WO2013179872A1 - Ether compound and method for producing same - Google Patents
Ether compound and method for producing same Download PDFInfo
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- WO2013179872A1 WO2013179872A1 PCT/JP2013/063120 JP2013063120W WO2013179872A1 WO 2013179872 A1 WO2013179872 A1 WO 2013179872A1 JP 2013063120 W JP2013063120 W JP 2013063120W WO 2013179872 A1 WO2013179872 A1 WO 2013179872A1
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- compound
- compound represented
- general formula
- palladium
- toluene
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- NLFAZODGSPWXLX-UHFFFAOYSA-N C(C=C1)C=C1Oc(cc1)ccc1-c1cccc(-c(cc2)ccc2OC2=CC=C=C2)c1 Chemical compound C(C=C1)C=C1Oc(cc1)ccc1-c1cccc(-c(cc2)ccc2OC2=CC=C=C2)c1 NLFAZODGSPWXLX-UHFFFAOYSA-N 0.000 description 1
- UGBGBYZZURFPEI-UHFFFAOYSA-N c(cc1)ccc1Oc(cc1)ccc1-c1cccc(-c(cc2)ccc2Oc2ccccc2)c1 Chemical compound c(cc1)ccc1Oc(cc1)ccc1-c1cccc(-c(cc2)ccc2Oc2ccccc2)c1 UGBGBYZZURFPEI-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
- C07C205/35—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C205/36—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
- C07C205/38—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system the oxygen atom of at least one of the etherified hydroxy groups being further bound to a carbon atom of a six-membered aromatic ring, e.g. nitrodiphenyl ethers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Definitions
- 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)
- various functional polymer materials for example, polyimide, polyamide, polycarbodiimide
- 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.
- Non-patent Document 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 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.
- 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).
- 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).
- 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).
- amine compounds are known to be useful as photoelectric conversion element (organic solar battery) materials (Non-Patent Document 5).
- further improvement of characteristics is desired, and accordingly, creation of new organic materials is required.
- 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.
- 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)
- the present invention relates to 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.
- various functional polymer materials for example, polyimide, polyamide, polycarbodiimide
- various functional electronic materials for example, organic electroluminescent element material, organic transistor element material, photoelectric conversion element material
- the present invention is a compound represented by the general formula (1).
- a 1 and A 2 each independently represent a nitro group or an amino group
- 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.
- 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.
- 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).
- 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.
- 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.
- the compound represented by the formula (2) can be produced, for example, by reacting 1,3-bis (4′-methoxyphenyl) benzene with hydroiodic 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].
- dinitrobenzene examples include 1,2-dinitrobenzene, 1,3-dinitrobenzene and 1,4-dinitrobenzene, and 1,3-dinitrobenzene and 1,4-dinitrobenzene are preferred.
- halogenated nitrobenzene examples include chloronitrobenzene, bromonitrobenzene and fluoronitrobenzene, chloronitrobenzene and fluoronitrobenzene are preferred, and chloronitrobenzene is more preferred.
- 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.
- 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.
- About 0.1 mol, more preferably about 0.95 to 1.05 mol is used.
- inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium phosphate, potassium phosphate, sodium bicarbonate, potassium bicarbonate,
- the base 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.
- the organic solvent include aliphatic hydrocarbon solvents such as pentane, hexane, octane, and cyclohexane,
- aromatic hydrocarbon solvents such as benzene, toluene, o-xylene, m-xylene, p-xylene, mixed xylene, mesitylene, cumene, pseudocumene, tetralin
- 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 sulf
- 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.
- 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.
- 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.
- 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.
- the metal compound include a zero-valent metal or a metal compound containing a monovalent to divalent metal ion, and more preferably a copper compound containing a copper atom or a copper ion in the molecule.
- 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.
- metal compounds include metal copper, cuprous chloride, cuprous bromide, cuprous iodide, cuprous oxide, cuprous acetate, cupric chloride, cupric bromide, iodine.
- 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 ( ⁇ -C 5 H 5 ) 2 , Organic coordination complexes,
- 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 ,
- 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
- inorganic or 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
- 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.
- 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.
- an inert gas for example, nitrogen, argon, helium.
- the reaction may be carried out under normal pressure, and may be carried out under reduced pressure or under pressure as desired.
- 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.
- the compound represented by the general formula (1-A) can be isolated and purified by a known method such as a recrystallization method or a chromatography method, if desired.
- the production method of the compound represented by the general formula (1-B) in which A 1 and A 2 are simultaneously amino groups is not particularly limited, 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 preferred 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.
- the hydrogen source examples 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 hydrogen supply capability, more preferably hydrogen and hydrazine can be mentioned, and hydrogen is more preferable.
- a protonic acid for example, hydrogen chloride, hydrogen bromide
- a reducing agent for example, iron, tin, stannous chloride, etc.
- the hydrogen source itself has hydrogen supply capability, more preferably hydrogen and hydrazine can be mentioned, and hydrogen is more preferable.
- hydrogen 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) to an amino group is used.
- the hydrogen source is converted to 4 moles per 1 mole of the compound represented by the general formula (1-A) in terms of 1 mole of hydrogen. About 8 mol is used, more preferably about 6 mol.
- 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.
- the metal atom in a form supported on a carrier such as carbon, alumina, silica, zeolite, barium sulfate or the like.
- 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 about 4% by mass relative to the compound represented by the
- the reaction is preferably performed in the presence of an organic solvent.
- organic solvent include aliphatic hydrocarbon solvents such as pentane, hexane, octane, and cyclohexane,
- aromatic hydrocarbon solvents such as benzene, toluene, o-xylene, m-xylene, p-xylene, mixed xylene, mesitylene, cumene, pseudocumene, tetralin
- alcohol solvents such as methanol, ethanol, isopropyl alcohol, butanol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol,
- ester solvents such as ethyl acetate, butyl acetate, amyl acetate,
- 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,
- organic solvents such as aprotic polar solvents such as 3-di-n-butyl-2-imidazolidinone and hexamethylphosphoramide. 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 6
- 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.
- the reaction temperature when the compound represented by the general formula (1-A) and a hydrogen source are allowed to act is not particularly limited, but is generally about 0 to 200 ° C., preferably 10 to 150 ° C. The temperature is preferably about 20 to 120 ° C.
- 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.
- 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).
- an inert gas for example, nitrogen, argon, helium
- 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.
- the compound represented by the general formula (1-B) can be isolated and purified by a known method such as a recrystallization method or a chromatography method, if desired.
- the compound represented by the general formula (1-B) and the 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.
- the structures of the compounds represented by the general formula (1-A) and the general formula (1-B) are elemental analysis, MS (FD-MS) analysis, IR analysis, 1 H-NMR, 13 C-NMR, etc. These can be identified by various analysis methods.
- 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. Further, when producing the compounds represented by the general formula (1-A) and the general formula (1-B), the reaction apparatus used can be equipped with various stirring apparatuses.
- 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.
- various functional polymer materials for example, polyimide, polyamide, polycarbodiimide
- various functional electronic materials for example, organic electroluminescent element material, organic transistor element material, photoelectric conversion element material
- nitro compounds and amine compounds which are useful raw materials.
- 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.
- 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 finely powdered potassium carbonate 17 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. Further, the mixture was stirred at 145 to 150 ° C.
- 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 for 1 hour at 60-68 ° C. under a gas atmosphere (during this time, the reaction mixture absorbed 0.42 mol of hydrogen).
- 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, 42.5 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.
- 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. Further, the mixture was stirred at 145 to 150 ° C. for 8 hours while removing toluene and water from the reaction mixture.
- 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 to 85 ° C. and hydrogenated (during this time, the reaction mixture absorbed 0.42 moles of hydrogen) The reaction mixture was filtered hot at 85 ° C.
- a thermal oxide film (SiO 2 ) having a thickness of 200 nm was formed on a silicon substrate having a resistivity of 0.02 ⁇ ⁇ cm as a gate electrode.
- 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.
- an organic semiconductor layer (thickness: 80 nm) made of the compound represented by the formula (a) was formed.
- the source electrode and drain electrode had a thickness of 80 nm, a channel width of 2 mm, and a channel length of 50 ⁇ m.
- 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 and the gate bias was ⁇ 50 V and 0 V, the drain current value was measured, and the current on / off ratio was determined to be 4.7 ⁇ 10 3 . The threshold voltage of this organic transistor was ⁇ 12V.
- a novel ether compound represented by the general formula (1) According to the present invention, it is possible to provide a novel ether compound represented by the general formula (1).
- various functional polymer materials for example, polyimide, polyamide, polycarbodiimide
- various functional electronic materials for example, organic electroluminescent element material, organic transistor element material, photoelectric conversion element material
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Abstract
Provided are an ether compound of a specific structure useful as a raw material when producing a functional polymer material or functional electronic material and a method for producing this compound. A compound represented by general formula (1) and a method for producing this compound. (In the formula, A1 and A2 each independently represent a nitro group or amino group.)
Description
本発明は、新規な構造を有するエーテル化合物に関する。
さらに詳しくは、各種の機能性高分子材料(例えば、ポリイミド、ポリアミド、ポリカルボジイミド)、各種の機能性電子材料(例えば、有機電界発光素子材料、有機トランジスタ素子材料、光電変換素子材料)の製造原料として有用なエーテル化合物、および該化合物の製造方法に関する。 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.
さらに詳しくは、各種の機能性高分子材料(例えば、ポリイミド、ポリアミド、ポリカルボジイミド)、各種の機能性電子材料(例えば、有機電界発光素子材料、有機トランジスタ素子材料、光電変換素子材料)の製造原料として有用なエーテル化合物、および該化合物の製造方法に関する。 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.
近年、社会のニーズに伴って、各種の機能性高分子材料、および各種の機能性電子材料の開発が活発に行われている。各種の機能性高分子材料としては、例えば、種々のポリイミド、ポリアミド、ポリカルボジイミドなどが開発されてきている。各種の特性を有するポリイミドの製造原料として、種々のアミン化合物が提案されており、例えば、4,4’-ビス(アミノフェノキシ)ジフェニルスルフォン、4,4’-ビス(アミノフェノキシ)ベンゾフェノンは有用な化合物であることが報告されている(非特許文献1)。
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).
また、分子内にエーテル結合を有するアミン化合物、例えば、4,4’-ビス(アミノフェノキシ)ビフェニル、1,3-ビス(アミノフェノキシ)ベンゼン、および1,4-ビス(アミノフェノキシ)ベンゼンも各種ポリイミドの製造原料として有用な化合物であることが報告されている(非特許文献1)。現在では、各種の機能性高分子材料を用いる分野においては、様々な特性の改良が望まれており、その特性の改良を行うためにも、製造原料として新規なアミン化合物が求められている。
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 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.
また、種々のアミン化合物は、各種の機能性電子材料(例えば、有機電界発光素子材料、有機トランジスタ素子材料、光電変換素子材料)として有用であることが知られている。
有機電界発光素子材料として、アミン化合物は、例えば、正孔注入輸送材料、発光材料として有用であることが知られている(非特許文献2)。
また、有機トランジスタ素子材料として、アミン化合物は、例えば、p-型の有機トランジスタ材料として有用であることが知られている(非特許文献3、4)。さらに、光電変換素子(有機太陽電池)材料として、アミン化合物は有用であることが知られている(非特許文献5)。
これら各種の機能性電子材料の分野においても、更なる特性改良が望まれており、それに伴い、新規な有機材料の創出が求められている。 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).
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.
有機電界発光素子材料として、アミン化合物は、例えば、正孔注入輸送材料、発光材料として有用であることが知られている(非特許文献2)。
また、有機トランジスタ素子材料として、アミン化合物は、例えば、p-型の有機トランジスタ材料として有用であることが知られている(非特許文献3、4)。さらに、光電変換素子(有機太陽電池)材料として、アミン化合物は有用であることが知られている(非特許文献5)。
これら各種の機能性電子材料の分野においても、更なる特性改良が望まれており、それに伴い、新規な有機材料の創出が求められている。 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).
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.
本発明の課題は、前記特定構造を有するエーテル化合物を提供することである。さらに詳しくは、分子内にエーテル結合およびニトロ基を有する化合物、および分子内にエーテル結合およびアミノ基を有する化合物、および該化合物の製造方法を提供することである。
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.
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.
本発明者らは、各種の化合物に関し、鋭意検討した結果、本発明を完成するに至った。すなわち、本発明は、
(i)一般式(1)で表される化合物であり、
(式中、A1およびA2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)
(i)一般式(1)で表される化合物であり、
(式中、A1およびA2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)塩基の存在下、式(2)で表される化合物と、ジニトロベンゼン及びハロゲン化ニトロベンゼンから選ばれた少なくとも1種の化合物を反応させることを特徴とする一般式(1-A)で表される化合物の製造方法であり、
(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,
(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)触媒の存在下、一般式(1-A)で表される化合物と、水素源を作用させることから成る一般式(1-B)で表される化合物の製造方法に関するものである。
(Iii) The present invention relates to 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.
(Iii) The present invention relates to 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.
本発明により、各種の機能性高分子材料(例えば、ポリイミド、ポリアミド、ポリカルボジイミド)、および各種の機能性電子材料(例えば、有機電界発光素子材料、有機トランジスタ素子材料、光電変換素子材料)を製造する際に有用な原料であるエーテル化合物、および該化合物の製造方法を提供することが可能になった。
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.
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.
以下、本発明に関し詳細に説明する。
本発明は、一般式(1)で表される化合物である。
(式中、A1およびA2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)
本発明は、一般式(1)で表される化合物である。
(式中、A1およびA2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)
一般式(1)で表される化合物において、A1およびA2はそれぞれ独立に、ニトロ基またはアミノ基を表し、より好ましくは、A1およびA2が同時に、ニトロ基またはアミノ基を表す。また、一般式(1)で表される化合物において、A1およびA2はそれぞれ独立に、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、メタ位またはパラ位を表し、さらに好ましくは、A1およびA2が同時に、メタ位またはパラ位を表す。
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)で表される化合物は、より好ましくは、一般式(1-A)または一般式(1-B)で表される化合物である。
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.
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.
一般式(1)において、A1およびA2が同時にニトロ基である一般式(1-A)で表される化合物の製造方法に関しては、塩基の存在下、式(2)で表される化合物と、ジニトロベンゼン及びハロゲン化ニトロベンゼンから選ばれる少なくとも1種の化合物を反応させることにより製造することができる。
Regarding the method for producing a compound represented by the general formula (1-A) in which A 1 and A 2 are simultaneously nitro groups in the general formula (1), 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.
Regarding the method for producing a compound represented by the general formula (1-A) in which A 1 and A 2 are simultaneously nitro groups in the general formula (1), 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.
式(2)で表される化合物は、例えば、1,3-ビス(4’-メトキシフェニル)ベンゼンと、ヨウ化水素酸、または三臭化ホウ素を作用させることにより製造することができる[例えば、J.Amer.Chem.Soc.,66,628(1944)、
J.Mater.Chem.,9、661(1999)、J.Med.Chem.,51、6725(2008)に記載の方法を参考にすることができる]。 The compound represented by the formula (2) can be produced, for example, by reacting 1,3-bis (4′-methoxyphenyl) benzene with hydroiodic 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].
J.Mater.Chem.,9、661(1999)、J.Med.Chem.,51、6725(2008)に記載の方法を参考にすることができる]。 The compound represented by the formula (2) can be produced, for example, by reacting 1,3-bis (4′-methoxyphenyl) benzene with hydroiodic 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].
ジニトロベンゼンの具体例としては、1,2-ジニトロベンゼン、1,3-ジニトロベンゼン、1,4-ジニトロベンゼンが挙げられ、1,3-ジニトロベンゼン、1,4-ジニトロベンゼンが好ましい。
ハロゲン化ニトロベンゼンの具体例としては、クロロニトロベンゼン、ブロモニトロベンゼン、フルオロニトロベンゼンが挙げられ、クロロニトロベンゼン、フルオロニトロベンゼンが好ましく、クロロニトロベンゼンがより好ましい。 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.
ハロゲン化ニトロベンゼンの具体例としては、クロロニトロベンゼン、ブロモニトロベンゼン、フルオロニトロベンゼンが挙げられ、クロロニトロベンゼン、フルオロニトロベンゼンが好ましく、クロロニトロベンゼンがより好ましい。 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.
ハロゲン化ニトロベンゼンの好ましい具体例としては、例えば、2-クロロニトロベンゼン、3-クロロニトロベンゼン、4-クロロニトロベンゼン、2-ブロモニトロベンゼン、3-ブロモニトロベンゼン、4-ブロモニトロベンゼン、2-フルオロニトロベンゼン、3-フルオロニトロベンゼン、4-フルオロニトロベンゼンなどが挙げられる。
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.
なお、一般式(1-A)で表される化合物において、ニトロ基がエーテル結合に対してメタ位である化合物を製造する場合、より好ましくは、塩基の存在下、式(2)で表される化合物とジニトロベンゼンを反応させる。
また、一般式(1-A)で表される化合物において、ニトロ基がエーテル結合に対してオルト位またはパラ位である化合物を製造する場合、より好ましくは、塩基の存在下、式(2)で表される化合物とハロゲン化ニトロベンゼンを反応させる。 In the case of producing a compound represented by the general formula (1-A) in which the nitro group is in the meta position with respect to the ether bond, it is more preferably represented by the formula (2) in the presence of a base. The compound is reacted with dinitrobenzene.
In the case of producing a compound represented by the general formula (1-A) in which the nitro group is ortho or para to the ether bond, more preferably, in the presence of a base, the formula (2) Is reacted with a halogenated nitrobenzene.
また、一般式(1-A)で表される化合物において、ニトロ基がエーテル結合に対してオルト位またはパラ位である化合物を製造する場合、より好ましくは、塩基の存在下、式(2)で表される化合物とハロゲン化ニトロベンゼンを反応させる。 In the case of producing a compound represented by the general formula (1-A) in which the nitro group is in the meta position with respect to the ether bond, it is more preferably represented by the formula (2) in the presence of a base. The compound is reacted with dinitrobenzene.
In the case of producing a compound represented by the general formula (1-A) in which the nitro group is ortho or para to the ether bond, more preferably, in the presence of a base, the formula (2) Is reacted with a halogenated nitrobenzene.
一般式(1-A)で表される化合物の製造において使用するジニトロベンゼン及びハロゲン化ニトロベンゼンの量は、一般には、当該化合物を1種類のみ反応させる場合は、式(2)で表される化合物1モルに対して、1.8~2.2モル程度、より好ましくは、1.9~2.1モル程度、さらに好ましくは、1.95~2.05モル程度使用する。又、当該化合物から2種類選択して反応させる場合は、式(2)で表される化合物1モルに対して、それぞれ0.8~1.2モル程度、より好ましくは、0.9~1.1モル程度、さらに好ましくは、0.95~1.05モル程度使用する。
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. In the case of reacting by selecting two kinds from the compounds, about 0.8 to 1.2 moles, more preferably 0.9 to 1, respectively, per 1 mole of the compound represented by the formula (2). About 0.1 mol, more preferably about 0.95 to 1.05 mol is used.
一般式(1-A)で表される化合物の製造において使用する塩基としては、
例えば、炭酸ナトリウム、炭酸カリウム、炭酸セシウム、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、リン酸ナトリウム、リン酸カリウム、炭酸水素ナトリウム、炭酸水素カリウムなどの無機塩基、
例えば、ナトリウムメトキシド、カリウムメトキシド、ナトリウムエトキシド、カリウムエトキシド、ナトリウム-tert-ブトキシド、カリウム-tert-ブトキシド、ナトリウム(2,4,6-トリ-tert-ブチルフェノラート)、カリウム(2,4,6-トリ-tert-ブチルフェノラート)、カリウム(2,6-ジ-tert-ブチル-4-メチルフェノラート)などの金属アルコキシド、
例えば、酢酸ナトリウム、酢酸カリウム、トリエチルアミン、トリイソプロピルアミン、トリ-n-ブチルアミン、ジイソプロピルエチルアミン、ピリジン、キノリン、ピコリン、テトラ-n-ブチルアンモニウムブロマイド、1,8-ジアザビシクロ[5.4.0]-7-ウンデセン(DBU)、1,5-ジアザビシクロ[4.3.0]-5-ノネン(DBN)、N,N,N’,N’-テトラメチルエチレンジアミンなどの有機塩基などを挙げることができ、より好ましくは、無機塩基である。
係る塩基は1種を単独で使用してもよく、あるいは複数併用してもよい。塩基の使用量は、一般には、使用するジニトロベンゼン及びハロゲン化ニトロベンゼンの総量に対して、0.8~4.0当量であり、好ましくは、1.0~3.0当量使用する。 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), and metal alkoxides such as potassium (2,6-di-tert-butyl-4-methylphenolate),
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.
例えば、炭酸ナトリウム、炭酸カリウム、炭酸セシウム、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、リン酸ナトリウム、リン酸カリウム、炭酸水素ナトリウム、炭酸水素カリウムなどの無機塩基、
例えば、ナトリウムメトキシド、カリウムメトキシド、ナトリウムエトキシド、カリウムエトキシド、ナトリウム-tert-ブトキシド、カリウム-tert-ブトキシド、ナトリウム(2,4,6-トリ-tert-ブチルフェノラート)、カリウム(2,4,6-トリ-tert-ブチルフェノラート)、カリウム(2,6-ジ-tert-ブチル-4-メチルフェノラート)などの金属アルコキシド、
例えば、酢酸ナトリウム、酢酸カリウム、トリエチルアミン、トリイソプロピルアミン、トリ-n-ブチルアミン、ジイソプロピルエチルアミン、ピリジン、キノリン、ピコリン、テトラ-n-ブチルアンモニウムブロマイド、1,8-ジアザビシクロ[5.4.0]-7-ウンデセン(DBU)、1,5-ジアザビシクロ[4.3.0]-5-ノネン(DBN)、N,N,N’,N’-テトラメチルエチレンジアミンなどの有機塩基などを挙げることができ、より好ましくは、無機塩基である。
係る塩基は1種を単独で使用してもよく、あるいは複数併用してもよい。塩基の使用量は、一般には、使用するジニトロベンゼン及びハロゲン化ニトロベンゼンの総量に対して、0.8~4.0当量であり、好ましくは、1.0~3.0当量使用する。 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), and metal alkoxides such as potassium (2,6-di-tert-butyl-4-methylphenolate),
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.
一般式(1-A)で表される化合物の製造においては、有機溶媒の非存在下で実施することも可能であるが、好ましくは有機溶媒の存在下で実施する。
係る有機溶媒としては、例えば、ペンタン、ヘキサン、オクタン、シクロヘキサンなどの脂肪族炭化水素溶媒、
例えば、ベンゼン、トルエン、o-キシレン、m-キシレン、p-キシレン、混合キシレン、メシチレン、クメン、プソイドクメン、テトラリンなどの芳香族炭化水素溶媒、
例えば、1,4-ジオキサン、テトラヒドロフラン、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジイソプロピルエーテル、ジイソブチルエーテル、シクロペンチルメチルエーテル、アニソール、ジフェニルエーテルなどのエーテル系溶媒、
例えば、ジメチルスルフォキサイド、ジメチルスルフォン、スルフォラン、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチル-2-ピロリドン、1,3-ジメチル-2-イミダゾリジノン、1,3-ジエチル-2-イミダゾリジノン、1,3-ジ-n-ブチル-2-イミダゾリジノン、ヘキサメチルホスホルアミド、アセトニトリル、プロピオニトリル、ブチロニトリルなどの非プロトン性極性溶媒などの有機溶媒を挙げることができ、より好ましくは、非プロトン性極性溶媒である。
これらの有機溶媒は、1種を単独で使用してもよく、あるいは複数併用してもよい。 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.
係る有機溶媒としては、例えば、ペンタン、ヘキサン、オクタン、シクロヘキサンなどの脂肪族炭化水素溶媒、
例えば、ベンゼン、トルエン、o-キシレン、m-キシレン、p-キシレン、混合キシレン、メシチレン、クメン、プソイドクメン、テトラリンなどの芳香族炭化水素溶媒、
例えば、1,4-ジオキサン、テトラヒドロフラン、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジイソプロピルエーテル、ジイソブチルエーテル、シクロペンチルメチルエーテル、アニソール、ジフェニルエーテルなどのエーテル系溶媒、
例えば、ジメチルスルフォキサイド、ジメチルスルフォン、スルフォラン、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチル-2-ピロリドン、1,3-ジメチル-2-イミダゾリジノン、1,3-ジエチル-2-イミダゾリジノン、1,3-ジ-n-ブチル-2-イミダゾリジノン、ヘキサメチルホスホルアミド、アセトニトリル、プロピオニトリル、ブチロニトリルなどの非プロトン性極性溶媒などの有機溶媒を挙げることができ、より好ましくは、非プロトン性極性溶媒である。
これらの有機溶媒は、1種を単独で使用してもよく、あるいは複数併用してもよい。 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.
一般式(1-A)で表される化合物の製造において、有機溶媒の使用量は、特に制限するものではないが、一般には式(2)で表される化合物の濃度が0.05~6M程度、より好ましくは0.08~5M程度となる量に調製する。
尚、塩基として無機塩基を用いて一般式(1-A)で表される化合物を製造する場合、生成する水を反応系外に留去しながら反応を実施することは好ましいことである。 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 the case of producing the compound represented by the general formula (1-A) using an inorganic base as a base, it is preferable to carry out the reaction while distilling off generated water out of the reaction system.
尚、塩基として無機塩基を用いて一般式(1-A)で表される化合物を製造する場合、生成する水を反応系外に留去しながら反応を実施することは好ましいことである。 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 the case of producing the compound represented by the general formula (1-A) using an inorganic base as a base, it is preferable to carry out the reaction while distilling off generated water out of the reaction system.
一般式(1-A)で表される化合物の製造において、式(2)で表される化合物、ジニトロベンゼン及びハロゲン化ニトロベンゼン、塩基、および有機溶媒の供給方法に関しては、特に制限するものではないが、例えば、
(ア)有機溶媒の存在下、式(2)で表される化合物および塩基の混合物に、ジニトロベンゼン及び/又はハロゲン化ニトロベンゼンを供給する方法、
(イ)有機溶媒の存在下、ジニトロベンゼン及び/又はハロゲン化ニトロベンゼンに、式(2)で表される化合物および塩基を供給する方法、
(ウ)有機溶媒の存在下、式(2)で表される化合物、ジニトロベンゼン及び/又はハロゲン化ニトロベンゼンおよび塩基を、一括で供給する方法、などを挙げることができる。
このように、一般式(1-A)で表される化合物は、塩基の存在下、式(2)で表される化合物と、ジニトロベンゼン及びハロゲン化ニトロベンゼンから選ばれた少なくとも1種を反応させることにより製造することができるが、ハロゲン化ニトロベンゼンを用いる場合には、所望により、さらに金属化合物を存在させてもよい。 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.
(ア)有機溶媒の存在下、式(2)で表される化合物および塩基の混合物に、ジニトロベンゼン及び/又はハロゲン化ニトロベンゼンを供給する方法、
(イ)有機溶媒の存在下、ジニトロベンゼン及び/又はハロゲン化ニトロベンゼンに、式(2)で表される化合物および塩基を供給する方法、
(ウ)有機溶媒の存在下、式(2)で表される化合物、ジニトロベンゼン及び/又はハロゲン化ニトロベンゼンおよび塩基を、一括で供給する方法、などを挙げることができる。
このように、一般式(1-A)で表される化合物は、塩基の存在下、式(2)で表される化合物と、ジニトロベンゼン及びハロゲン化ニトロベンゼンから選ばれた少なくとも1種を反応させることにより製造することができるが、ハロゲン化ニトロベンゼンを用いる場合には、所望により、さらに金属化合物を存在させてもよい。 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.
係る金属化合物としては、好ましくは、周期律表の第10~11族から選ばれる金属化合物であり、より好ましくは、銅化合物、パラジウム化合物、またはニッケル化合物であり、さらに好ましくは、銅化合物、またはパラジウム化合物である。
尚、金属化合物としては、0価の金属、または1価~2価の金属イオンを含有して成る金属化合物が挙げられ、より好ましくは、分子内に銅原子または銅イオンを含有して成る銅化合物、分子内にパラジウム原子またはパラジウムイオンを含有して成るパラジウム化合物、あるいは分子内にニッケル原子またはニッケルイオンを含有して成るニッケル化合物であり、さらに好ましくは、分子内に銅原子または銅イオンを含有して成る銅化合物、あるいは分子内にパラジウム原子またはパラジウムイオンを含有して成るパラジウム化合物である。 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, and more preferably a copper compound 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.
尚、金属化合物としては、0価の金属、または1価~2価の金属イオンを含有して成る金属化合物が挙げられ、より好ましくは、分子内に銅原子または銅イオンを含有して成る銅化合物、分子内にパラジウム原子またはパラジウムイオンを含有して成るパラジウム化合物、あるいは分子内にニッケル原子またはニッケルイオンを含有して成るニッケル化合物であり、さらに好ましくは、分子内に銅原子または銅イオンを含有して成る銅化合物、あるいは分子内にパラジウム原子またはパラジウムイオンを含有して成るパラジウム化合物である。 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, and more preferably a copper compound 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.
係る金属化合物としては、例えば、金属銅、塩化第一銅、臭化第一銅、ヨウ化第一銅、酸化第一銅、酢酸第一銅、塩化第二銅、臭化第二銅、ヨウ化第二銅、酸化第二銅、酢酸第二銅、硫酸銅、炭酸銅、トリフルオロメタンスルフォン酸銅、トリフルオロメタンスルフォン酸銅のベンゼン錯体、ビス(2,4-ペンタンジオナート)銅、ビス(トリフルオロ-2,4-ペンタンジオナート)銅、ビス(ヘキサフルオロアセチルアセトナート)銅、グルコン酸銅、安息香酸銅、ナフテン酸銅、フタル酸モノブチル銅、ジエチルジチオカルバミン酸銅などの銅化合物、
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,
あるいは、例えば、塩化パラジウム、臭化パラジム、ヨウ化パラジウム、酢酸パラジム、ビス(2,4-ペンタジオナート)パラジウム、ビス(ジベンジリデンアセトン)パラジウム、ビス(ベンゾニトリル)パラジウムジクロライド、アリルパラジウムクロライドのダイマー、K2PdCl4、K2PdCl6、K2Pd(NO3)4、トリス(ジベンジリデンアセトン)ジパラジウム、ジクロロビス(エチレン)パラジウム、Pd(π-C5H5)2などの無機、有機配位錯体、
例えば、ビス(エチレンジアミン)パラジウムジクロライド、PdCl2(NH3)2、PdCl2[N(C2H5)3]2、Pd(NO3)2(NH3)6などのN-配位錯体、
例えば、ビス[1,2-ビス(ジフェニルホスフィノ)エタン]パラジウム、Pd[P(CH3)3]4、Pd[P(C2H5)3]4、Pd[P(n-C3H7)3]4、Pd[P(iso-C3H7)3]4、Pd[P(n-C4H9)3]4、Pd[P(tert-C4H9)3]4、Pd[P(Cyc-C6H11)3]4、Pd[P(C6H5)3]4、Pd[P(o-CH3-C6H4)3]4、PdCO2[P(C6H5)3]4、Pd(C2H4)[P(C6H5)3]2、PdCl2[P(C6H5)3]2、PdCl2[P(n-C4H9)3]2、PdCl2[P(tert-C4H9)3]2、PdBr2[P(C6H5)3]2、PdBr2[P(n-C4H9)3]2、PdBr2[P(tert-C4H9)3]2、PdCl2[P(OCH3)3]2、PdBr2[P(OCH3)3]2、PdI2[P(OCH3)3]2、PdCl(C6H5)[P(C6H5)3]2などのホスフィン配位錯体、さらにはPd/炭素などのパラジウム化合物、 Alternatively, 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 ( nC 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,
例えば、ビス(エチレンジアミン)パラジウムジクロライド、PdCl2(NH3)2、PdCl2[N(C2H5)3]2、Pd(NO3)2(NH3)6などのN-配位錯体、
例えば、ビス[1,2-ビス(ジフェニルホスフィノ)エタン]パラジウム、Pd[P(CH3)3]4、Pd[P(C2H5)3]4、Pd[P(n-C3H7)3]4、Pd[P(iso-C3H7)3]4、Pd[P(n-C4H9)3]4、Pd[P(tert-C4H9)3]4、Pd[P(Cyc-C6H11)3]4、Pd[P(C6H5)3]4、Pd[P(o-CH3-C6H4)3]4、PdCO2[P(C6H5)3]4、Pd(C2H4)[P(C6H5)3]2、PdCl2[P(C6H5)3]2、PdCl2[P(n-C4H9)3]2、PdCl2[P(tert-C4H9)3]2、PdBr2[P(C6H5)3]2、PdBr2[P(n-C4H9)3]2、PdBr2[P(tert-C4H9)3]2、PdCl2[P(OCH3)3]2、PdBr2[P(OCH3)3]2、PdI2[P(OCH3)3]2、PdCl(C6H5)[P(C6H5)3]2などのホスフィン配位錯体、さらにはPd/炭素などのパラジウム化合物、 Alternatively, 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 ( nC 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,
また、例えば、塩化ニッケル、臭化ニッケル、ビス(2,4-ペンタジオナート)ニッケルなどの無機、有機配位錯体、例えば、Ni[P(C6H5)3]4、NiCl2[P(C6H5)3]2などのホスフィン配位錯体などのニッケル化合物を挙げることができる。より好ましい金属化合物は、塩化第一銅、臭化第一銅、ヨウ化第一銅などのハロゲン化第一銅、あるいは、酢酸パラジウムなどの無機、有機配位錯体パラジウムである。
金属化合物は、1種を単独で使用してもよく、あるいは複数併用してもよい。また、金属化合物の使用量に関しては特に制限されるものではないが、ハロゲン化ニトロベンゼンの総量に対して、一般には、0.01~50モル%程度であり、より好ましくは、0.1~30モル%程度である。 Further, for example, inorganic or 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%.
金属化合物は、1種を単独で使用してもよく、あるいは複数併用してもよい。また、金属化合物の使用量に関しては特に制限されるものではないが、ハロゲン化ニトロベンゼンの総量に対して、一般には、0.01~50モル%程度であり、より好ましくは、0.1~30モル%程度である。 Further, for example, inorganic or 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%.
一般式(1-A)で表される化合物を製造する際の反応温度に関しては、特に制限するものではないが、一般には、20~220℃程度、好ましくは、40~200℃程度、より好ましくは、50~180℃程度で実施する。
一般式(1-A)で表される化合物を製造する際の反応時間に関しては、特に制限するものではないが、一般には、1~40時間程度、より好ましくは、2~30時間程度で実施することができる。 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.
一般式(1-A)で表される化合物を製造する際の反応時間に関しては、特に制限するものではないが、一般には、1~40時間程度、より好ましくは、2~30時間程度で実施することができる。 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.
また、一般式(1-A)で表される化合物を製造する際の反応は、大気雰囲気下で実施することができるが、一般には、不活性ガス(例えば、窒素、アルゴン、ヘリウム)存在下で実施することが好ましい。
一般式(1-A)で表される化合物の製造に際して、反応は、常圧下で実施してもよく、所望により、減圧下または加圧下で実施することも可能である。 In addition, 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, and may be carried out under reduced pressure or under pressure as desired.
一般式(1-A)で表される化合物の製造に際して、反応は、常圧下で実施してもよく、所望により、減圧下または加圧下で実施することも可能である。 In addition, 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, and may be carried out under reduced pressure or under pressure as desired.
このような方法で製造される一般式(1-A)で表される化合物は、反応終了後、例えば、必要に応じ、有機溶媒を留去した後に、水の存在下で結晶として単離することができる。また、一般式(1-A)で表される化合物は、所望により、再結晶法、クロマトグラフィー法などの公知の方法により単離、精製することができる。
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. In addition, the compound represented by the general formula (1-A) can be isolated and purified by a known method such as a recrystallization method or a chromatography method, if desired.
尚、一般式(1)において、A1およびA2が同時にアミノ基である一般式(1-B)で表される化合物の製造方法に関しては、特に制限するものではないが、好ましくは、一般式(1-A)で表される化合物中のニトロ基を還元し、アミノ基へ変換することにより製造することができる。
In the general formula (1), the production method of the compound represented by the general formula (1-B) in which A 1 and A 2 are simultaneously amino groups is not particularly limited, 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.
一般式(1-B)で表される化合物の製造方法としては、好ましくは、一般式(1-A)で表される化合物と、水素源を作用させる(水素化反応)ことから成る製造方法であり、
より好ましくは、触媒の存在下、一般式(1-A)で表される化合物と、水素源を作用させることから成る製造方法である。 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 preferred 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.
より好ましくは、触媒の存在下、一般式(1-A)で表される化合物と、水素源を作用させることから成る製造方法である。 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 preferred 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.
水素源としては、例えば、プロトン酸(例えば、塩化水素、臭化水素)と還元剤(例えば、鉄、スズ、塩化第一スズなど)との組み合わせを包含するものであるが、より好ましくは、水素源自体が、水素供給能力を有するものであり、より好ましくは、水素、ヒドラジンを挙げることができ、より好ましくは、水素である。
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 hydrogen supply capability, more preferably hydrogen and hydrazine can be mentioned, and hydrogen is more preferable.
尚、水素源として水素を用いる場合、水素は気体状態で使用してもよく、また有機溶媒に溶解させた溶液状態で使用してもよい。
水素源の使用量は、特に制限するものではないが、一般式(1-A)で表される化合物中のニトロ基をアミノ基に変換するに充分な量を使用するものであり、過剰量の水素源の存在下で実施することも可能であるが、一般には、水素源は、水素1モルに換算して、一般式(1-A)で表される化合物1モルに対して、4~8モル程度使用し、より好ましくは、6モル程度使用する。 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) to an amino group is used. However, in general, the hydrogen source is converted to 4 moles per 1 mole of the compound represented by the general formula (1-A) in terms of 1 mole of hydrogen. About 8 mol is used, more preferably about 6 mol.
水素源の使用量は、特に制限するものではないが、一般式(1-A)で表される化合物中のニトロ基をアミノ基に変換するに充分な量を使用するものであり、過剰量の水素源の存在下で実施することも可能であるが、一般には、水素源は、水素1モルに換算して、一般式(1-A)で表される化合物1モルに対して、4~8モル程度使用し、より好ましくは、6モル程度使用する。 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) to an amino group is used. However, in general, the hydrogen source is converted to 4 moles per 1 mole of the compound represented by the general formula (1-A) in terms of 1 mole of hydrogen. About 8 mol is used, more preferably about 6 mol.
触媒としては、好ましくは、周期律表の第8~第10族から選ばれる金属原子を含有して成る金属触媒であり、より好ましくは、鉄、ロジウム、ニッケル、パラジウム、ルテニウム、コバルトまたは白金原子を含有して成る金属触媒であり、さらに好ましくは、パラジウム原子を含有して成るパラジウム触媒である。
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.
なお、触媒としては、該金属原子を、例えば、炭素、アルミナ、シリカ、ゼオライト、硫酸バリウムなどの担体に坦持させた形態で使用することは好ましい。係る触媒としては、例えば、塩化第二鉄/活性炭、パラジウム/炭素、パラジウム/アルミナ、パラジウム/硫酸バリウム、白金、酸化白金、白金/炭素、白金/シリカ、ロジウム/炭素、ロジウム/アルミナ、ルテニウム/炭素、ラネーニッケル、ラネーコバルトなどを挙げることができ、より好ましくは、パラジウム/炭素、パラジウム/アルミナなどのパラジウム触媒である。
触媒の使用量は、特に制限するものではないが、一般には、一般式(1-A)で表される化合物に対して、0.01~40質量%程度、より好ましくは、0.1~30質量%程度である。 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 about 4% by mass relative to the compound represented by the general formula (1-A). It is about 30% by mass.
触媒の使用量は、特に制限するものではないが、一般には、一般式(1-A)で表される化合物に対して、0.01~40質量%程度、より好ましくは、0.1~30質量%程度である。 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 about 4% by mass relative to the compound represented by the general formula (1-A). It is about 30% by mass.
触媒の存在下、一般式(1-A)で表される化合物と、水素源を作用させる際には、好ましくは、有機溶媒の存在下で実施する。
係る有機溶媒としては、例えば、ペンタン、ヘキサン、オクタン、シクロヘキサンなどの脂肪族炭化水素溶媒、
例えば、ベンゼン、トルエン、o-キシレン、m-キシレン、p-キシレン、混合キシレン、メシチレン、クメン、プソイドクメン、テトラリンなどの芳香族炭化水素溶媒、
例えば、メタノール、エタノール、イソプロピルアルコール、ブタノール、シクロヘキサノール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールなどのアルコール系溶媒、
例えば、酢酸エチル、酢酸ブチル、酢酸アミルなどのエステル系溶媒、 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,
係る有機溶媒としては、例えば、ペンタン、ヘキサン、オクタン、シクロヘキサンなどの脂肪族炭化水素溶媒、
例えば、ベンゼン、トルエン、o-キシレン、m-キシレン、p-キシレン、混合キシレン、メシチレン、クメン、プソイドクメン、テトラリンなどの芳香族炭化水素溶媒、
例えば、メタノール、エタノール、イソプロピルアルコール、ブタノール、シクロヘキサノール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールなどのアルコール系溶媒、
例えば、酢酸エチル、酢酸ブチル、酢酸アミルなどのエステル系溶媒、 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,
例えば、1,4-ジオキサン、テトラヒドロフラン、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジイソプロピルエーテル、ジイソブチルエーテル、シクロペンチルメチルエーテル、アニソール、ジフェニルエーテルなどのエーテル系溶媒、
例えば、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチル-2-ピロリドン、1,3-ジメチル-2-イミダゾリジノン、1,3-ジエチル-2-イミダゾリジノン、1,3-ジ-n-ブチル-2-イミダゾリジノン、ヘキサメチルホスホルアミドなどの非プロトン性極性溶媒などの有機溶媒を挙げることができる。
これらの有機溶媒は、1種を単独で使用してもよく、あるいは複数併用してもよい。
尚、有機溶媒の使用量は、特に制限するものではないが、一般には、一般式(1-A)で表される化合物の濃度が、0.05~6M程度、より好ましくは、0.08~5M程度となる量に調製する。 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, Examples thereof include organic solvents such as aprotic polar solvents such as 3-di-n-butyl-2-imidazolidinone and hexamethylphosphoramide.
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 an amount of about 5M.
例えば、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチル-2-ピロリドン、1,3-ジメチル-2-イミダゾリジノン、1,3-ジエチル-2-イミダゾリジノン、1,3-ジ-n-ブチル-2-イミダゾリジノン、ヘキサメチルホスホルアミドなどの非プロトン性極性溶媒などの有機溶媒を挙げることができる。
これらの有機溶媒は、1種を単独で使用してもよく、あるいは複数併用してもよい。
尚、有機溶媒の使用量は、特に制限するものではないが、一般には、一般式(1-A)で表される化合物の濃度が、0.05~6M程度、より好ましくは、0.08~5M程度となる量に調製する。 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, Examples thereof include organic solvents such as aprotic polar solvents such as 3-di-n-butyl-2-imidazolidinone and hexamethylphosphoramide.
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 an amount of about 5M.
一般式(1-B)で表される化合物の製造において、一般式(1-A)で表される化合物、触媒、有機溶媒および水素源の供給方法に関しては、特に制限するものではないが、例えば、
(エ)有機溶媒の存在下、一般式(1-A)で表される化合物および触媒の混合物に、水素源を供給する方法、
(オ)有機溶媒の存在下、予め触媒を存在させて、一般式(1-A)で表される化合物の供給と共に、水素源を供給する方法、などを挙げることができる。 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 in which a catalyst is previously present in the presence of an organic solvent and a hydrogen source is supplied together with the supply of the compound represented by the general formula (1-A).
(エ)有機溶媒の存在下、一般式(1-A)で表される化合物および触媒の混合物に、水素源を供給する方法、
(オ)有機溶媒の存在下、予め触媒を存在させて、一般式(1-A)で表される化合物の供給と共に、水素源を供給する方法、などを挙げることができる。 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 in which a catalyst is previously present in the presence of an organic solvent and a hydrogen source is supplied together with the supply of the compound represented by the general formula (1-A).
一般式(1-A)で表される化合物と、水素源を作用させる際の反応温度に関しては、特に制限するものではないが、一般には、0~200℃程度、好ましくは、10~150℃程度、より好ましくは、20~120℃程度で実施する。
また、一般式(1-A)で表される化合物と、水素源を作用させる際の反応時間に関しては、特に制限するものではないが、一般には、1~100時間程度、より好ましくは、2~60時間程度で実施することができる。
また、一般式(1-A)で表される化合物と水素源との反応は、水素源と共に、例えば、不活性ガス(例えば、窒素、アルゴン、ヘリウム)の共存下で実施することができる。
一般式(1-A)で表される化合物と、水素源を作用させる際、該反応は、常圧下で実施してもよく、所望に応じ、減圧下または加圧下で実施することも可能である。 The reaction temperature when the compound represented by the general formula (1-A) and a hydrogen source are allowed to act is not particularly limited, but is generally about 0 to 200 ° C., preferably 10 to 150 ° C. The temperature is preferably about 20 to 120 ° C.
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.
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 carried out under normal pressure, and may be carried out under reduced pressure or under pressure as desired. is there.
また、一般式(1-A)で表される化合物と、水素源を作用させる際の反応時間に関しては、特に制限するものではないが、一般には、1~100時間程度、より好ましくは、2~60時間程度で実施することができる。
また、一般式(1-A)で表される化合物と水素源との反応は、水素源と共に、例えば、不活性ガス(例えば、窒素、アルゴン、ヘリウム)の共存下で実施することができる。
一般式(1-A)で表される化合物と、水素源を作用させる際、該反応は、常圧下で実施してもよく、所望に応じ、減圧下または加圧下で実施することも可能である。 The reaction temperature when the compound represented by the general formula (1-A) and a hydrogen source are allowed to act is not particularly limited, but is generally about 0 to 200 ° C., preferably 10 to 150 ° C. The temperature is preferably about 20 to 120 ° C.
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.
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 carried out under normal pressure, and may be carried out under reduced pressure or under pressure as desired. is there.
このような方法で製造される一般式(1-B)で表される化合物は、分子中にアミノ基を有していることから、例えば、酸(例えば、塩化水素、臭化水素、硫酸)を作用させて、塩(例えば、塩酸塩、臭酸塩、硫酸塩)として単離することもできる。
その一般式(1-B)で表される化合物の塩は、塩基(例えば、アンモニア、水酸化ナトリウム、水酸化カリウム)を作用させることにより、一般式(1-B)で表される化合物へと変換することができる。
また、一般式(1-B)で表される化合物は、所望により、再結晶法、クロマトグラフィー法などの公知の方法により単離、精製することができる。
また、一般式(1-B)で表される化合物および該化合物の塩は、有機溶媒および/または水の存在下、例えば、活性炭、ゼオライトなどを作用させて、精製することもできる。 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.
In addition, the compound represented by the general formula (1-B) can be isolated and purified by a known method such as a recrystallization method or a chromatography method, if desired.
In addition, the compound represented by the general formula (1-B) and the 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.
その一般式(1-B)で表される化合物の塩は、塩基(例えば、アンモニア、水酸化ナトリウム、水酸化カリウム)を作用させることにより、一般式(1-B)で表される化合物へと変換することができる。
また、一般式(1-B)で表される化合物は、所望により、再結晶法、クロマトグラフィー法などの公知の方法により単離、精製することができる。
また、一般式(1-B)で表される化合物および該化合物の塩は、有機溶媒および/または水の存在下、例えば、活性炭、ゼオライトなどを作用させて、精製することもできる。 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.
In addition, the compound represented by the general formula (1-B) can be isolated and purified by a known method such as a recrystallization method or a chromatography method, if desired.
In addition, the compound represented by the general formula (1-B) and the 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.
なお、一般式(1-A)および一般式(1-B)で表される化合物の構造は、元素分析、MS(FD-MS)分析、IR分析、1H-NMR、13C-NMRなどの各種分析方法により同定することができる。
一般式(1-A)および一般式(1-B)で表される化合物を製造するに際して、使用する反応装置の種類、形態に関しては特に制限するものではないが、一般には、槽型、管型、塔型の反応装置を用いることができる。また、各製造工程を、回分式(バッチ式)で実施することができ、さらには、連続的に実施することも可能である。
また一般式(1-A)および一般式(1-B)で表される化合物を製造するに際して、使用する反応装置は、様々な撹拌装置を備えることができる。係る撹拌装置としては、例えば、パドル型撹拌機、プロペラ型撹拌機、タービン型撹拌機、ホモジナイザー、ホモミキサー、ラインミキサー、ラインホモミキサーなどの高速撹拌機、さらにはスタティックミキサー、コロイドミル、オリフィスミキサー、フロージェットミキサーなどを挙げることができる。
尚、各製造工程における反応の進行は、例えば、薄層クロマトグラフィー、高速液体クロマトグラフィー、ガスクロマトグラフィーなどの方法で追跡することができる。 The structures of the compounds represented by the general formula (1-A) and the general formula (1-B) are elemental analysis, MS (FD-MS) analysis, IR analysis, 1 H-NMR, 13 C-NMR, etc. These can be identified by various analysis methods.
When 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.
Further, when producing the compounds represented by the general formula (1-A) and the general formula (1-B), the reaction apparatus 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.
一般式(1-A)および一般式(1-B)で表される化合物を製造するに際して、使用する反応装置の種類、形態に関しては特に制限するものではないが、一般には、槽型、管型、塔型の反応装置を用いることができる。また、各製造工程を、回分式(バッチ式)で実施することができ、さらには、連続的に実施することも可能である。
また一般式(1-A)および一般式(1-B)で表される化合物を製造するに際して、使用する反応装置は、様々な撹拌装置を備えることができる。係る撹拌装置としては、例えば、パドル型撹拌機、プロペラ型撹拌機、タービン型撹拌機、ホモジナイザー、ホモミキサー、ラインミキサー、ラインホモミキサーなどの高速撹拌機、さらにはスタティックミキサー、コロイドミル、オリフィスミキサー、フロージェットミキサーなどを挙げることができる。
尚、各製造工程における反応の進行は、例えば、薄層クロマトグラフィー、高速液体クロマトグラフィー、ガスクロマトグラフィーなどの方法で追跡することができる。 The structures of the compounds represented by the general formula (1-A) and the general formula (1-B) are elemental analysis, MS (FD-MS) analysis, IR analysis, 1 H-NMR, 13 C-NMR, etc. These can be identified by various analysis methods.
When 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.
Further, when producing the compounds represented by the general formula (1-A) and the general formula (1-B), the reaction apparatus 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.
本発明により、各種の機能性高分子材料(例えば、ポリイミド、ポリアミド、ポリカルボジイミド)、各種の機能性電子材料(例えば、有機電界発光素子材料、有機トランジスタ素子材料、光電変換素子材料)を製造する際の有用な原料であるニトロ化合物およびアミン化合物を提供することが可能になった。さらには、該化合物の製造方法を提供することが可能になった。すなわち、例えば、本発明の化合物であるジアミン化合物中の二つのアミノ基を、公知の方法に従って、テトラアリール化して製造されるテトラアリールジアミン化合物は、有機トランジスタ素子材料として好適に用いることができる。
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.
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.
以下、実施例により本発明をさらに詳細に説明するが、本発明はこれらに限定されるものではない。
(実施例1)
窒素雰囲気下、1,3-ビス(4’-ヒドロキシフェニル)ベンゼン26.2g(0.10モル)、1,3-ジニトロベンゼン34.2g(0.203モル)および微粉末状の炭酸カリウム17.1g(0.124モル)を、N,N-ジメチルホルムアミド(130ml)およびトルエン(10ml)の混合溶媒に加えた後、反応混合物からトルエンおよび水を留去しながら、140~145℃で2時間撹拌した。さらに、反応混合物からトルエンおよび水を留去しながら、145~150℃で4時間撹拌した。
その後、N,N-ジメチルホルムアミドを減圧下で濃縮し、残渣に水(200ml)、およびトルエン(500ml)を加え抽出した。トルエン層を分離後、トルエンを減圧下で留去した。残渣をシリカゲルカラムクロマトグラフィー(溶出液:トルエン)で分離して、目的とする1,3-ビス[4’-(3”-ニトロフェニルオキシ)フェニル]ベンゼン45.5gを黄色の結晶として得た(収率90%)。尚、この化合物はトルエンから再結晶することができた。融点113~115℃。この化合物の純度は、高速液体クロマトグラフィーの分析の結果、99.8%以上(面積比)であった。 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 finely powdered potassium carbonate 17 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. Further, the mixture was stirred at 145 to 150 ° C. for 4 hours while removing toluene and water 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 desired 1,3-bis [4 ′-(3 ″ -nitrophenyloxy) phenyl] benzene as yellow crystals. (Yield 90%) This compound could be recrystallized from toluene, mp 113-115 ° C. The purity of this compound was 99.8% or more (area) as a result of high performance liquid chromatography analysis. Ratio).
(実施例1)
窒素雰囲気下、1,3-ビス(4’-ヒドロキシフェニル)ベンゼン26.2g(0.10モル)、1,3-ジニトロベンゼン34.2g(0.203モル)および微粉末状の炭酸カリウム17.1g(0.124モル)を、N,N-ジメチルホルムアミド(130ml)およびトルエン(10ml)の混合溶媒に加えた後、反応混合物からトルエンおよび水を留去しながら、140~145℃で2時間撹拌した。さらに、反応混合物からトルエンおよび水を留去しながら、145~150℃で4時間撹拌した。
その後、N,N-ジメチルホルムアミドを減圧下で濃縮し、残渣に水(200ml)、およびトルエン(500ml)を加え抽出した。トルエン層を分離後、トルエンを減圧下で留去した。残渣をシリカゲルカラムクロマトグラフィー(溶出液:トルエン)で分離して、目的とする1,3-ビス[4’-(3”-ニトロフェニルオキシ)フェニル]ベンゼン45.5gを黄色の結晶として得た(収率90%)。尚、この化合物はトルエンから再結晶することができた。融点113~115℃。この化合物の純度は、高速液体クロマトグラフィーの分析の結果、99.8%以上(面積比)であった。 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 finely powdered potassium carbonate 17 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. Further, the mixture was stirred at 145 to 150 ° C. for 4 hours while removing toluene and water 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 desired 1,3-bis [4 ′-(3 ″ -nitrophenyloxy) phenyl] benzene as yellow crystals. (Yield 90%) This compound could be recrystallized from toluene, mp 113-115 ° C. The purity of this compound was 99.8% or more (area) as a result of high performance liquid chromatography analysis. Ratio).
(実施例2)
実施例1で製造した1,3-ビス[4’-(3”-ニトロフェニルオキシ)フェニル]ベンゼン35.3g(0.07モル)を含有するトルエン(80ml)溶液を、常圧下、水素ガス雰囲気下で、5質量%パラジウム/炭素(50質量%含水品、4.24g)を含むトルエン(50ml)溶液に撹拌下、65℃で、3時間を要して加えた。さらに常圧下、水素ガス雰囲気下、60~68℃で1時間撹拌し、水素化を行った(この間に、反応混合物は、水素0.42モルを吸収した)。
反応混合物を熱濾過(65℃)し、パラジウム/炭素を濾別した後、濾液のトルエン溶液からトルエンを濃縮した。トルエン溶液から、析出している結晶を濾過し、目的とする1,3-ビス[4’-(3”-アミノフェニルオキシ)フェニル]ベンゼン29.2gをほぼ無色の結晶として得た(収率94%)。尚、この化合物はトルエンから再結晶することができた。融点118~120℃
この化合物の純度は、高速液体クロマトグラフィーの分析の結果、99.8%以上(面積比)であった。 (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 for 1 hour at 60-68 ° C. under a gas atmosphere (during this time, the reaction mixture absorbed 0.42 mol of hydrogen).
The reaction mixture was filtered hot (65 ° C.), palladium / carbon was filtered off, 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.
実施例1で製造した1,3-ビス[4’-(3”-ニトロフェニルオキシ)フェニル]ベンゼン35.3g(0.07モル)を含有するトルエン(80ml)溶液を、常圧下、水素ガス雰囲気下で、5質量%パラジウム/炭素(50質量%含水品、4.24g)を含むトルエン(50ml)溶液に撹拌下、65℃で、3時間を要して加えた。さらに常圧下、水素ガス雰囲気下、60~68℃で1時間撹拌し、水素化を行った(この間に、反応混合物は、水素0.42モルを吸収した)。
反応混合物を熱濾過(65℃)し、パラジウム/炭素を濾別した後、濾液のトルエン溶液からトルエンを濃縮した。トルエン溶液から、析出している結晶を濾過し、目的とする1,3-ビス[4’-(3”-アミノフェニルオキシ)フェニル]ベンゼン29.2gをほぼ無色の結晶として得た(収率94%)。尚、この化合物はトルエンから再結晶することができた。融点118~120℃
この化合物の純度は、高速液体クロマトグラフィーの分析の結果、99.8%以上(面積比)であった。 (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 for 1 hour at 60-68 ° C. under a gas atmosphere (during this time, the reaction mixture absorbed 0.42 mol of hydrogen).
The reaction mixture was filtered hot (65 ° C.), palladium / carbon was filtered off, 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.
(実施例3)
窒素雰囲気下、1,3-ビス(4’-ヒドロキシフェニル)ベンゼン26.2g(0.10モル)、および85質量%水酸化カリウム13.6g(0.206モル)をジメチルスルフォキサイド(80ml)に加え、70℃で30分間撹拌した。
この混合物に、4-クロロニトロベンゼン32.5g(0.206モル)、ジメチルスルフォキサイド(100ml)、およびトルエン(20ml)を加えた後、反応混合物からトルエンおよび水を留去しながら、100~115℃で8時間撹拌した。
その後、ジメチルスルフォキサイドを減圧下で濃縮し、残渣に水(200ml)、およびトルエン(700ml)を加え、抽出した。
トルエン層を分離後、トルエンを減圧下で留去した。残渣をシリカゲルカラムクロマトグラフィー(溶出液:トルエン)で分離して、目的とする1,3-ビス[4’-(4”-ニトロフェニルオキシ)フェニル]ベンゼン30.7gを黄色の結晶として得た(収率61%)。融点151~153℃
この化合物の純度は、高速液体クロマトグラフィーの分析の結果、99.7%以上(面積比)であった。 (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, 42.5 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.
窒素雰囲気下、1,3-ビス(4’-ヒドロキシフェニル)ベンゼン26.2g(0.10モル)、および85質量%水酸化カリウム13.6g(0.206モル)をジメチルスルフォキサイド(80ml)に加え、70℃で30分間撹拌した。
この混合物に、4-クロロニトロベンゼン32.5g(0.206モル)、ジメチルスルフォキサイド(100ml)、およびトルエン(20ml)を加えた後、反応混合物からトルエンおよび水を留去しながら、100~115℃で8時間撹拌した。
その後、ジメチルスルフォキサイドを減圧下で濃縮し、残渣に水(200ml)、およびトルエン(700ml)を加え、抽出した。
トルエン層を分離後、トルエンを減圧下で留去した。残渣をシリカゲルカラムクロマトグラフィー(溶出液:トルエン)で分離して、目的とする1,3-ビス[4’-(4”-ニトロフェニルオキシ)フェニル]ベンゼン30.7gを黄色の結晶として得た(収率61%)。融点151~153℃
この化合物の純度は、高速液体クロマトグラフィーの分析の結果、99.7%以上(面積比)であった。 (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, 42.5 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.
(実施例4)
窒素雰囲気下、1,3-ビス(4’-ヒドロキシフェニル)ベンゼン26.2g(0.10モル)、4-クロロニトロベンゼン32.0g(0.203モル)および微粉末状の炭酸カリウム17.1g(0.124モル)を、N,N-ジメチルホルムアミド(130ml)およびトルエン(10ml)の混合溶媒に加えた後、反応混合物からトルエンおよび水を留去しながら、140~145℃で2時間撹拌した。さらに、反応混合物からトルエンおよび水を留去しながら、145~150℃で8時間撹拌した。その後、トルエン、および一部のN,N-ジメチルホルムアミド(10ml)を減圧下で留去し、70℃で熱濾過した。濾液に水(600ml)を加え、室温に冷却した。
析出した結晶を濾過、水洗後、60℃で乾燥し、目的とする1,3-ビス[4’-(4”-ニトロフェニルオキシ)フェニル]ベンゼン49.2gを黄色の結晶として得た(収率97%)。尚、この化合物は融点151~153℃であった。この化合物の純度は、高速液体クロマトグラフィーの分析の結果、99.7%以上(面積比)であった。 (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. Further, the mixture was stirred at 145 to 150 ° C. for 8 hours while removing toluene and water 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.
窒素雰囲気下、1,3-ビス(4’-ヒドロキシフェニル)ベンゼン26.2g(0.10モル)、4-クロロニトロベンゼン32.0g(0.203モル)および微粉末状の炭酸カリウム17.1g(0.124モル)を、N,N-ジメチルホルムアミド(130ml)およびトルエン(10ml)の混合溶媒に加えた後、反応混合物からトルエンおよび水を留去しながら、140~145℃で2時間撹拌した。さらに、反応混合物からトルエンおよび水を留去しながら、145~150℃で8時間撹拌した。その後、トルエン、および一部のN,N-ジメチルホルムアミド(10ml)を減圧下で留去し、70℃で熱濾過した。濾液に水(600ml)を加え、室温に冷却した。
析出した結晶を濾過、水洗後、60℃で乾燥し、目的とする1,3-ビス[4’-(4”-ニトロフェニルオキシ)フェニル]ベンゼン49.2gを黄色の結晶として得た(収率97%)。尚、この化合物は融点151~153℃であった。この化合物の純度は、高速液体クロマトグラフィーの分析の結果、99.7%以上(面積比)であった。 (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. Further, the mixture was stirred at 145 to 150 ° C. for 8 hours while removing toluene and water 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.
(実施例5)
実施例4で製造した1,3-ビス[4’-(4”-ニトロフェニルオキシ)フェニル]ベンゼン35.3g(0.07モル)を含有するN,N-ジメチルホルムアミド(30ml)溶液を、常圧下、水素ガス雰囲気下で、5質量%パラジウム/アルミナ(0.5g)を含むN,N-ジメチルホルムアミド(120ml)溶液に撹拌下、70℃で加えた。さらに常圧下、水素ガス雰囲気下、70~85℃で7時間撹拌し、水素化を行った(この間に、反応混合物は、水素0.42モルを吸収した)。反応混合物を85℃で熱濾過し、パラジウム/アルミナを濾別した後、濾液に水(150ml)を加え、室温に冷却した。析出している結晶を濾過し、目的とする1,3-ビス[4’-(4”-アミノフェニルオキシ)フェニル]ベンゼン29.4gをほぼ無色の結晶として得た(収率94%)。尚、この化合物はトルエンから再結晶することができた(融点227~229℃)。この化合物の純度は、高速液体クロマトグラフィーの分析の結果、99.8%以上(面積比)であった。 (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 to 85 ° C. and hydrogenated (during this time, the reaction mixture absorbed 0.42 moles 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.
実施例4で製造した1,3-ビス[4’-(4”-ニトロフェニルオキシ)フェニル]ベンゼン35.3g(0.07モル)を含有するN,N-ジメチルホルムアミド(30ml)溶液を、常圧下、水素ガス雰囲気下で、5質量%パラジウム/アルミナ(0.5g)を含むN,N-ジメチルホルムアミド(120ml)溶液に撹拌下、70℃で加えた。さらに常圧下、水素ガス雰囲気下、70~85℃で7時間撹拌し、水素化を行った(この間に、反応混合物は、水素0.42モルを吸収した)。反応混合物を85℃で熱濾過し、パラジウム/アルミナを濾別した後、濾液に水(150ml)を加え、室温に冷却した。析出している結晶を濾過し、目的とする1,3-ビス[4’-(4”-アミノフェニルオキシ)フェニル]ベンゼン29.4gをほぼ無色の結晶として得た(収率94%)。尚、この化合物はトルエンから再結晶することができた(融点227~229℃)。この化合物の純度は、高速液体クロマトグラフィーの分析の結果、99.8%以上(面積比)であった。 (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 to 85 ° C. and hydrogenated (during this time, the reaction mixture absorbed 0.42 moles 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.
(応用例1)
実施例2で製造した1,3-ビス[4’-(3”-アミノフェニルオキシ)フェニル]ベンゼン4.44g(0.01モル)、4-ヨードビフェニル14g(0.05モル)、ヨウ化第一銅0.057g(0.0003モル)、およびカリウム-tert-ブトキシド5.6g(0.05モル)をトルエン(150ml)に加え、さらにトリ-tert-ブチルホスフィン0.12g(0.0006モル)を加えた後、反応混合物を、105℃で14時間撹拌した。反応混合物を濾過し、濾液のトルエン溶液からトルエンを留去した。残渣をシリカゲルカラムクロマトグラフィー(溶出液:トルエン)で分離して、式(a)で表される化合物6.6gをほぼ無色の結晶として得た(収率63%)。この化合物のガラス転移温度は84℃であった。
(Application 1)
4.44-g (0.01 mol) of 1,3-bis [4 ′-(3 ″ -aminophenyloxy) phenyl] benzene prepared in Example 2 and 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 toluene solution of the filtrate, 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.
実施例2で製造した1,3-ビス[4’-(3”-アミノフェニルオキシ)フェニル]ベンゼン4.44g(0.01モル)、4-ヨードビフェニル14g(0.05モル)、ヨウ化第一銅0.057g(0.0003モル)、およびカリウム-tert-ブトキシド5.6g(0.05モル)をトルエン(150ml)に加え、さらにトリ-tert-ブチルホスフィン0.12g(0.0006モル)を加えた後、反応混合物を、105℃で14時間撹拌した。反応混合物を濾過し、濾液のトルエン溶液からトルエンを留去した。残渣をシリカゲルカラムクロマトグラフィー(溶出液:トルエン)で分離して、式(a)で表される化合物6.6gをほぼ無色の結晶として得た(収率63%)。この化合物のガラス転移温度は84℃であった。
(Application 1)
4.44-g (0.01 mol) of 1,3-bis [4 ′-(3 ″ -aminophenyloxy) phenyl] benzene prepared in Example 2 and 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 toluene solution of the filtrate, 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.
(応用例2)
ゲート電極としての抵抗率0.02Ω・cmのシリコン基板に、厚さ200nmの熱酸化膜(SiO2)を形成した。ここで、シリコン基板自体がゲート電極となり、シリコン基板表面に形成されたSiO2層がゲート絶縁層となる。このシリコン基板を60℃に加温し、その上に、応用例1で製造した式(a)で表される化合物のトルエン溶液(濃度:0.7質量%)を塗布し、トルエンを蒸発させて、式(a)で表される化合物から成る有機半導体層(厚み:80nm)を形成した。さらに、この上に、マスクを用いて、金を蒸着してソース電極およびドレイン電極を形成した。尚、ソース電極およびドレイン電極の厚みは80nmであり、チャネル幅は2mm、チャネル長は50μmであった。以上のように作製した有機トランジスタは、p-型の有機トランジスタ素子としての特性を示した。有機トランジスタの電流-電圧(I-V)特性の飽和領域から、電荷移動度を求めたところ、2×10-3(cm2/Vsec)であった。さらに、ドレインバイアス-50Vとし、ゲートバイアス-50Vおよび0Vにした時のドレイン電流値を測定し、電流のオン/オフ比を求めたところ、4.7×103であった。尚、この有機トランジスタの閾値電圧は、-12Vであった。
(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. Furthermore, using this mask, gold was vapor-deposited to form a source electrode and a drain electrode. 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 and the gate bias was −50 V and 0 V, the drain current value was measured, and the current on / off ratio was determined to be 4.7 × 10 3 . The threshold voltage of this organic transistor was −12V.
ゲート電極としての抵抗率0.02Ω・cmのシリコン基板に、厚さ200nmの熱酸化膜(SiO2)を形成した。ここで、シリコン基板自体がゲート電極となり、シリコン基板表面に形成されたSiO2層がゲート絶縁層となる。このシリコン基板を60℃に加温し、その上に、応用例1で製造した式(a)で表される化合物のトルエン溶液(濃度:0.7質量%)を塗布し、トルエンを蒸発させて、式(a)で表される化合物から成る有機半導体層(厚み:80nm)を形成した。さらに、この上に、マスクを用いて、金を蒸着してソース電極およびドレイン電極を形成した。尚、ソース電極およびドレイン電極の厚みは80nmであり、チャネル幅は2mm、チャネル長は50μmであった。以上のように作製した有機トランジスタは、p-型の有機トランジスタ素子としての特性を示した。有機トランジスタの電流-電圧(I-V)特性の飽和領域から、電荷移動度を求めたところ、2×10-3(cm2/Vsec)であった。さらに、ドレインバイアス-50Vとし、ゲートバイアス-50Vおよび0Vにした時のドレイン電流値を測定し、電流のオン/オフ比を求めたところ、4.7×103であった。尚、この有機トランジスタの閾値電圧は、-12Vであった。
(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. Furthermore, using this mask, gold was vapor-deposited to form a source electrode and a drain electrode. 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 and the gate bias was −50 V and 0 V, the drain current value was measured, and the current on / off ratio was determined to be 4.7 × 10 3 . The threshold voltage of this organic transistor was −12V.
本発明により、一般式(1)で表される新規なエーテル化合物を提供することが可能になった。本発明により、各種の機能性高分子材料(例えば、ポリイミド、ポリアミド、ポリカルボジイミド)、各種の機能性電子材料(例えば、有機電界発光素子材料、有機トランジスタ素子材料、光電変換素子材料)を製造する際に有用な原料となる化合物、および該化合物の製造方法を提供することが可能になった。
According to the present invention, it is 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.
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PCT/JP2013/063120 WO2013179872A1 (en) | 2012-05-31 | 2013-05-10 | Ether compound and method for producing same |
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Cited By (3)
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JP2015137232A (en) * | 2014-01-20 | 2015-07-30 | Jx日鉱日石エネルギー株式会社 | METHOD FOR PRODUCING NORBORNANE-2-SPIRO-α-CYCLOALKANONE-α'-SPIRO-2''-NORBORNANE-5,5'',6,6''-TETRACARBOXYLIC ACID AND ESTERS THEREOF |
JP2015137230A (en) * | 2014-01-20 | 2015-07-30 | Jx日鉱日石エネルギー株式会社 | METHOD FOR PRODUCING NORBORNANE-2-SPIRO-α-CYCLOALKANONE-α'-SPIRO-2''-NORBORNANE-5,5'',6,6''-TETRACARBOXYLIC ACID AND ESTERS THEREOF |
CN108129379A (en) * | 2018-01-26 | 2018-06-08 | 常州市阳光药业有限公司 | Oxo-bis-(N-Methyl-o-phthalimide)Synthetic method |
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JP2015137232A (en) * | 2014-01-20 | 2015-07-30 | Jx日鉱日石エネルギー株式会社 | METHOD FOR PRODUCING NORBORNANE-2-SPIRO-α-CYCLOALKANONE-α'-SPIRO-2''-NORBORNANE-5,5'',6,6''-TETRACARBOXYLIC ACID AND ESTERS THEREOF |
JP2015137230A (en) * | 2014-01-20 | 2015-07-30 | Jx日鉱日石エネルギー株式会社 | METHOD FOR PRODUCING NORBORNANE-2-SPIRO-α-CYCLOALKANONE-α'-SPIRO-2''-NORBORNANE-5,5'',6,6''-TETRACARBOXYLIC ACID AND ESTERS THEREOF |
CN108129379A (en) * | 2018-01-26 | 2018-06-08 | 常州市阳光药业有限公司 | Oxo-bis-(N-Methyl-o-phthalimide)Synthetic method |
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JP6192172B2 (en) | 2017-09-06 |
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