JP2016069283A - Ester compound and production process for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ester compound with specific structure useful as a raw-material in the production of a functional polymer material that has an excellent processability (solvent dissolvability), rigidity and heat resistance, and has no problem in the safety of handling, and to provide a production process for the compound.SOLUTION: Provided is an ester compound represented by a general formula (1), and a production process for the compound; and a production process for the ester compound substituted with an amino group, including the reaction of the ester compound substituted with a nitro group with a hydrogen source preferably under the presence of a catalyst. (Xand Xare each independently a nitro group or an amino group.).SELECTED DRAWING: None

Description

The present invention relates to a novel ester compound. More specifically, the present invention relates to various functional polymer materials such as polyamide, polyimide and epoxy resin raw materials, ester compounds useful as functional polymer materials such as epoxy compound curing agents, and methods for producing the compounds. .

In recent years, functional polymer materials have been required to satisfy various properties typified by processability (solvent solubility), rigidity, and heat resistance in applications as composite materials in addition to thermal and mechanical manufacturing methods. Yes. Polyimide resin is attracting attention as such a material, but polyimide resin has a drawback that it is difficult to process while having high performance. For example, the most typical aromatic polyimide consisting of 4,4'-diaminodiphenyl ether and pyromellitic anhydride (Du'pont, trade name "Vespel" is insoluble and infusible, so it is specially called powder sintering molding For this reason, it is difficult to obtain a processed product having a complicated shape by this method, and in order to obtain a satisfactory molded product, the molded product must be further processed by cutting or the like. There is a major drawback.
Moreover, many diamine compounds useful as raw materials for functional polymer materials are positive for mutagenicity, and there is concern about safety in handling.

In order to improve such a defect, various methods for improving the diamine component of the raw material have been tried.
For example, aromatic raw materials such as paraphenylenediamine, benzidine, 4,4′-diaminobenzanilide, and 4,4′-diaminodiphenyl ether are used as raw materials for producing polyimides having excellent heat resistance and mechanical properties and soluble in organic solvents. An amino compound having an amino group at the para position has been proposed (Patent Document 1, Patent Document 2, and Patent Document 3).
Diaminodiphenoxybenzophenones have been proposed as raw materials for producing polyamides having good transparency, heat resistance, mechanical strength and excellent processing characteristics (Patent Document 4).
Bis (aminobenzoyloxy) biphenyls have been proposed as a diamine compound as a resin raw material having excellent flexibility and moldability (Patent Document 5).
A novel aromatic diamine compound useful as a polymerizable monomer material such as polyimide, polyamide and polyamideimide, or a curing agent such as polyurethane and epoxy resin has been proposed (Patent Document 6).
Furthermore, a diamine compound having an ether bond in the molecule, for example, a polyimide (copolymer polyamide) using 3,4′-diaminodiphenyl ether and 1,4-bis (4-aminophenoxy) benzene has been proposed. (Patent Documents 7 and 8)
However, conventional diamine compounds are not always satisfactory in order to meet the recent demand for higher performance of functional polymer materials.

JP-A-9-118748 Japanese Patent Laid-Open No. 9-118749 JP 2004-137407 A Japanese Patent Laid-Open No. 11-158268 JP-A-5-194339 JP 2006-219396 A JP-A-1-204930 JP-A-4-252226

An object of the present invention is to provide a functional polymer material that is excellent in processability (solvent solubility), rigidity, and heat resistance and has no problem in handling safety.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention

（式中、Ｘ_１およびＸ_２はそれぞれ独立に、ニトロ基またはアミノ基を表す。） (i) an ester compound represented by the general formula (1),

(Wherein, X ₁ and X ₂ each independently represent a nitro group or an amino group)

（式中、Ｘはハロゲン原子を表す） (Ii) A process for producing a compound represented by the general formula (1A) comprising reacting a compound represented by the formula (2) and a compound represented by the general formula (3) in the presence of a base,

(Wherein X represents a halogen atom)

に関する。
(Iii) a method for producing a compound represented by the general formula (1B) comprising reacting a compound represented by the general formula (1A) and a hydrogen source in the presence of a catalyst;

About.

According to the present invention, there are provided various functional polymer materials, for example, monomer materials for polymerization such as polyimide, polyamide and polyamideimide, and ester compounds useful as curing agents such as epoxy resins, and methods for producing the compounds. It became possible.

（式中、Ｘ₁およびＸ₂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 provides an ester compound represented by the general formula (1).

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

In the ester compound represented by the general formula (1), X ₁ and X ₂ each independently represent a nitro group or an amino group, and more preferably X ₁ and X ₂ simultaneously represent a nitro group or an amino group. In the ester compound represented by the general formula (1), X ₁ and X ₂ each independently represent an ortho position, a meta position or a para position with respect to the ester bond (—O—CO—), Preferably it represents a meta position or a para position, more preferably X ₁ and X ₂ represent a meta position or a para position at the same time.

The compound represented by the general formula (1) is more preferably a compound represented by the general formula (1A) or the general formula (1B).

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

（式中、Ｘはハロゲン原子を表す） In the general formula (1), the method for producing the compound represented by the general formula (1A) in which X ₁ and X ₂ are simultaneously nitro groups is not particularly limited, but preferably in the presence of a base, the formula It can be produced by reacting the compound represented by (2) with the compound represented by the general formula (3).

(Wherein X represents a halogen atom)

In the compound represented by the general formula (3), the nitro group represents an ortho position, a meta position or a para position, more preferably a meta position or a para position with respect to the carbonyl group.
In the general formula (3), X represents a halogen atom, more preferably a fluorine atom, a chlorine atom or a bromine atom, still more preferably a fluorine atom or a chlorine atom, and particularly preferably a chlorine atom.
The amount of the compound represented by the general formula (3) used in the production of the compound represented by the general formula (1A) is generally 2.0 to 3 with respect to 1 mol of the compound represented by the formula (2). About 2.0 mol, more preferably about 2.0 to 2.5 mol, and still more preferably about 2.02 to 2.1 mol are used.

Examples of the base used in the production of the compound represented by the general formula (1A) include sodium carbonate, potassium carbonate, cesium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium phosphate, potassium phosphate, Inorganic bases such as sodium bicarbonate and 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), 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 usage-amount of a base is 2-3 mol with respect to the total amount of the compound represented by General formula (3), Preferably 2.02-2.1 mol is used.

The production of the compound represented by the general formula (1A) 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 ethers such as ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, aliphatic hydrocarbons such as hexane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, and ethyl acetate. , Esters such as butyl acetate, and aprotic polar solvents such as N, N-dimethylformamide and 1,3-dimethyl-2-imidazolidinone can be used.
These organic solvents may be used alone or in combination.
The amount of the organic solvent used is usually preferably 0.1 to 30 times the weight, more preferably 0.3 to 20 times the weight, and still more preferably 0.5 to 10 times the weight of the raw material.

The reaction temperature for producing the compound represented by the general formula (1A) is not particularly limited, but is generally about 0 to 200 ° C, preferably about 30 to 150 ° C, more preferably, It implements at about 80-110 degreeC.
The reaction time for producing the compound represented by the general formula (1A) is not particularly limited, but is generally about 1 to 40 hours, more preferably about 5 to 24 hours. .
The reaction for producing the compound represented by the general formula (1A) can be carried out in the atmosphere, but is generally carried out in the presence of an inert gas (for example, nitrogen, argon, helium). It is preferable.
In the production of the compound represented by the general formula (1A), the reaction may be carried out under normal pressure, and may be carried out under reduced pressure or under pressure as desired.

The general formula (1A) produced by such a method can be filtered and isolated when crystals are precipitated after the reaction is completed, otherwise the reaction solution is concentrated or directly in water. The product precipitated by discharge can be filtered and isolated.
Further, the compound represented by the general formula (1A) can be isolated and purified by a known method such as a recrystallization method or a chromatography method, if desired.

Incidentally, in the general formula (1), for the preparation of compounds in which X ₁ and X ₂ are represented by the general formula (1B) is an amino group at the same time, is not particularly limited, preferably the general formula ( It can be produced by reducing the nitro group in the compound represented by 1A) and converting it to an amino group.
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.). The source itself is capable of supplying hydrogen, more preferably hydrogen or hydrazine, and more preferably hydrogen.
In addition, when using hydrogen as a hydrogen source, hydrogen may be used in a gaseous state and may be used in a solution state dissolved in an organic solvent.
The amount of the hydrogen source used is not particularly limited, but an amount sufficient to convert the nitro group in the compound represented by the general formula (1A) to an amino group is used, and an excess amount of hydrogen Although it can be carried out in the presence of a source, in general, the hydrogen source is used in an amount of about 4 to 8 mol per mol of the compound represented by the general formula (1A) in terms of 1 mol of hydrogen. More preferably, about 6 mol is used.

The catalyst is preferably a metal catalyst containing a metal atom selected from Groups 8 to 10 of the periodic table, more preferably an iron, rhodium, nickel, palladium, ruthenium, cobalt or platinum atom. And more preferably a palladium catalyst containing a palladium atom.
The catalyst is preferably used in a form in which the metal atom is supported on a carrier such as carbon, alumina, silica, zeolite, or barium sulfate.
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 30% by mass with respect to the compound represented by the general formula (1A). %.

When the compound represented by the general formula (1A) 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.
The organic solvent is not particularly limited as long as it is inert to the reaction. For example, an aliphatic hydrocarbon solvent such as pentane, hexane, octane, cyclohexane,
For example, aromatic hydrocarbon solvents such as benzene, toluene, o-xylene, m-xylene, p-xylene, mixed xylene, mesitylene, cumene, pseudocumene, tetralin,
For example, alcohol solvents such as methanol, ethanol, isopropyl alcohol, butanol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol,
For example, ester solvents such as ethyl acetate, butyl acetate, amyl acetate,
For example, ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diisopropyl ether, diisobutyl ether, cyclopentyl methyl ether, anisole, diphenyl ether,
For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1, An organic solvent such as an aprotic polar solvent such as 3-di-n-butyl-2-imidazolidinone and hexamethylphosphoramide can be used.
These organic solvents may be used alone or in combination.
The amount of the organic solvent used is not particularly limited, but generally, the concentration of the compound represented by the general formula (1A) is about 0.05 to 6M, more preferably 0.08 to 5M. Prepare to an appropriate amount.

In the production of the compound represented by the general formula (1B), the method for supplying the compound represented by the general formula (1A), the catalyst, the organic solvent and the hydrogen source is not particularly limited.
(A) A method of supplying a hydrogen source to a mixture of a compound represented by the general formula (1A) and a catalyst in the presence of an organic solvent,
(A) 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 (1A) can be exemplified.

The reaction temperature when the compound represented by the general formula (1A) and the hydrogen source are allowed to act is not particularly limited, but is generally about 0 to 200 ° C, preferably about 10 to 150 ° C. More preferably, it implements at about 20-120 degreeC.
The reaction pressure is usually about normal pressure to 50 atm.
Further, the reaction time when the compound represented by the general formula (1A) and the hydrogen source are allowed to act is not particularly limited, but is generally about 1 to 100 hours, more preferably about 2 to 60 hours. Can be implemented.
In addition, the reaction between the compound represented by the general formula (1A) 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 (1A) and a hydrogen source are allowed to act, the reaction may be carried out under normal pressure, or under reduced pressure or under pressure as desired.

Since the compound represented by the general formula (1B) produced by such a method has an amino group in the molecule, for example, an acid (for example, hydrogen chloride, hydrogen bromide, sulfuric acid) acts on the compound. And can be isolated as a salt (eg, hydrochloride, odorate, sulfate).
The salt of the compound represented by the general formula (1B) is converted into the compound represented by the general formula (1B) by the action of a base (for example, ammonia, sodium hydroxide, potassium hydroxide). Can do.
Moreover, the compound represented by general formula (1B) can be isolated and refine | purified by well-known methods, such as a recrystallization method and a chromatography method, as needed.
In addition, the compound represented by the general formula (1B) and a salt of the compound can be purified by the action of, for example, activated carbon or zeolite in the presence of an organic solvent and / or water.
In addition, the structure of the compound represented by general formula (1A) and general formula (1B) is various analysis methods, such as elemental analysis, MS (FD-MS) analysis, IR analysis, < ¹ > H-NMR, < ¹³ > C-NMR. Can be identified.

When producing the compounds represented by the general formula (1A) and the general formula (1B), the type and form of the reaction apparatus to be used are not particularly limited, but generally, a tank type, a tube type, a column type These reactors can be used. Moreover, each manufacturing process can be implemented by a batch type (batch type), and also can be implemented continuously.
Moreover, when manufacturing the compound represented by General formula (1A) and General formula (1B), the reaction apparatus to be used can be equipped with various stirring apparatuses. Such stirrers include, for example, paddle type stirrers, propeller type stirrers, turbine type stirrers, homogenizers, homomixers, line mixers, line homomixers, and other high speed stirrers, as well as static mixers, colloid mills, and orifice mixers. And a flow jet mixer.
The progress of the reaction in each production process can be traced by a method such as thin layer chromatography, high performance liquid chromatography, or gas chromatography.
In the general formula (1), when X ₁ and X ₂ are different, for example, the compound represented by the general formula (1C) in which X ₁ is a nitro group and X ₂ is an amino group is a compound represented by the general formula (1A) It can be produced by the same method as that for the compound represented by the general formula (1B). It is produced in the process of producing the compound represented by the general formula (1B), and can be isolated by chromatography or the like if desired.
Adjusting the amount of hydrogen source used while following the progress of the reaction in the same manner as the compound represented by the general formula (1B), for example, by thin layer chromatography, high performance liquid chromatography, gas chromatography, etc. Can be obtained with relatively high purity.

窒素雰囲気下、式(２)の化合物４０.６ｇ(０.１３ ｍｏｌ)をメチルイソブチルケトン(４６１.２ｇ）に溶解し、さらに、ピリジン２２.８ｇ(０.２９ ｍｏｌ)を加え１０５ ℃に加熱した。この溶液に４−ニトロベンゾイルクロライド５３.４ｇ(０.２９ ｍｏｌ)のメチルイソブチルケトン(８０ｇ)溶液を１時間要して滴下した。この反応混合物を１１０ ℃にて４時間撹拌した。この反応混合物から、メチルイソブチルケトンを減圧下で留去し、残渣に５０ ℃でメタノールを滴下した後、室温まで冷却後、析出している固体を濾別し、メタノール洗浄を行った。この固体を６０ ℃で１４時間乾燥して化合物(１Ａ―１)７７.１ｇを白色の固体として得た(収率９６.９％)。
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％以上(面積比)であった。この化合物について熱分析測定を行ったところ、ガラス転移温度は２６４.９℃であった。
得られた化合物は、下記の分析結果より目的の化合物であることを確認した。
・ＭＳ：（ＥＩ）ｍ/z ６０８Ｍ＋）
・元素分析値：実測値（Ｃ：６９.０１％、Ｈ：５.２５％、Ｎ：４.６２％）
；理論値（Ｃ：６９.０７％、Ｈ：５.３０％、Ｎ：４.６０％）
・Ａｍｅｓ試験：陰性
Example 1 Production of a compound represented by the following formula (1A-1)

Under a nitrogen atmosphere, 40.6 g (0.13 mol) of the compound of formula (2) is dissolved in methyl isobutyl ketone (461.2 g), and further 22.8 g (0.29 mol) of pyridine is added and heated to 105 ° C. did. To this solution, a solution of 53.4 g (0.29 mol) of 4-nitrobenzoyl chloride in methyl isobutyl ketone (80 g) was added dropwise over 1 hour. The reaction mixture was stirred at 110 ° C. for 4 hours. From this reaction mixture, methyl isobutyl ketone was distilled off under reduced pressure. Methanol was added dropwise to the residue at 50 ° C., and after cooling to room temperature, the precipitated solid was separated by filtration and washed with methanol. This solid was dried at 60 ° C. for 14 hours to obtain 77.1 g of Compound (1A-1) as a white solid (yield 96.9%).
As a result of analysis by high performance liquid chromatography, the purity of this compound was 99% or more (area ratio). When thermal analysis measurement was performed on this compound, the glass transition temperature was 264.9 ° C.
The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 608M +)
Elemental analysis values: measured values (C: 69.01%, H: 5.25%, N: 4.62%)
; Theoretical value (C: 69.07%, H: 5.30%, N: 4.60%)
Ames test: negative

(Example 2)
Under a nitrogen atmosphere, 7.5 g (0.02 mol) of the compound of formula (2) was dissolved in N, N-dimethylformamide (10 g), and 4.0 g (0.05 mol) of pyridine was further added and heated to 80 ° C. To this solution, a solution of 9.5 g (0.05 mol) of 4-nitrobenzoyl chloride in N, N-dimethylformamide (14 g) was added dropwise over 1 hour. The reaction mixture was stirred at 120 ° C. for 4 hours. To this reaction mixture, an aqueous sodium hydrogen carbonate solution was added dropwise at 50 ° C., and after cooling to room temperature, the precipitated solid was separated by filtration, washed with water and washed with methanol.
This solid was dried at 60 ° C. for 14 hours to obtain 11.6 g of Compound (1A-1) as a white solid (yield 79.2%). The purity of this compound was 98.9% (area ratio) as a result of analysis by high performance liquid chromatography.

(Example 3)
In Example 1, 71.6 g of Compound (1A-1) was obtained according to the procedure described in Example 1 except that 29.3 g (0.29 mol) of triethylamine was used instead of pyridine. (Rate 90.0%).
As a result of analysis by high performance liquid chromatography, the purity of this compound was 99% or more (area ratio).

実施例１で製造した化合物(１Ａ−１)１８.３ｇ(０.０３ ｍｏｌ)を９０℃で加熱溶解させたＮ,Ｎ-ジメチルホルムアミド(２６０ ｍｌ)溶液を常圧下、水素ガス雰囲気下で５質量％パラジウム/アルミナを含むＮ,Ｎ-ジメチルホルムアミド(７０ ｍｌ)溶液に撹拌下、７５ ℃で２時間を要して加えた。さらに常圧下、水素ガス雰囲気下、７５℃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０.１８ molを吸収した)。室温に冷却後反応混合物を濾過し、５質量％パラジウム/アルミナを濾別した後、濾液からＮ,Ｎ-ジメチルホルムアミドを減圧下で留去した。残渣に８０ ℃で水を滴下した後、室温に冷却後、析出している固体を濾別し、水洗を行った。
この固体を６０℃で１４時間減圧乾燥して化合物(１Ｂ-１)１６.２ｇを白色の固体として得た(収率９８.０％)。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％以上(面積比)であった。この化合物について熱分析測定を行ったところ、ガラス転移温度は２６５.３℃であった。
得られた化合物は、下記の分析結果より目的の化合物であることを確認した。
・ＭＳ：（ＥＩ）ｍ/z ５４８Ｍ＋）
・元素分析値：実測値（Ｃ：７６.５８％、Ｈ：６.５９％、Ｎ：５.１４％）
；理論値（Ｃ：７６.６２％、Ｈ：６.６１％、Ｎ：５.１１％）
・Ａｍｅｓ試験：陰性
(Example 4) Production of a compound represented by the following formula (1B-1)

An N, N-dimethylformamide (260 ml) solution in which 18.3 g (0.03 mol) of the compound (1A-1) produced in Example 1 was dissolved by heating at 90 ° C. was added under atmospheric pressure and a hydrogen gas atmosphere. The mixture was added to a N, N-dimethylformamide (70 ml) solution containing mass% palladium / alumina at 75 ° C. over 2 hours with stirring. Furthermore, hydrogenation was performed by stirring at 75 ° C. for 1 hour under normal pressure and hydrogen gas atmosphere (during this time, the reaction mixture absorbed 0.18 mol of hydrogen). After cooling to room temperature, the reaction mixture was filtered and 5 mass% palladium / alumina was filtered off, and then N, N-dimethylformamide was distilled off from the filtrate under reduced pressure. Water was added dropwise to the residue at 80 ° C., and after cooling to room temperature, the precipitated solid was separated by filtration and washed with water.
This solid was dried under reduced pressure at 60 ° C. for 14 hours to obtain 16.2 g of compound (1B-1) as a white solid (yield 98.0%). As a result of analysis by high performance liquid chromatography, the purity of this compound was 99% or more (area ratio). When this compound was subjected to thermal analysis measurement, the glass transition temperature was 265.3 ° C.
The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 548M +)
Elemental analysis values: measured values (C: 76.58%, H: 6.59%, N: 5.14%)
Theoretical value (C: 76.62%, H: 6.61%, N: 5.11%)
Ames test: negative

窒素雰囲気下、式(２)の化合物２０.３ｇ(０.０６５ ｍｏｌ)をメチルイソブチルケトン(２３０ｇ)に溶解し、さらに、ピリジン１１.４(０.１４５ｍｏｌ)を加え、１０５ ℃に加熱した。この溶液に３−ニトロベンゾイルクロライド２６.７ｇ(０.１４５ ｍｏｌ）のメチルイソブチルケトン(４０ｇ)溶液を１時間要して滴下した。この反応混合物を１１０℃４時間撹拌した。この反応混合物から、メチルイソブチルケトンを減圧下で留去し、残渣に５０℃でメタノールを滴下した後、室温まで冷却後、析出している固体を濾別し、メタノール洗浄を行った。この固体を６０℃で１４時間乾燥して化合物(１Ａ−２)３８.６ｇを白色の固体として得た(収率９６.９％）。
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％以上(面積比)であった。この化合物について熱分析測定を行ったところ、ガラス転移温度は２１２.２℃であった。得られた化合物は下記の分析結果より目的の化合物であることを確認した。
・ＭＳ：（ＥＩ）ｍ/z ６０８Ｍ＋）
・元素分析値：実測値（Ｃ：６９.０３％、Ｈ：５.２７％、Ｎ：４.６３％）
；理論値（Ｃ：６９.０７％、Ｈ：５.３０％、Ｎ：４.６０％）
・Ａｍｅｓ試験：陰性
(Example 5) Production of a compound represented by the following formula (1A-2)

Under a nitrogen atmosphere, 20.3 g (0.065 mol) of the compound of formula (2) was dissolved in methyl isobutyl ketone (230 g), pyridine 11.4 (0.145 mol) was further added, and the mixture was heated to 105 ° C. To this solution, a solution of 26.7 g (0.145 mol) of 3-nitrobenzoyl chloride in methyl isobutyl ketone (40 g) was added dropwise over 1 hour. The reaction mixture was stirred at 110 ° C. for 4 hours. From this reaction mixture, methyl isobutyl ketone was distilled off under reduced pressure, methanol was added dropwise to the residue at 50 ° C., and the mixture was cooled to room temperature. The precipitated solid was filtered off and washed with methanol. This solid was dried at 60 ° C. for 14 hours to obtain 38.6 g of Compound (1A-2) as a white solid (yield 96.9%).
As a result of analysis by high performance liquid chromatography, the purity of this compound was 99% or more (area ratio). When this compound was subjected to thermal analysis measurement, the glass transition temperature was 212.2 ° C. The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 608M +)
Elemental analysis value: Actual measurement value (C: 69.03%, H: 5.27%, N: 4.63%)
; Theoretical value (C: 69.07%, H: 5.30%, N: 4.60%)
Ames test: negative

実施例５で製造した化合物(１Ａ−２)１８.３ｇ(０.０３ ｍｏｌ)を９０ ℃で加熱溶解させたＮ,Ｎ-ジメチルホルムアミド(２６０ｍｌ)溶液を常圧下、水素ガス雰囲気下で５質量％パラジウム/アルミナを含むＮ,Ｎ-ジメチルホルムアミド(７０ ｍｌ)溶液に撹拌下、７５℃で２時間を要して加えた。さらに常圧下、水素ガス雰囲気下、７５℃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０.１８ ｍｏｌを吸収した)。
室温に冷却後反応混合物を濾過し、５質量％パラジウム/アルミナを濾別した後、濾液からＮ,Ｎ-ジメチルホルムアミドを減圧下で留去した。残渣に８０ ℃で水を滴下した後、室温に冷却後、析出している固体を濾別し、水洗を行った。この固体を６０℃で１４時間減圧乾燥して化合物(１Ｂ−２)１５.９ｇ を白色の固体として得た(収率９６.０％)。
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％以上（面積比）であった。
この化合物について熱分析測定を行ったところ、ガラス転移温度は２３５.３℃であった。得られた化合物は、下記の分析結果より目的の化合物であることを確認した。
・ＭＳ：（ＥＩ）ｍ/z ５４８Ｍ＋）
・元素分析値：実測値（Ｃ：７６.５７％、Ｈ：６.５７％、Ｎ：５.１３％）
；理論値（Ｃ：７６.６２％、Ｈ：６.６１％、Ｎ：５.１１％）
Ａｍｅｓ試験：陰性
(Example 6) Production of a compound represented by the following formula (1B-2)

5 mass of N, N-dimethylformamide (260 ml) solution obtained by dissolving 18.3 g (0.03 mol) of the compound (1A-2) produced in Example 5 with heating at 90 ° C. under normal pressure and hydrogen gas atmosphere. It was added to N, N-dimethylformamide (70 ml) solution containing% palladium / alumina at 75 ° C. over 2 hours with stirring. Further, hydrogenation was performed by stirring at 75 ° C. for 1 hour under a normal pressure and hydrogen gas atmosphere (during this time, the reaction mixture absorbed 0.18 mol of hydrogen).
After cooling to room temperature, the reaction mixture was filtered and 5 mass% palladium / alumina was filtered off, and then N, N-dimethylformamide was distilled off from the filtrate under reduced pressure. Water was added dropwise to the residue at 80 ° C., and after cooling to room temperature, the precipitated solid was separated by filtration and washed with water. This solid was dried under reduced pressure at 60 ° C. for 14 hours to obtain 15.9 g of Compound (1B-2) as a white solid (yield 96.0%).
The purity of this compound was 99% or more (area ratio) as a result of analysis by high performance liquid chromatography.
When this compound was subjected to thermal analysis measurement, the glass transition temperature was 235.3 ° C. The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 548M +)
Elemental analysis values: measured values (C: 76.57%, H: 6.57%, N: 5.13%)
Theoretical value (C: 76.62%, H: 6.61%, N: 5.11%)
Ames test: negative

  The compound of the present invention is useful as a raw material for various functional polymer materials excellent in processability (solvent solubility), rigidity and heat resistance, and is highly safe from the viewpoint of positive mutagenicity.

Claims (3)

An ester compound represented by the general formula (1).

(In the formula, X ₁ and X ₂ each independently represent a nitro group or an amino group.)
A method for producing a compound represented by the general formula (1A), comprising reacting a compound represented by the formula (2) and a compound represented by the general formula (3) in the presence of a base.

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