preferably at least 0.001 mol, more preferably 0.01 mol to 1 mol, per 1 mol of the aromatic halogen compound used in the present invention. If the amount is 0.001 mol or more, the reaction sufficiently occurs.

  The solvent used in the present invention is a solvent in which the aromatic halogen compound is dissolved, and is not particularly limited as long as it does not inhibit the reaction. Examples of the solvent include alcohols such as methanol, ethanol and isopropyl alcohol; alkanes such as pentane, hexane and octane; cyclic alkanes such as cyclohexane; benzene, toluene, aromatic hydrocarbons such as xylene, mesitylene, tetralin and diphenylmethane; Aliphatic ethers such as glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate; 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene Aromatic ethers such as 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole; ethyl acetate, n-butyl acetate, ethyl lactate, n-bu lactate Aliphatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, n-butyl benzoate and other aromatic esters; N, N-dimethylformamide, N, N-dimethylacetamide Amide solvents such as; dimethyl sulfoxide, tetrahydrofuran, acetone, chloroform, methylene chloride and the like. Preferred are aromatic hydrocarbons, aliphatic esters, aromatic esters, aliphatic ethers, and aromatic ethers. These may be used alone or in combination of two or more.

  Not only the solvent in the dehalogenation hydrogenation reaction, but also the solvent used in separately preparing the palladium catalyst may be the one mentioned above. In either case, it is preferable to use after degassing with nitrogen bubble beforehand.

  In the dehalogenation hydrogenation reaction, a mixture of an aromatic halogen compound, a palladium catalyst, a base and a solvent is preferably reacted by heating under reflux. The reaction temperature is usually selected in the range of 50 to 200 ° C., preferably 70 to 150 ° C. The reaction time is usually selected in the range of 1 to 48 hours, preferably 2 to 24 hours. Furthermore, it is preferable to carry out the reaction under a nitrogen stream or an argon stream.

  After completion of the dehalogenation hydrogenation reaction, the reaction product is preferably washed with water, and the solvent is preferably removed and dried.

By the above reaction, a hydrogen atom is substituted at the position of the halogen atom in the aromatic halogen compound. As an example, the outline of the reaction for dehydrohalogenating N, N'-bis (4-bromophenyl) -N, N'-bis (4-tolyl) benzidine is shown in the following reaction formula (1).

  The aromatic compound reduced in halogen atom by the above manufacturing method is used as it is or mixed with other raw materials for an organic electronic material. Organic electronic devices are produced from organic electronic materials.

  For example, in the case of an organic thin film EL device, a hole injection layer of an organic compound, a hole transport layer, a light emitting layer, an electron injection layer, and the like are included between two electrodes. The aromatic compound or the organic electronic material of the present invention may be used in any of these layers.

  Hereinafter, the embodiments of the present invention will be described by way of examples, but the present invention is not limited to these examples. In addition, "ml" is described as "mL" below.

(Preparation of palladium catalyst)
In a glove box under a nitrogen atmosphere, weigh tris (dibenzylideneacetone) dipalladium (73.2 mg, 80 μmol) into a sample tube at room temperature, add anisole (15 mL) and stir for 30 minutes to give solution 1 Obtained. Similarly, tri-tert-butylphosphine (129.6 mg, 640 μmol) was weighed into another sample tube, anisole (5 mL) was added and stirred for 5 minutes to obtain solution 2. The solution 1 and the solution 2 were mixed and stirred at room temperature for 30 minutes to obtain an anisole solution (4 mM) of a palladium catalyst. The above-mentioned anisole was used after being deaerated beforehand by nitrogen bubble for 30 minutes or more, and all the above operations were performed under nitrogen stream.

Example 1
In a three-necked round-bottomed flask, N, N'-bis (4-bromophenyl) -N, N'-bis (4-tolyl) benzidine (8 mmol) and anisole (20 mL) degassed beforehand by nitrogen bubble for at least 30 minutes. Was added under a nitrogen stream, and the palladium catalyst solution (1.0 mL, 4 μmol) prepared above was further added to obtain a mixture 1. In addition, until the completion of heating and reflux described later, all operations were performed under a nitrogen stream.

  The mixture 1 was stirred for 30 minutes, and then a 10% aqueous solution of tetraethylammonium hydroxide (12 mL) previously degassed by nitrogen bubble for 30 minutes or more was added to obtain a mixture 2.

  The mixture 2 was heated under reflux at 95 ° C. for 2 hours under a nitrogen stream to cause a dehalogenation reaction.

After completion of the reaction, the aqueous phase was removed from the reaction system, and after washing the organic phase with water, the solvent was removed to recover the product. The product was confirmed to be N, N′-diphenyl-N, N′-bis (4-tolyl) benzidine by mass measurement and NMR measurement of the product. The recovery rate was also found to be 100%. The outline of the above reaction is shown in the following reaction formula (1).

The ¹ H-NMR spectrum of N, N′-bis (4-bromophenyl) -N, N′-bis (4-tolyl) benzidine, which is a raw material of this example, is shown in FIG. 1. Further, ¹ H-NMR spectrum of N, N′-diphenyl-N, N′-bis (4-tolyl) benzidine is shown in FIG. 2. From the result of ¹ H-NMR measurement of the obtained product, it was confirmed that the signal from the raw material was not contained in the product.

(Example 2)
The reaction was carried out in the same manner as in Example 1 except that the solvent anisole (15 mL + 5 mL) used in the catalyst preparation and the solvent anisole (20 mL) used in the dehalogenation reaction were each changed to the same amount of toluene. . According to mass measurement and NMR measurement of the product, the product is the same N, N'-diphenyl-N, N'-bis (4-tolyl) benzidine as in Example 1, and the recovery rate is 100%. The

(Example 3)
The reaction was performed in the same manner as in Example 1 except that the solvent anisole (20 mL) for the dehalogenation reaction was changed to THF (tetrahydrofuran) (20 mL). After completion of the reaction, the reaction solution was dropped into water and reprecipitated. As a result of collecting the formed precipitate, the product was the same N, N'-diphenyl-N, N'-bis (4-tolyl) benzidine as in Example 1, and the recovery rate was 74%.

(Example 4)
In the same manner as in Example 1, except that the raw material N, N'-bis (4-bromophenyl) -N, N'-bis (4-tolyl) benzidine was changed to 1-bromonaphthalene (8 mmol) The reaction was done. According to mass measurement and NMR measurement of the product, the products were naphthalene (65.6%) and unreacted 1-bromonaphthalene (34.4%).

The outline of the above reaction is shown in the following reaction formula (2).

  It was confirmed from Examples 1 to 4 that the aromatic halogen compounds could be dehalogenated and hydrogenated in a high yield.

(Example of synthesis of aromatic halogen compound polymer)
Polymers of aromatic halogen compounds were synthesized by the following procedure. The outline of the synthesis is shown in the following reaction formula (3).

  In a three-necked round bottom flask, Monomer 1 (2.0 mmol, 0.964 g), Monomer 2 (5.0 mmol, 2.767 g) and Monomer 3 (4.0 mmol, 541 g) and anisole (20 mL) were added under a nitrogen stream, and further, the palladium catalyst solution (7.5 mL, 3 μmol) prepared above was added to obtain a mixture 1. In addition, until the completion of heating and reflux described later, all operations were performed under a nitrogen stream.

After stirring mixture 1 for 30 minutes, 1 M aqueous potassium carbonate solution (230 mL) was added to obtain mixture 2. The solvents anisole and potassium carbonate aqueous solution were used after degassing with nitrogen bubble for 30 minutes or more in advance. The mixture 2 was heated under reflux at 95 ° C. for 2 hours to synthesize a polymer.

  After completion of the reaction, the aqueous phase was removed from the reaction system, the organic phase was washed with water, and the organic phase was poured into methanol-water (volume ratio 9: 1). The resulting precipitate was suction filtered and washed with methanol-water (volume ratio 9: 1). The obtained precipitate was dissolved in toluene, dropped into methanol and reprecipitated. The resulting precipitate was suction filtered, dissolved in toluene, triphenylphosphine polymer-bound styrene-divinylbenzene copolymer (Strem Chemicals, 200 mg per 100 mg of polymer) was added and stirred overnight. After completion of the stirring, unreacted triphenylphosphine polymer-bound styrene-divinylbenzene copolymer and insoluble matter were removed by filtration, and the filtrate was dropped into methanol-acetone (volume ratio 8: 3) to reprecipitate. The resulting precipitate was suction filtered and washed with methanol-acetone (volume ratio 8: 3). The resulting precipitate was dried under vacuum to obtain a polymer containing aromatic halogen compound sites.

  It was 42,000 when the weight average molecular weight of the obtained polymer was measured by GPC (polystyrene conversion) which used THF for the eluting solvent.

  Using this polymer as a sample, 20 mg is heated and burned by an automatic sample combustion device for ion chromatography pretreatment (Mitsubishi Chemical Analytech Co., Ltd. Model No. AQF-100), the product gas is absorbed into the absorbing solution, and then the combustion ion chromatograph As a result of quantifying the amount of ions in the absorbing liquid with (Dionex Co., Ltd., Model No. ICS-1600), the amount of Br in the polymer was 1400 ppm.

  Also, 300 mg of the polymer sample and ultrapure water were placed in a fluorine resin container, and kept at 100 ° C. for 2 hours, and filtration was performed. The filtrate was measured with an ion chromatograph (Model No. ICS-2000 manufactured by Dionex). It was found that the amount of free Br ions contained in is 10 ppm or less.

  From the above two measurement results, it is inferred that Br contained in the polymer sample is present in a state of being chemically bonded to the polymer.

(Example 5)
The polymer sample (0.75 g) and toluene (14.7 mL) prepared above were added to a three-necked round bottom flask under nitrogen stream, and 20% aqueous tetraethylammonium hydroxide solution (9.0 mL) was further added. In addition, until the completion of heating and reflux described later, all operations were performed under a nitrogen stream. Further, the palladium catalyst solution prepared above (0.4 mL, 1.6 μmol) was added. The above-mentioned toluene and 20% aqueous solution of tetraethylammonium hydroxide were used after degassing with nitrogen bubble for 30 minutes or more in advance. The mixture was heated under reflux at 95 ° C. for 2 hours under reflux to carry out a dehalogenation reaction.

  Using this dehydrohalogenated polymer as a sample, 20 mg is heated and burned by the above-mentioned automatic sample burner for ion chromatography pretreatment, the product gas is absorbed in the absorbing liquid, and then the above-mentioned combustion ion chromatograph As a result of quantifying the amount of ions in the absorbent, the amount of Br in this polymer sample was 7 ppm. From the above, it was confirmed that the Br content of the polymer containing the aromatic halogen compound site was significantly reduced by the dehydrohalogenation.

Claims (7)

Comprising the step of dehalogenating aromatic halogen compounds palladium catalyst, a base and in the presence of a solvent, wherein the aromatic halogen compound is an aromatic amine compound, wherein the palladium catalyst is a palladium complex ligand is a phosphine A method for producing an aromatic compound, which is a compound, and wherein the dehalogenation step is a step of replacing a halogen atom of the aromatic halogen compound with a hydrogen atom, and the base contains a quaternary ammonium hydroxide. Comprising the step of dehalogenating aromatic halogen compounds palladium catalyst, a base and in the presence of a solvent, the palladium catalyst, the ligand is a palladium complex is a tri -tert- butylphosphine, wherein the step of dehalogenation Is a step of replacing a halogen atom of the aromatic halogen compound with a hydrogen atom, and the method for producing an aromatic compound, wherein the base contains a quaternary ammonium hydroxide.   The manufacturing method of the aromatic compound of Claim 1 or 2 whose halogen atom of the said aromatic halogen compound is a bromine or an iodine.   The method for producing an aromatic compound according to any one of claims 1 to 3, wherein the aromatic halogen compound is a product produced using another aromatic halogen compound as a raw material.   The method for producing an aromatic compound according to claim 4, wherein the product aromatic halogen compound is an oligomer or a polymer.   The manufacturing method of the aromatic compound in any one of Claims 1-5 whose said palladium complex is a palladium (0) complex. The method for producing an aromatic compound according to any one of claims 1 to 6, wherein the dehalogenation is a reaction substantially free of hydrogen gas.