JPWO2013179872A1 - ETHER COMPOUND AND METHOD FOR PRODUCING THE COMPOUND - Google Patents

Abstract

An ether compound having a specific structure useful as a raw material for producing a functional polymer material or a functional electronic material, and a method for producing the compound. A compound represented by the general formula (1) and a method for producing the compound. (Wherein, A1 and A2 each independently represents a nitro group or an amino group)

Description

The present invention relates to an ether compound having a novel structure.
More specifically, various functional polymer materials (for example, polyimide, polyamide, polycarbodiimide) and various functional electronic materials (for example, organic electroluminescent element material, organic transistor element material, photoelectric conversion element material) The present invention relates to an ether compound useful as a compound and a method for producing the compound.

  In recent years, various functional polymer materials and various functional electronic materials have been actively developed in accordance with social needs. As various functional polymer materials, for example, various polyimides, polyamides, polycarbodiimides, and the like have been developed. Various amine compounds have been proposed as raw materials for producing polyimides having various characteristics. For example, 4,4′-bis (aminophenoxy) diphenylsulfone and 4,4′-bis (aminophenoxy) benzophenone are useful. It is reported that it is a compound (nonpatent literature 1).

  Various amine compounds having an ether bond in the molecule, such as 4,4′-bis (aminophenoxy) biphenyl, 1,3-bis (aminophenoxy) benzene, and 1,4-bis (aminophenoxy) benzene, are also available. It has been reported that it is a compound useful as a raw material for producing polyimide (Non-Patent Document 1). At present, in the field of using various functional polymer materials, improvement of various properties is desired, and in order to improve the properties, a new amine compound is required as a raw material for production.

Various amine compounds are known to be useful as various functional electronic materials (for example, organic electroluminescent element materials, organic transistor element materials, photoelectric conversion element materials).
As organic electroluminescent element materials, amine compounds are known to be useful as, for example, hole injection transport materials and light emitting materials (Non-patent Document 2).
Moreover, as an organic transistor element material, an amine compound is known to be useful as, for example, a p-type organic transistor material (Non-Patent Documents 3 and 4). Furthermore, amine compounds are known to be useful as photoelectric conversion element (organic solar battery) materials (Non-Patent Document 5).
In the field of these various functional electronic materials, further improvement of characteristics is desired, and accordingly, creation of new organic materials is required.

Polymer, 37, 3683 (1996) J. Mater. Chem., 10, 1 (2000) Chem. Rev., 107, 1066 (2007) Angew.Chem.Int.Ed., 47, 4070 (2008) Chem. Rev., 110, 6689 (2010)

An object of the present invention is to provide an ether compound having the specific structure. More specifically, the present invention provides a compound having an ether bond and a nitro group in the molecule, a compound having an ether bond and an amino group in the molecule, and a method for producing the compound.

(式中、Ａ_１およびＡ_２はそれぞれ独立に、ニトロ基またはアミノ基を表す)As a result of intensive studies on various compounds, the present inventors have completed the present invention. That is, the present invention
(I) a compound represented by the general formula (1),

(In the formula, A ₁ and A ₂ each independently represent a nitro group or an amino group)

(Ii) In the general formula (1-A), the compound represented by the formula (2) is reacted with at least one compound selected from dinitrobenzene and halogenated nitrobenzene in the presence of a base. A method for producing the compound represented,

(Iii) The present invention relates to a method for producing a compound represented by the general formula (1-B) comprising reacting a compound represented by the general formula (1-A) and a hydrogen source in the presence of a catalyst.

According to the present invention, various functional polymer materials (for example, polyimide, polyamide, polycarbodiimide) and various functional electronic materials (for example, organic electroluminescent element material, organic transistor element material, photoelectric conversion element material) are manufactured. It has become possible to provide an ether compound that is a useful raw material and a method for producing the compound.

(式中、Ａ_１およびＡ_２はそれぞれ独立に、ニトロ基またはアミノ基を表す)Hereinafter, the present invention will be described in detail.
The present invention is a compound represented by the general formula (1).

(In the formula, A ₁ and A ₂ each independently represent a nitro group or an amino group)

In the compound represented by the general formula (1), A ₁ and A ₂ each independently represent a nitro group or an amino group, and more preferably, A ₁ and A ₂ simultaneously represent a nitro group or an amino group. In the compound represented by the general formula (1), A ₁ and A ₂ each independently represent an ortho position, a meta position, or a para position with respect to the ether bond (—O—), and more preferably, It represents the meta position or the para position, and more preferably, A ₁ and A ₂ simultaneously represent the meta position or the para position.

一般式(１−Ａ)で表される化合物において、ニトロ基は、エーテル結合
（−Ｏ−）に対して、オルト位、メタ位またはパラ位を表し、より好ましくは、二つのニトロ基は同時に、メタ位またはパラ位を表す。
一般式(１−Ｂ)で表される化合物において、アミノ基は、エーテル結合
（−Ｏ−）に対して、オルト位、メタ位またはパラ位を表し、より好ましくは、二つのアミノ基は同時に、メタ位またはパラ位を表す。The compound represented by the general formula (1) is more preferably a compound represented by the general formula (1-A) or the general formula (1-B).

In the compound represented by the general formula (1-A), the nitro group represents an ortho position, a meta position or a para position with respect to the ether bond (—O—), and more preferably, the two nitro groups are simultaneously formed. , Represents a meta position or a para position.
In the compound represented by the general formula (1-B), the amino group represents an ortho position, a meta position, or a para position with respect to the ether bond (—O—), and more preferably, the two amino groups are simultaneously formed. , Represents a meta position or a para position.

In the general formula (1), regarding the method for producing the compound represented by the general formula (1-A) in which A ₁ and A ₂ are simultaneously nitro groups, the compound represented by the formula (2) in the presence of a base And at least one compound selected from dinitrobenzene and halogenated nitrobenzene can be produced.

The compound represented by the formula (2) can be produced, for example, by reacting 1,3-bis (4′-methoxyphenyl) benzene with hydriodic acid or boron tribromide [for example, J. Amer. Chem. Soc., 66, 628 (1944),
The method described in J. Mater. Chem., 9, 661 (1999), J. Med. Chem., 51, 6725 (2008) can be referred to].

Specific examples of dinitrobenzene include 1,2-dinitrobenzene, 1,3-dinitrobenzene, and 1,4-dinitrobenzene, and 1,3-dinitrobenzene and 1,4-dinitrobenzene are preferred.
Specific examples of the halogenated nitrobenzene include chloronitrobenzene, bromonitrobenzene and fluoronitrobenzene, chloronitrobenzene and fluoronitrobenzene are preferred, and chloronitrobenzene is more preferred.

  Preferable specific examples of the halogenated nitrobenzene include, for example, 2-chloronitrobenzene, 3-chloronitrobenzene, 4-chloronitrobenzene, 2-bromonitrobenzene, 3-bromonitrobenzene, 4-bromonitrobenzene, 2-fluoronitrobenzene, 3-fluoro Examples thereof include nitrobenzene and 4-fluoronitrobenzene.

In the compound represented by the general formula (1-A), when a compound in which the nitro group is in the meta position with respect to the ether bond is produced, it is more preferably represented by the formula (2) in the presence of a base. The compound is reacted with dinitrobenzene.
Moreover, in the compound represented by the general formula (1-A), when a compound in which the nitro group is ortho or para to the ether bond is produced, more preferably, in the presence of a base, the formula (2) Is reacted with a halogenated nitrobenzene.

  The amount of dinitrobenzene and halogenated nitrobenzene used in the production of the compound represented by the general formula (1-A) is generally the compound represented by the formula (2) when only one kind of the compound is reacted. About 1.8 to 2.2 mol, more preferably about 1.9 to 2.1 mol, and still more preferably about 1.95 to 2.05 mol are used with respect to 1 mol. Moreover, when making it react by selecting 2 types from the said compound, it is about 0.8-1.2 mol respectively with respect to 1 mol of compounds represented by Formula (2), More preferably, it is 0.9-1 About 0.1 mol, more preferably about 0.95 to 1.05 mol is used.

As the base used in the production of the compound represented by the general formula (1-A),
For example, inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium phosphate, potassium phosphate, sodium bicarbonate, potassium bicarbonate,
For example, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium tert-butoxide, potassium tert-butoxide, sodium (2,4,6-tri-tert-butylphenolate), potassium (2 , 4,6-tri-tert-butylphenolate), potassium (2,6-di-tert-butyl-4-methylphenolate) and the like,
For example, sodium acetate, potassium acetate, triethylamine, triisopropylamine, tri-n-butylamine, diisopropylethylamine, pyridine, quinoline, picoline, tetra-n-butylammonium bromide, 1,8-diazabicyclo [5.4.0]- And organic bases such as 7-undecene (DBU), 1,5-diazabicyclo [4.3.0] -5-nonene (DBN), N, N, N ′, N′-tetramethylethylenediamine, and the like. More preferably, it is an inorganic base.
Such bases may be used alone or in combination. The amount of the base used is generally 0.8 to 4.0 equivalents, preferably 1.0 to 3.0 equivalents, based on the total amount of dinitrobenzene and halogenated nitrobenzene used.

The production of the compound represented by the general formula (1-A) can be carried out in the absence of an organic solvent, but is preferably carried out in the presence of an organic solvent.
Examples of the organic solvent include aliphatic hydrocarbon solvents such as pentane, hexane, octane, and cyclohexane,
For example, aromatic hydrocarbon solvents such as benzene, toluene, o-xylene, m-xylene, p-xylene, mixed xylene, mesitylene, cumene, pseudocumene, tetralin,
For example, ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diisopropyl ether, diisobutyl ether, cyclopentyl methyl ether, anisole, diphenyl ether,
For example, dimethyl sulfoxide, dimethyl sulfone, sulfolane, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3 -Organic solvents such as aprotic polar solvents such as diethyl-2-imidazolidinone, 1,3-di-n-butyl-2-imidazolidinone, hexamethylphosphoramide, acetonitrile, propionitrile, butyronitrile More preferred are aprotic polar solvents.
These organic solvents may be used alone or in combination.

In the production of the compound represented by the general formula (1-A), the amount of the organic solvent used is not particularly limited, but generally the concentration of the compound represented by the formula (2) is 0.05 to 6M. The amount is adjusted to about 0.08 to 5M.
In addition, when manufacturing the compound represented with general formula (1-A) using an inorganic base as a base, it is preferable to implement reaction, distilling the water to produce | generate out of a reaction system.

In the production of the compound represented by the general formula (1-A), the method for supplying the compound represented by the formula (2), dinitrobenzene and halogenated nitrobenzene, base, and organic solvent is not particularly limited. But for example
(A) A method of supplying dinitrobenzene and / or halogenated nitrobenzene to a mixture of a compound represented by formula (2) and a base in the presence of an organic solvent,
(A) a method of supplying a compound represented by the formula (2) and a base to dinitrobenzene and / or halogenated nitrobenzene in the presence of an organic solvent;
(C) In the presence of an organic solvent, a method of supplying a compound represented by the formula (2), dinitrobenzene and / or halogenated nitrobenzene and a base in a lump can be exemplified.
Thus, the compound represented by the general formula (1-A) is reacted with the compound represented by the formula (2) and at least one selected from dinitrobenzene and halogenated nitrobenzene in the presence of a base. However, when halogenated nitrobenzene is used, a metal compound may be present if desired.

The metal compound is preferably a metal compound selected from Groups 10 to 11 of the periodic table, more preferably a copper compound, a palladium compound, or a nickel compound, and still more preferably a copper compound, or It is a palladium compound.
Examples of the metal compound include a zero-valent metal or a metal compound containing a monovalent to divalent metal ion, more preferably a copper containing a copper atom or a copper ion in the molecule. Compound, palladium compound containing palladium atom or palladium ion in the molecule, or nickel compound containing nickel atom or nickel ion in the molecule, more preferably copper atom or copper ion in the molecule It is a copper compound containing, or a palladium compound containing palladium atoms or palladium ions in the molecule.

  Examples of such metal compounds include metal copper, cuprous chloride, cuprous bromide, cuprous iodide, cuprous oxide, cuprous acetate, cupric chloride, cupric bromide, iodine. Cupric oxide, cupric oxide, cupric acetate, copper sulfate, copper carbonate, copper trifluoromethanesulfonate, benzene complex of copper trifluoromethanesulfonate, bis (2,4-pentanedionate) copper, bis ( (Trifluoro-2,4-pentanedionate) copper, bis (hexafluoroacetylacetonate) copper, copper gluconate, copper benzoate, copper naphthenate, monobutyl copper phthalate, copper diethyldithiocarbamate,

Or, for example, palladium chloride, paradium bromide, palladium iodide, paradium acetate, bis (2,4-pentadionato) palladium, bis (dibenzylideneacetone) palladium, bis (benzonitrile) palladium dichloride, allyl palladium chloride. Inorganic such as dimer, K ₂ PdCl ₄ , K ₂ PdCl ₆ , K ₂ Pd (NO ₃ ) ₄ , tris (dibenzylideneacetone) dipalladium, dichlorobis (ethylene) palladium, Pd (π-C ₅ H ₅ ) ₂ , Organic coordination complexes,
For example, N-coordination complexes such as bis (ethylenediamine) palladium dichloride, PdCl ₂ (NH ₃ ) ₂ , PdCl ₂ [N (C ₂ H ₅ ) ₃ ] ₂ , Pd (NO ₃ ) ₂ (NH ₃ ) ₆ ,
For example, bis [1,2-bis (diphenylphosphino) ethane] palladium, Pd [P (CH ₃ ) ₃ ] ₄ , Pd [P (C ₂ H ₅ ) ₃ ] ₄ , Pd [P (n-C _{3 H 7) 3] 4, Pd} [P (iso-C 3 H 7) 3] 4, Pd [P (n-C 4 H 9) 3] 4, Pd [P (tert-C 4 H 9) 3] _{4, Pd [P (Cyc-} C 6 H 11) 3] 4, Pd [P (C 6 H 5) 3] 4, Pd [P (o-CH 3 -C 6 H 4) 3] 4, PdCO 2 [P (C ₆ H ₅ ) ₃ ] ₄ , Pd (C ₂ H ₄ ) [P (C ₆ H ₅ ) ₃ ] ₂ , PdCl ₂ [P (C ₆ H ₅ ) ₃ ] ₂ , PdCl ₂ [P ( _{n-C 4 H 9) 3} ] 2, PdCl 2 [P (tert-C 4 H 9) 3] 2, PdBr 2 [P (C 6 H 5) 3] 2, PdBr 2 [P (n-C 4 H _{9) 3] , PdBr 2 [P (tert-} C 4 H 9) 3] 2, PdCl 2 [P (OCH 3) 3] 2, PdBr 2 [P (OCH 3) 3] 2, PdI 2 [P (OCH 3) 3 _{] 2, PdCl (C 6 H} 5) [P (C 6 H 5) 3] phosphine coordination complexes such as _2, more palladium compound such as Pd / carbon,

Further, for example, inorganic and organic coordination complexes such as nickel chloride, nickel bromide, bis (2,4-pentadionate) nickel, such as Ni [P (C ₆ H ₅ ) ₃ ] ₄ , NiCl ₂ [P A nickel compound such as a phosphine coordination complex such as (C ₆ H ₅ ) ₃ ] ₂ can be given. More preferred metal compounds are cuprous halides such as cuprous chloride, cuprous bromide and cuprous iodide, or inorganic and organic coordination complex palladium such as palladium acetate.
A metal compound may be used individually by 1 type, or may be used together. The amount of the metal compound used is not particularly limited, but is generally about 0.01 to 50 mol%, more preferably 0.1 to 30% with respect to the total amount of halogenated nitrobenzene. About mol%.

The reaction temperature for producing the compound represented by the general formula (1-A) is not particularly limited, but is generally about 20 to 220 ° C, preferably about 40 to 200 ° C, more preferably. Is carried out at about 50 to 180 ° C.
The reaction time for producing the compound represented by the general formula (1-A) is not particularly limited, but is generally about 1 to 40 hours, more preferably about 2 to 30 hours. can do.

The reaction for producing the compound represented by the general formula (1-A) can be carried out in an air atmosphere, but generally in the presence of an inert gas (for example, nitrogen, argon, helium). It is preferable to carry out.
In the production of the compound represented by the general formula (1-A), the reaction may be carried out under normal pressure, or, if desired, under reduced pressure or under pressure.

  The compound represented by the general formula (1-A) produced by such a method is isolated as a crystal in the presence of water after completion of the reaction, for example, after distilling off the organic solvent as necessary. be able to. Moreover, the compound represented by general formula (1-A) can be isolated and refine | purified by well-known methods, such as a recrystallization method and a chromatography method, as needed.

Incidentally, in the general formula (1), with respect to the method for producing a compound represented by the general formula A ₁ and A ₂ is an amino group at the same time (1-B), is not particularly limited, preferably, generally It can be produced by reducing the nitro group in the compound represented by the formula (1-A) and converting it to an amino group.

The production method of the compound represented by the general formula (1-B) is preferably a production method comprising reacting the compound represented by the general formula (1-A) with a hydrogen source (hydrogenation reaction). And
More preferably, it is a production method comprising reacting a compound represented by the general formula (1-A) with a hydrogen source in the presence of a catalyst.

  Examples of the hydrogen source include a combination of a protonic acid (for example, hydrogen chloride, hydrogen bromide) and a reducing agent (for example, iron, tin, stannous chloride, etc.). More preferably, The hydrogen source itself has a hydrogen supply capability, more preferably hydrogen or hydrazine, and more preferably hydrogen.

In addition, when using hydrogen as a hydrogen source, hydrogen may be used in a gaseous state and may be used in a solution state dissolved in an organic solvent.
The amount of the hydrogen source to be used is not particularly limited, but an amount sufficient to convert the nitro group in the compound represented by the general formula (1-A) into an amino group is used. However, in general, the hydrogen source is converted to 4 moles per mole of the compound represented by the general formula (1-A) in terms of 1 mole of hydrogen. About 8 mol is used, and more preferably about 6 mol is used.

  The catalyst is preferably a metal catalyst containing a metal atom selected from Groups 8 to 10 of the periodic table, more preferably an iron, rhodium, nickel, palladium, ruthenium, cobalt or platinum atom. And more preferably a palladium catalyst containing a palladium atom.

As the catalyst, it is preferable to use the metal atom in a form supported on a carrier such as carbon, alumina, silica, zeolite, barium sulfate or the like. Such catalysts include, for example, ferric chloride / activated carbon, palladium / carbon, palladium / alumina, palladium / barium sulfate, platinum, platinum oxide, platinum / carbon, platinum / silica, rhodium / carbon, rhodium / alumina, ruthenium / Carbon, Raney nickel, Raney cobalt and the like can be mentioned, and palladium catalysts such as palladium / carbon and palladium / alumina are more preferable.
The amount of the catalyst used is not particularly limited, but is generally about 0.01 to 40% by mass, more preferably 0.1 to 0.1% by mass with respect to the compound represented by the general formula (1-A). It is about 30% by mass.

When the compound represented by the general formula (1-A) and a hydrogen source are allowed to act in the presence of a catalyst, the reaction is preferably performed in the presence of an organic solvent.
Examples of the organic solvent include aliphatic hydrocarbon solvents such as pentane, hexane, octane, and cyclohexane,
For example, aromatic hydrocarbon solvents such as benzene, toluene, o-xylene, m-xylene, p-xylene, mixed xylene, mesitylene, cumene, pseudocumene, tetralin,
For example, alcohol solvents such as methanol, ethanol, isopropyl alcohol, butanol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol,
For example, ester solvents such as ethyl acetate, butyl acetate, amyl acetate,

For example, ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diisopropyl ether, diisobutyl ether, cyclopentyl methyl ether, anisole, diphenyl ether,
For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1, An organic solvent such as an aprotic polar solvent such as 3-di-n-butyl-2-imidazolidinone and hexamethylphosphoramide can be used.
These organic solvents may be used alone or in combination.
The amount of the organic solvent used is not particularly limited, but generally, the concentration of the compound represented by the general formula (1-A) is about 0.05 to 6M, more preferably 0.08. Prepare to an amount of about ~ 5M.

In the production of the compound represented by the general formula (1-B), the method for supplying the compound represented by the general formula (1-A), the catalyst, the organic solvent and the hydrogen source is not particularly limited. For example,
(D) A method of supplying a hydrogen source to a mixture of a compound represented by the general formula (1-A) and a catalyst in the presence of an organic solvent,
(E) A method of supplying a hydrogen source together with the supply of the compound represented by the general formula (1-A) in the presence of an organic solvent in advance.

Although it does not restrict | limit especially regarding the reaction temperature at the time of making the compound represented with general formula (1-A) and a hydrogen source act, Generally about 0-200 degreeC, Preferably, it is 10-150 degreeC About 20 degreeC, More preferably, it implements at about 20-120 degreeC.
Further, the reaction time when the compound represented by the general formula (1-A) and the hydrogen source are allowed to act is not particularly limited, but is generally about 1 to 100 hours, more preferably 2 It can be carried out in about 60 hours.
In addition, the reaction between the compound represented by the general formula (1-A) and the hydrogen source can be carried out together with the hydrogen source, for example, in the presence of an inert gas (for example, nitrogen, argon, helium).
When the compound represented by the general formula (1-A) and a hydrogen source are allowed to act, the reaction may be performed under normal pressure, or may be performed under reduced pressure or increased pressure as desired. is there.

Since the compound represented by the general formula (1-B) produced by such a method has an amino group in the molecule, for example, an acid (for example, hydrogen chloride, hydrogen bromide, sulfuric acid) And can be isolated as a salt (for example, hydrochloride, bromide, sulfate).
The salt of the compound represented by the general formula (1-B) is converted into the compound represented by the general formula (1-B) by the action of a base (for example, ammonia, sodium hydroxide, potassium hydroxide). And can be converted.
Moreover, the compound represented by general formula (1-B) can be isolated and refine | purified by well-known methods, such as a recrystallization method and a chromatography method, as needed.
In addition, the compound represented by the general formula (1-B) and a salt of the compound can be purified by the action of, for example, activated carbon or zeolite in the presence of an organic solvent and / or water.

In addition, the structure of the compound represented by general formula (1-A) and general formula (1-B) is elemental analysis, MS (FD-MS) analysis, IR analysis, ¹ H-NMR, ¹³ C-NMR, etc. These can be identified by various analysis methods.
In producing the compounds represented by the general formula (1-A) and the general formula (1-B), the type and form of the reaction apparatus to be used are not particularly limited. Type and column type reactors can be used. Moreover, each manufacturing process can be implemented by a batch type (batch type), and also can be implemented continuously.
Moreover, when manufacturing the compound represented by General formula (1-A) and General formula (1-B), the reaction apparatus to be used can be equipped with various stirring apparatuses. Such stirrers include, for example, paddle type stirrers, propeller type stirrers, turbine type stirrers, homogenizers, homomixers, line mixers, line homomixers, and other high speed stirrers, as well as static mixers, colloid mills, and orifice mixers. And a flow jet mixer.
The progress of the reaction in each production process can be traced by a method such as thin layer chromatography, high performance liquid chromatography, or gas chromatography.

According to the present invention, various functional polymer materials (for example, polyimide, polyamide, polycarbodiimide) and various functional electronic materials (for example, organic electroluminescent element material, organic transistor element material, photoelectric conversion element material) are manufactured. It has become possible to provide nitro compounds and amine compounds which are useful raw materials. Furthermore, it has become possible to provide a method for producing the compound. That is, for example, a tetraaryldiamine compound produced by tetraarylating two amino groups in the diamine compound which is the compound of the present invention according to a known method can be suitably used as an organic transistor element material.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.
Example 1
Under a nitrogen atmosphere, 26.2 g (0.10 mol) of 1,3-bis (4′-hydroxyphenyl) benzene, 34.2 g (0.203 mol) of 1,3-dinitrobenzene and 17 of fine powdery potassium carbonate 0.1 g (0.124 mol) was added to a mixed solvent of N, N-dimethylformamide (130 ml) and toluene (10 ml), and then toluene and water were distilled off from the reaction mixture at 140 to 145 ° C. Stir for hours. Furthermore, it stirred at 145-150 degreeC for 4 hours, distilling toluene and water off from the reaction mixture.
Thereafter, N, N-dimethylformamide was concentrated under reduced pressure, and water (200 ml) and toluene (500 ml) were added to the residue for extraction. After separating the toluene layer, toluene was distilled off under reduced pressure. The residue was separated by silica gel column chromatography (eluent: toluene) to obtain 45.5 g of the target 1,3-bis [4 ′-(3 ″ -nitrophenyloxy) phenyl] benzene as yellow crystals. (Yield 90%) This compound could be recrystallized from toluene, melting point 113-115 ° C. The purity of this compound was 99.8% or more (area) as a result of high performance liquid chromatography analysis. Ratio).

(Example 2)
A toluene (80 ml) solution containing 35.3 g (0.07 mol) of 1,3-bis [4 ′-(3 ″ -nitrophenyloxy) phenyl] benzene prepared in Example 1 was subjected to hydrogen gas under normal pressure. Under an atmosphere, it was added to a toluene (50 ml) solution containing 5% by mass palladium / carbon (50% by mass water-containing product, 4.24 g) with stirring at 65 ° C. over 3 hours. Hydrogenation was carried out by stirring at 60-68 ° C. for 1 hour under a gas atmosphere (during this time, the reaction mixture absorbed 0.42 mol of hydrogen).
The reaction mixture was subjected to hot filtration (65 ° C.) to separate palladium / carbon, and then toluene was concentrated from the toluene solution of the filtrate. The precipitated crystals were filtered from the toluene solution to obtain 29.2 g of the objective 1,3-bis [4 ′-(3 ″ -aminophenyloxy) phenyl] benzene as almost colorless crystals (yield) 94%) This compound could be recrystallized from toluene, mp 118-120 ° C.
The purity of this compound was 99.8% or more (area ratio) as a result of analysis by high performance liquid chromatography.

(Example 3)
Under a nitrogen atmosphere, 26.2 g (0.10 mol) of 1,3-bis (4′-hydroxyphenyl) benzene and 13.6 g (0.206 mol) of 85% by weight potassium hydroxide were added to dimethyl sulfoxide ( 80 ml) and stirred at 70 ° C. for 30 minutes.
To this mixture, 32.5 g (0.206 mol) of 4-chloronitrobenzene, dimethyl sulfoxide (100 ml), and toluene (20 ml) were added, and then toluene and water were distilled off from the reaction mixture. Stir at ~ 115 ° C for 8 hours.
Thereafter, dimethyl sulfoxide was concentrated under reduced pressure, and water (200 ml) and toluene (700 ml) were added to the residue for extraction.
After separating the toluene layer, toluene was distilled off under reduced pressure. The residue was separated by silica gel column chromatography (eluent: toluene) to obtain 30.7 g of the target 1,3-bis [4 ′-(4 ″ -nitrophenyloxy) phenyl] benzene as yellow crystals. (Yield 61%) Melting point 151-153 ° C
The purity of this compound was 99.7% or more (area ratio) as a result of analysis by high performance liquid chromatography.

Example 4
Under a nitrogen atmosphere, 26.2 g (0.10 mol) of 1,3-bis (4′-hydroxyphenyl) benzene, 32.0 g (0.203 mol) of 4-chloronitrobenzene and 17.1 g of finely powdered potassium carbonate (0.124 mol) was added to a mixed solvent of N, N-dimethylformamide (130 ml) and toluene (10 ml), followed by stirring at 140 to 145 ° C. for 2 hours while distilling off toluene and water from the reaction mixture. did. Furthermore, it stirred at 145-150 degreeC for 8 hours, distilling toluene and water off from the reaction mixture. Thereafter, toluene and a part of N, N-dimethylformamide (10 ml) were distilled off under reduced pressure, followed by hot filtration at 70 ° C. Water (600 ml) was added to the filtrate and cooled to room temperature.
The precipitated crystals were filtered, washed with water, and dried at 60 ° C. to obtain 49.2 g of the desired 1,3-bis [4 ′-(4 ″ -nitrophenyloxy) phenyl] benzene as yellow crystals (yield). The compound had a melting point of 151 to 153 ° C. The purity of the compound was 99.7% or more (area ratio) as a result of analysis by high performance liquid chromatography.

(Example 5)
A solution of N, N-dimethylformamide (30 ml) containing 35.3 g (0.07 mol) of 1,3-bis [4 ′-(4 ″ -nitrophenyloxy) phenyl] benzene prepared in Example 4 was used. The mixture was added to a N, N-dimethylformamide (120 ml) solution containing 5 mass% palladium / alumina (0.5 g) under stirring at 70 ° C. under normal pressure and hydrogen gas atmosphere, and further under normal pressure under hydrogen gas atmosphere. The mixture was stirred for 7 hours at 70-85 ° C. and hydrogenated (during this time, the reaction mixture absorbed 0.42 mol of hydrogen) The reaction mixture was filtered hot at 85 ° C. and the palladium / alumina was filtered off. Then, water (150 ml) was added to the filtrate and cooled to room temperature, and the precipitated crystals were filtered to obtain the desired 1,3-bis [4 ′-(4 ″ -aminophenyloxy) phenyl] benzene 29. .4g with almost colorless crystals Obtained was (94% yield). This compound could be recrystallized from toluene (melting point: 227-229 ° C.). The purity of this compound was 99.8% or more (area ratio) as a result of analysis by high performance liquid chromatography.

(Application 1)
4.43 g (0.01 mol) of 1,3-bis [4 ′-(3 ″ -aminophenyloxy) phenyl] benzene prepared in Example 2, 14 g (0.05 mol) of 4-iodobiphenyl, iodide Cuprous 0.057 g (0.0003 mol) and potassium tert-butoxide 5.6 g (0.05 mol) were added to toluene (150 ml), and further 0.12 g (0.0006) of tri-tert-butylphosphine. The reaction mixture was stirred for 14 hours at 105 ° C. The reaction mixture was filtered and toluene was distilled off from the filtrate in toluene, and the residue was separated by silica gel column chromatography (eluent: toluene). As a result, 6.6 g of the compound represented by the formula (a) was obtained as almost colorless crystals (yield 63%), and the glass transition temperature of this compound was 84 ° C.

(Application example 2)
A thermal oxide film (SiO ₂ ) having a thickness of 200 nm was formed on a silicon substrate having a resistivity of 0.02 Ω · cm as a gate electrode. Here, the silicon substrate itself becomes the gate electrode, and the SiO ₂ layer formed on the surface of the silicon substrate becomes the gate insulating layer. This silicon substrate is heated to 60 ° C., and a toluene solution (concentration: 0.7 mass%) of the compound represented by the formula (a) produced in Application Example 1 is applied thereon, and the toluene is evaporated. Thus, an organic semiconductor layer (thickness: 80 nm) made of the compound represented by the formula (a) was formed. Further, a source electrode and a drain electrode were formed thereon by vapor-depositing gold using a mask. The source electrode and drain electrode had a thickness of 80 nm, a channel width of 2 mm, and a channel length of 50 μm. The organic transistor fabricated as described above exhibited characteristics as a p-type organic transistor element. The charge mobility was determined from the saturation region of the current-voltage (IV) characteristics of the organic transistor and found to be 2 × 10 ⁻³ (cm ² / Vsec). Furthermore, when the drain bias was −50 V, the drain current value was measured when the gate bias was −50 V and 0 V, and the current on / off ratio was determined, it was 4.7 × 10 ³ . The threshold voltage of this organic transistor was −12V.

  According to the present invention, it has become possible to provide a novel ether compound represented by the general formula (1). According to the present invention, various functional polymer materials (for example, polyimide, polyamide, polycarbodiimide) and various functional electronic materials (for example, organic electroluminescent element material, organic transistor element material, photoelectric conversion element material) are manufactured. It has become possible to provide a compound that is a useful raw material and a method for producing the compound.

Claims (3)

The compound represented by General formula (1).

(In the formula, A ₁ and A ₂ each independently represent a nitro group or an amino group) In the presence of a base, the compound represented by the formula (2) is reacted with at least one compound selected from dinitrobenzene and halogenated nitrobenzene. Compound production method.

A process for producing a compound represented by the general formula (1-B) comprising reacting a compound represented by the general formula (1-A) and a hydrogen source in the presence of a catalyst.