JP2020070255A - Bis(amino or nitrophenoxy) benzene compound, method for producing the same, and polyimide - Google Patents

Abstract

To provide a novel bis (amino or nitrophenoxy) benzene derivative, a method for producing the same, and polyimide synthesis.SOLUTION: The present invention relates to a compound represented by the following formula (1) and a method for producing the compound (where R, R, R, R, R, R, R, R, R, R, Rand Rindependently represent a hydrogen atom or a substituent selected from a C1 to 6 optionally substituted alkyl group and a C1 to 3 alkoxy group, at least one of R, R, Rand Ris the above-mentioned substituent, at least one of R, R, Rand Ris the above-mentioned substituent, and at least one of R, R, Rand Ris the above-mentioned substituent, and A and B independently represent a nitro group or an amino group), excluding 1,4-bis(4-amino-2-methyl phenoxy)-2,3,5-trimethyl benzene.SELECTED DRAWING: None

Description

  TECHNICAL FIELD The present invention relates to bis (aminophenoxy) benzene and derivatives thereof which are useful as a raw material for highly functional polymers such as polyimide and various organic compounds, and a method for producing the same. Further, the present invention relates to (aminophenoxy) (nitrophenoxy) benzene, bis (nitrophenoxy) benzene, which are precursors of the diamine compound, and derivatives thereof, and a method for producing these compounds.

  High-speed, large-capacity communication is required for printed wiring boards and the like used in the field of information and communication, and therefore higher frequency bands are expected to be used than before. However, there is a problem that the transmission loss increases as the frequency becomes higher. Transmission loss is divided into contributions of resistance loss and dielectric loss. Among them, the resistance loss has a characteristic of changing to heat in proportion to the frequency, and the dielectric loss has a characteristic of being proportional to frequency, dielectric loss tangent, and relative permittivity.

  A material that can withstand use in a high frequency band is required to have not only heat resistance but also excellent electrical characteristics, particularly a low dielectric constant and a low dielectric loss tangent. Polyimide resins (PI) and polyamide resins are known as excellent high heat resistant materials (Non-Patent Documents 1 and 2). However, these resins have a highly polar imide group or amide group structure in the molecule, and due to these contributions, the dielectric constant (k) of many PIs usually exceeds 3.0. is there. In addition, for example, polyphenylene ether resin (PPE) is known as a material having excellent electrical characteristics (Patent Document 1, Non-Patent Documents 1 and 2). However, they are thermoplastic and have problems such as poor fluidity during melting and poor solvent solubility.

JP, 2005-82793, A

Pathrick R. et al. A. et al, "Journal of Applied Polymer Science", vol. 132, p. 41684-41692, 2015. Akhter Z. et al, "Polymer Bulletin", vol. 74, p. 3889-3906, 2017.

  As a material having excellent high heat resistance and electric characteristics, a low dielectric constant of PI has been proposed. PI is an attractive material for molecular design with a low dielectric constant because of the variety of diamine designs that are its monomers. The basic idea of lowering the dielectric constant of PI lies in how to dilute (reduce) the imide group concentration that contributes to the high dielectric constant. In order to reduce the imide group concentration in PI, it is effective to employ a diamine having a trinuclear or higher aromatic ring instead of a binuclear compound such as oxydianiline, which is a typical aromatic diamine. However, as the imide group concentration is lowered, the heat resistance of PI is impaired. In order to reduce the imide group concentration and not to impair the heat resistance, a bulky hydrocarbon is introduced into the aromatic ring to allow free rotation of the ether bond at the aromatic amine site or the single bond between the imide ring and the aromatic ring. Is effective to inhibit the primary movement of the polyimide main chain.

  In view of the above circumstances, an object of the present invention is to provide bis (aminophenoxy) benzene and its derivatives, which are useful as resin raw materials such as polyimide resins, electronic materials, and intermediates and raw materials thereof.

  As a result of intensive studies on the problems of bis (aminophenoxy) benzene as described above, the present inventors have found that it is a bis (amino or nitrophenoxy) benzene compound having aminophenoxy or nitrophenoxy and being a trinuclear body. As a result, a novel compound having three aromatic rings each having at least one alkyl group or alkoxy group was produced, and the present invention was completed.

That is, the present invention provides a compound represented by the following formula (1) and a method for producing the compound.
(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ^{1 ′} , R ^{2 ′} , R ^{3 ′} , R ^{4 ′} , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently hydrogen. An atom or a substituent selected from an optionally substituted alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 3 carbon atoms, and at least one of R ¹ , R ² , R ³ and R ⁴ . One is the substituent, at least one of R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and R ^{4 ′} is the substituent, and at least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ Is a substituent, and A and B are each independently a nitro group or an amino group.)
However, 1,4-bis (4-amino-2-methylphenoxy) -2,3,5-trimethylbenzene is excluded.

  Since the bis (amino or nitrophenoxy) benzene compound of the present invention has at least one alkyl group in the benzene ring located in the center, it provides a polyimide resin having a low dielectric constant and a low dielectric loss tangent, and is suitable as a polyimide raw material. Can be used. Further, the bis (nitrophenoxy) benzene compound of the present invention can easily provide the bis (aminophenoxy) benzene compound by reducing the nitro group, and is useful as a polyimide raw material.

FIG. 1 is a chart of ¹ H-NMR spectrum of the compound produced in Example 1. FIG. 2 is a chart of ¹³ C-NMR spectrum of the compound produced in Example 1. FIG. 3 is a chart of the ¹ H-NMR spectrum of the compound produced in Example 2. FIG. 4 is a chart of the ¹³ C-NMR spectrum of the compound produced in Example 2. FIG. 5 is a chart of the ¹ H-NMR spectrum of the compound produced in Example 3. FIG. 6 is a chart of the ¹³ C-NMR spectrum of the compound produced in Example 3. FIG. 7 is a chart of the ¹ H-NMR spectrum of the compound produced in Example 4. FIG. 8 is a chart of the ¹³ C-NMR spectrum of the compound produced in Example 4. FIG. 9 is a chart of the ¹ H-NMR spectrum of the compound produced in Example 5. FIG. 10 is a chart of ¹³ C-NMR spectrum of the compound produced in Example 5. FIG. 11 is a chart of ¹ H-NMR spectrum of the compound produced in Example 6. FIG. 12 is a chart of ¹³ C-NMR spectrum of the compound produced in Example 6. FIG. 13 is a chart of the ¹ H-NMR spectrum of the compound produced in Example 7. FIG. 14 is a chart of ¹³ C-NMR spectrum of the compound produced in Example 7. FIG. 15 is a chart of the ¹ H-NMR spectrum of the compound produced in Example 8. FIG. 16 is a chart of ¹³ C-NMR spectrum of the compound produced in Example 8.

The bis (amino or nitrophenoxy) benzene compound of the present invention is represented by the following formula (1). The details will be described below.

In the above formula (1), A and B are each independently an amino group or a nitro group. A diamine compound in which both A and B are amino groups (following (1-a)) is a compound represented by the above formula (1) in which at least one of A and B is a nitro group (following (1 It can be easily obtained by reducing the nitro group of -b) or (1-c)).

In the above formula (1), R ¹ , R ² , R ³ , R ⁴ , R ^{1 ′} , R ^{2 ′} , R ^{3 ′} , R ^{4 ′} , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independent of each other. And a substituent selected from a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms. The binding sites of R ¹ , R ² , R ³ , R ⁴ , R ^{1 ′} , R ^{2 ′} , R ^{3 ′} , R ^{4 ′} , R ⁵ , R ⁶ , R ⁷ and R ⁸ are not particularly limited. However, in a compound in which three of R ⁵ , R ⁶ , R ⁷ and R ⁸ are the substituents and the remaining one is a hydrogen atom, at least 1 of R ¹ , R ² , R ³ and R ⁴ is One substituent is in the ortho position of the group represented by A, and at least one substituent of R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and R ^{4 ′} is in the ortho position of the group represented by B. Is good.
In addition, R ¹ , R ² , R ³ , and R ⁴ and R ^{1 ′} , R ^{2 ′} , R ^{3 ′} , and R ^{4 ′} may be common, and in that case, in the following formula (1 ′) expressed.

The compound of the present invention has at least one of R ¹ , R ² , R ³ and R ⁴ , and at least one of R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and R ^{4 ′} , R ⁵ , R ⁶ and R ^7. And at least one of R ⁸ is independently a substituent selected from an optionally substituted alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 3 carbon atoms.

At least one of R ¹ , R ² , R ³ and R ⁴ , at least one of R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and R ^{4 ′} and at least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ The two may be different substituents, and two or more may be the same substituent. More specifically, at least one, preferably one or two, more preferably any one of R ¹ , R ² , R ³ and R ⁴ and R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and At least one, preferably one or two, and more preferably any one of R ^{4 ′} is independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. Good. One or more, preferably 1 to 4, more preferably 1 to 3, most preferably 1 or 2 of R ⁵ , R ⁶ , R ⁷ and R ⁸ is an alkyl group having 1 to 6 carbon atoms. Alternatively, it is preferably an alkoxy group having 1 to 3 carbon atoms.

  The alkyl group having 1 to 6 carbon atoms which may be substituted is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, an isobutyl group, or the like, or a bond to these carbon atoms. At least one of the hydrogen atoms is a group substituted with a halogen atom, an alkoxy group, a phenyl group or the like within a range that does not impair the effects of the present invention. It is preferably an unsubstituted alkyl group having 1 to 6 carbon atoms. Examples of the alkoxy group having 1 to 3 carbon atoms include methoxy group, ethoxy group, isopropoxy group, and propoxy group. More preferably, it is an unsubstituted alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably carbon. It is an alkyl group having 1 to 3 atoms, and most preferably a methyl group.

The compound represented by the above formula (1) of the present invention is represented by the following formula (1-d): 1,4-bis (4-amino-2-methylphenoxy) -2,3,5-trimethylbenzene Does not include.

One or two of R ⁵ , R ⁶ , R ⁷ and R ⁸ are an optionally substituted alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are compounds represented by the following formula (1a) or (1b), the rest being hydrogen atoms.
In each of the above formulas, R ¹ , R ² , R ³ , R ⁴ , R ^{1 ′} , R ^{2 ′} , R ^{3 ′} , and R ^{4 ′} are as described above, and R is independently substituted. Which may be an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, most preferably a methyl group, and A and B are as described above.
Of these, compounds represented by the following formula (1a ′) or (1b ′) are preferable.
In the above formulas, R, A, and B are as described above. R ′ and R ″ are each independently an optionally substituted alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and preferably R ^′ is a group represented by A. On the other hand, it is preferably in the ortho position or meta position, and R ^″ is in the ortho position or meta position with respect to the group represented by B.

Further, three of R ⁵ , R ⁶ , R ⁷ and R ⁸ are an optionally substituted alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and the remaining one is a hydrogen atom. As a certain compound, the compound of any one of following formula (1c), (1d), (1e), or (1f) is mentioned.
In the above, R, R ′ and R ″ are each independently an optionally substituted alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and A and B are as described above. In each formula, at least one of R'is in the ortho position of the group represented by A, and at least one of R '' is in the ortho position of the group represented by B. Preferred is a compound represented by the above formula (1c) in which R ′ is in the ortho position of the group represented by A and R ″ is in the ortho position of the group represented by B.

  More specifically, examples of the diamine compound represented by the above formula (1), in which A and B are both amino groups, include, for example, 1,4-bis (4-amino-2-methylphenoxy) -2-methylbenzene. 1,4-bis (4-amino-3-methylphenoxy) -2-methylbenzene, 1,4-bis (4-amino-3-methylphenoxy) -2,3,5-trimethylbenzene, and 1, Examples thereof include 3-bis (4-amino-2-methylphenoxy) -5-methylbenzene, but are not limited to these compounds. Examples of the dinitro compound represented by the above formula (1) in which both A and B are nitro groups include 1,4-bis (2-methyl-4-nitrophenoxy) -2-methylbenzene and 1,4- Bis (3-methyl-4-nitrophenoxy) -2-methylbenzene, 1,4-bis (3-methyl-4-nitrophenoxy) -2,3,5-trimethylbenzene, 1,3-bis (2- Examples thereof include methyl-4-nitrophenoxy) -5-methylbenzene, but are not limited to these compounds.

[Production method]
(1) Method for producing diamine compound represented by the following formula (1-a)
(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ^{1 ′} , R ^{2 ′} , R ^{3 ′} , R ^{4 ′} , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as described above).
The method for producing the diamine compound is not particularly limited and may be produced by any method. For example, it can be obtained by reducing the nitro group of the compound represented by the following general formula (1-b) or (1-c).
(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ^{1 ′} , R ^{2 ′} , R ^{3 ′} , R ^{4 ′} , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as described above. The street)

   The reduction reaction of the nitro group is not particularly limited, and a known method of reducing the nitro group to an amino group can be used. For example, examples of the method for reducing the aromatic dinitro compound include catalytic reduction, Beshan reduction, zinc dust reduction, tin chloride reduction, and hydrazine reduction.

  The solvent used for the reduction reaction is, for example, an alcohol solvent such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-methoxyethanol, and 2-ethoxyethanol, N, N-dimethylformamide, N, N-. Examples include amide-based solvents such as dimethylacetamide, N-methylpyrrolidone, and N, N′-dimethylimidazolidinone, and ether-based solvents such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and diethylene glycol. The solvent is not limited to these as long as it can be dissolved. The amount of the solvent may be adjusted appropriately.

  As the catalyst used for the reduction reaction, a catalyst known as a catalyst for each of the above reduction reactions may be used. Examples of the catalyst used for catalytic reduction or hydrazine reduction include activated carbon, carbon black, graphite, precious metal catalysts such as palladium, platinum and rhodium supported on alumina, Raney nickel catalyst, and sponge nickel catalyst. The amount of the catalyst is not particularly limited, but is usually 0.1 to 10 wt%.

  The reaction temperature and time of the reduction reaction may be appropriately selected. For example, the reaction may be performed at a temperature in the range of 50 to 150 ° C., preferably in the range of 60 to 130 ° C. for 1 to 35 hours, preferably 3 to 10 hours. The method of treating the reaction product is not particularly limited. For example, the compound represented by the general formula (1-a) can be obtained by removing the catalyst, cooling, and filtering the resulting solid, washing with water, and drying. Further, if necessary, a high-purity product can be obtained by refining again by a method such as crystallization filtration and column separation.

(2) Method for producing (di) nitro compound represented by the general formula (1-b) or (1-c) (di) represented by the general formula (1-b) or (1-c) The method for producing the nitro compound is not particularly limited and may be produced by any method. Preferably, one or more compounds represented by the following general formula (2) and one or more compounds represented by the following general formula (3) are heated in an organic solvent, preferably in the presence of a base, under heating. By performing a dehydration condensation reaction, the dinitro compound represented by the above general formula (1-b) is obtained.
In the formula (2), R ¹ , R ² , R ³ and R ⁴ are as described above. X is a halogen atom, for example, a chlorine atom or a fluorine atom, preferably a fluorine atom.
In the formula (3), R ⁵ , R ⁶ , R ⁷ and R ⁸ are as described above. Y is a hydrogen atom, an alkali metal or an alkaline earth metal, and is, for example, sodium or potassium, preferably potassium.

In another embodiment of the production method, one or more compounds represented by the following general formula (4) and one or more compounds represented by the following general formula (5) are prepared in an organic solvent, preferably in the presence of a base. Then, the dinitro compound represented by the general formula (1-b) is obtained by performing a dehydration condensation reaction under heating.
In the formula (4), R ¹ , R ² , R ³ and R ⁴ are as described above. Y is a hydrogen atom, an alkali metal or an alkaline earth metal, and is, for example, sodium or potassium, preferably potassium.
In formula (5), R ⁵ , R ⁶ , R ⁷ and R ⁸ are as described above, and X is a halogen atom, for example, iodine or bromine, preferably bromine.

For example, in the case of reacting 2-chloro-5-nitrotoluene as the compound represented by the general formula (2) with methylhydroquinone as the compound represented by the general formula (3), it is represented by the following reaction formula.

The starting material molar ratio of the compound represented by the general formula (2) and the compound represented by the general formula (3) is usually 1 mol of the compound represented by the general formula (3) to the compound represented by the general formula (2). Is in the range of 2 to 5 mol, preferably in the range of 2 to 3 mol. The reaction solvent is preferably used, and examples thereof include solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone. The amount of the solvent used is usually in the range of 1 to 20 parts by weight with respect to 1 part by weight of the compound represented by the general formula (3), but may be appropriately adjusted. The reaction temperature and reaction time may be appropriately adjusted. For example, the reaction may be performed at a temperature in the range of 100 to 200 ° C., preferably in the range of 130 to 160 ° C. for 0.5 to 12 hours, preferably 2 to 7 hours. The method of treating the reaction product is not particularly limited. For example, after the completion of the reaction, the reaction solution is cooled, or water is added to precipitate or reprecipitate solids or crystals which are separated by filtration, washed with water and dried to obtain the desired product.

  The starting material molar ratio of the compound represented by the general formula (4) to the compound represented by the general formula (5) is usually represented by the general formula (5) with respect to 1 mol of the compound represented by the general formula (4). The compound is in the range of 2 to 5 mol, preferably in the range of 2 to 3 mol. The reaction solvent is preferably used, and examples thereof include solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone. The amount of the solvent used is usually in the range of 1 to 20 parts by weight with respect to 1 part by weight of the compound represented by the general formula (3), but may be appropriately adjusted. The reaction temperature and reaction time may be appropriately adjusted. For example, the reaction may be carried out at a temperature in the range of 100 to 200 ° C., preferably in the range of 130 to 160 ° C. for 0.5 to 12 hours, preferably 2 to 7 hours. The method of treating the reaction product is not particularly limited. For example, after the completion of the reaction, the reaction solution is cooled, or water is added to precipitate or reprecipitate solids or crystals which are separated by filtration, washed with water and dried to obtain the desired product.

  The bis (aminophenoxy) benzene compound represented by the above formula (1-a) is useful as a raw material for polyimide. Further, the bis (nitrophenoxy) benzene compound represented by the formula (1-b) and the (aminophenoxy) (nitrophenoxy) benzene compound represented by the formula (1-c) are bis (aminophenoxy) as described above. ) Useful as a precursor of a benzene compound. The bis (aminophenoxy) benzene compound represented by the above formula (1-a) provides a polyimide compound by reacting with an acid anhydride, for example.

  The acid anhydride may be any conventionally known one that is used as a raw material for polyimide. For example, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, benzophenone-3,4,3 ′, 4′-tetracarboxylic dianhydride, 4,4 ′ -(2,2-hexafluoroisopropylidene) diphthalic acid dianhydride, 2,2-bis [3- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [4- ( 3,4-dicarboxyphenoxy) phenyl] propane dianhydride, and the group consisting of 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride and oxy-4,4′-diphthalic dianhydride. It is at least 1 or more selected from.

The reaction conditions and reaction ratio of the above diamine compound and acid anhydride are not particularly limited and may be appropriately selected according to a conventionally known method. For example, the reaction conditions are
The reaction may be performed at a temperature in the range of 25 to 30 ° C for 0.5 to 24 hours. The reaction ratio may be 1.00. The polyimide compound obtained preferably has a number average molecular weight of 2,000 to 200,000, preferably 10,000 to 50,000. The number average molecular weight is a value measured by, for example, GPC (gel permeation chromatography, THF).

  As the polyimide compound, any diamine compound other than the diamine compound of the present invention may be further reacted. The ratio of the diamine compound of the present invention to the total moles of all diamine compounds is preferably 10 mol% to 100 mol%. Examples of any diamine compound other than the diamine compound of the present invention include 1,4-phenylenediamine, 1,3-phenylenediamine, 1,2-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene. , M-xylylenediamine, p-xylylenediamine, 2,2′-dimethylbenzidine, 3,3′-dimethylbenzidine, 2,2′-bis (trifluoromethyl) benzidine, 4,4′-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminobenz Anilide, 1,3-bis (4-aminophenoxy) benzene 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) Phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl) sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9′-bis (4-aminophenyl) fluorene, One or more selected from the group consisting of 9,9'-bis [4- (4-aminophenoxy) phenyl] fluorene.

  Examples of the molded product made of the polyimide compound of the present invention include materials for high speed / large capacity communication.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.
The measuring method and apparatus used in the following examples are as follows.
SHIMADZU SPD-10A was used for HPLC measurement, and YAMATO MP-21 was used for melting point measurement.
^{For 1} H nuclear magnetic resonance spectrum analysis, JEOL's JNM-ECA600 type was used, and measurement was performed at a resonance frequency of 600 MHz. Deuterated chloroform was used as the measurement solvent.
^{For 13} C nuclear magnetic resonance spectral analysis, JEOL's JNM-ECA600 type was used, and measurement was performed at a resonance frequency of 150 MHz. Deuterated chloroform was used as the measurement solvent.
FT / IR-4100 manufactured by JASCO Corporation was used for the infrared spectroscopic measurement, and the measurement was performed by the KBr tablet method.
GCMS-QP2010 manufactured by SHIMADZU was used for mass spectrometry.
LCMS-IT-TOF manufactured by SHIMADZU was used for accurate mass spectrometry.

[Example 1]
Synthesis of 1,4-bis (2-methyl-4-nitrophenoxy) -2-methylbenzene In a 100 mL three-necked flask, 1.0 g (8.1 mmol) of methylhydroquinone and 2.9 g (16. (9 mmol), 1.5 g (10.6 mmol) of potassium carbonate, 20 mL of DMF, and a stirring magnet were charged and heated, and the reaction was carried out for 7 hours while maintaining the reaction temperature of 150 ° C. After completion of the reaction, the mixture was cooled and 100 mL of distilled water was added. The precipitated solid was filtered, washed and dried to obtain a crude product of 1,4-bis (2-methyl-4-nitrophenoxy) -2-methylbenzene. This was dissolved in acetonitrile, heated, heated, watered, cooled, filtered, washed and dried to obtain 2.2 g of purified 1,4-bis (2-methyl-4-nitrophenoxy) -2-methylbenzene. .. The purity measured by HPLC is 99.9%, mp. Was 179-180 ° C.
The ¹ H-NMR spectrum chart of the compound produced in Example 1 is shown in FIG. 1, and the ¹³ C-NMR spectrum chart is shown in FIG. The results of IR and GC-MS are as follows.
IR (KBr, cm < ^-1 >): 3435, 1590, 1509, 1483, 1344, 1241, 1196, 1180, 1094, 748.
GC-MS: m / z = 394 (M ⁺ ).

[Example 2]
Synthesis of 1,4-bis (4-amino-2-methylphenoxy) -2-methylbenzene 1,4-bis (2-methyl-4-nitrophenoxy) -2-obtained in Example 1 in a 300 mL autoclave. Methylbenzene (40.0 g) and 2-methoxyethanol (200 g) and 5% Pd / C (0.20 g) were charged, and catalytic hydrogenation reduction was performed while maintaining 80 ° C. at 0.8 MPa. After completion of the reaction, the catalyst was removed, and the mixture was cooled, hydrated, filtered, washed and dried to obtain 31.9 g of 1,4-bis (4-amino-2-methylphenoxy) -2-methylbenzene. The purity measured by HPLC is 99.6%, mp. Was 149-150 ° C.
The ¹ H-NMR spectrum chart of the compound produced in Example 2 is shown in FIG. 3, and the ¹³ C-NMR spectrum chart is shown in FIG. The results of IR, GC-MS, and HRMS are as follows.
IR (KBr, cm < ^-1 >): 3403, 3320, 3219, 1637, 1489, 1211, 1190.
GC-MS: m / z = 334 (M ⁺ ).
HRMS (ESI): 335.1736 (M + H) ⁺

[Example 3]
Synthesis of 1,4-bis (3-methyl-4-nitrophenoxy) -2-methylbenzene In a 100 mL three-necked flask, 1.0 g (8.1 mmol) of methylhydroquinone and 2.7 g (17.17. (0 mmol), 1.5 g (10.6 mmol) of potassium carbonate, 20 mL of DMF, and a stirring magnet were charged and heated, and the reaction was carried out for 5 hours while maintaining the reaction temperature of 150 ° C. After completion of the reaction, the mixture was cooled and 100 mL of distilled water was added. The precipitated solid was filtered, washed and dried to obtain 1,4-bis (3-methyl-4-nitrophenoxy) -2-methylbenzene (3.0 g). The purity measured by HPLC is 98.4%, mp. Was 139-141 ° C.
The ¹ H-NMR spectrum chart of the compound produced in Example 3 is shown in FIG. 5, and the ¹³ C-NMR spectrum chart is shown in FIG. The results of IR and GC-MS are as follows.
IR (KBr, cm < ^-1 >): 3448, 1615, 1577, 1509, 1477, 1337, 1278, 1238, 1188, 1076, 958, 753.
GC-MS: m / z = 394 (M ⁺ ).

[Example 4]
Synthesis of 1,4-bis (4-amino-3-methylphenoxy) -2-methylbenzene 1,4-bis (3-methyl-4-) obtained in Example 3 in a 30 mL two-necked flask equipped with a cooling tube. Nitrophenoxy) -2-methylbenzene (2.0 g) and 2-methoxyethanol (12 mL) and 5% Pd / C (0.30 g) were charged and the temperature was raised to 100 ° C. 3.3 mL of an aqueous hydrazine solution was added and the mixture was kept warm for 13 hours for reaction. After removing the catalyst, the solvent was distilled off and the residue was dried to obtain a crude product of 1,4-bis (4-amino-3-methylphenoxy) -2-methylbenzene. This was dissolved in ethyl acetate, hydrochloric acid was added to cause acid precipitation, and the precipitated solid was separated by filtration. This solid was added to ethyl acetate, an aqueous alkaline solution was further added, and the aqueous layer was removed. Activated carbon was added to the obtained oil layer for decolorization, filtration, the filtrate was concentrated, and 0.5 g of 1,4-bis (4-amino-3-methylphenoxy) -2-methylbenzene purified by drying under reduced pressure was added. Obtained. The purity measured by HPLC was 97.9%.
The ¹ H-NMR spectrum chart of the compound produced in Example 4 is shown in FIG. 7, and the ¹³ C-NMR spectrum chart is shown in FIG. The results of IR, GC-MS, and HRMS are as follows.
IR (KBr, cm < ^-1 >): 3403, 3320, 3219, 1637, 1489, 1211, 1190.
GC-MS: m / z = 334 (M +)
HRMS (ESI): 335.1732 (M + H) ⁺

[Example 5]
Synthesis of 1,4-bis (3-methyl-4-nitrophenoxy) -2,3,5-trimethylbenzene In a 100 mL three-necked flask, 1.0 g of trimethylhydroquinone, 2.2 g of 5-fluoro-2-nitrotoluene and 1 of potassium carbonate were added. After charging 0.2 g, 20 mL of DMF and a stirring magnet, the mixture was heated and reacted for 6 hours while maintaining the reaction temperature of 150 ° C. After completion of the reaction, the mixture was cooled and 100 mL of distilled water was added. The precipitated solid was filtered, washed and dried to obtain 2.5 g of 1,4-bis (3-methyl-4-nitrophenoxy) -2,3,5-trimethylbenzene. The purity measured by HPLC is 99.9%, mp. Was 163-169 ° C.
The ¹ H-NMR spectrum chart of the compound produced in Example 5 is shown in FIG. 9, and the ¹³ C-NMR spectrum chart is shown in FIG. The results of IR and GC-MS are as follows.
IR (KBr, cm ⁻¹ ): 3448, 1614, 1574, 1476, 1342, 1280, 1239, 1216, 1086.
GC-MS: m / z = 422 (M ⁺ ).

[Example 6]
Synthesis of 1,4-bis (4-amino-3-methylphenoxy) -2,3,5-trimethylbenzene The 1,4-bis (3-obtained in Example 5 was placed in a 30 mL two-necked flask equipped with a cooling tube. Methyl-4-nitrophenoxy) -2,3,5-trimethylbenzene (1.0 g), 2-methoxyethanol (10 mL) and 5% Pd / C (0.13 g) were charged and the temperature was raised to 80 ° C. 2.8 mL of an aqueous hydrazine solution was added and the mixture was kept warm for 35 hours for reaction. After removing the catalyst, the solvent was distilled off and the residue was dried to obtain a crude product of 1,4-bis (4-amino-3-methylphenoxy) -2,3,5-trimethylbenzene. This was dissolved in ethyl acetate, hydrochloric acid was added to cause acid precipitation, and the precipitated solid was separated by filtration. This solid was added to ethyl acetate, an aqueous alkaline solution was further added, and the aqueous layer was removed. An active substance was added to the obtained oil layer for decolorization, filtration, and the filtrate was concentrated and dried under reduced pressure to purify 1,4-bis (4-amino-3-methylphenoxy) -2,3,5-trimethyl. 0.6 g of benzene was obtained. The purity measured by HPLC was 97.0%.
The ¹ H-NMR spectrum chart of the compound produced in Example 6 is shown in FIG. 11, and the ¹³ C-NMR spectrum chart is shown in FIG. The results of IR, GC-MS, and HRMS are as follows.
IR (KBr, cm < ^-1 >): 3446, 3365, 3024, 2924, 1610, 1500, 1472, 1405, 1277, 1223, 1154, 1081, 858.
GC-MS: m / z = 362 (M ⁺ ).
HRMS (ESI): 363.2046 (M + H) ⁺

[Example 7]
Synthesis of 1,3-bis (2-methyl-4-nitrophenoxy) -5-methylbenzene In a 200 mL three-necked flask, 2.0 g of 5-methylresorcinol anhydride, 5.3 g of 2-fluoro-5-nitrotoluene and 3 g of potassium carbonate were added. After charging 0.0 g, 40 mL of DMF and a stirring magnet, the mixture was heated and allowed to react for 11 hours while maintaining the reaction temperature of 150 ° C. After completion of the reaction, the mixture was cooled and 200 mL of distilled water was added. The precipitated solid was filtered, washed and dried, dissolved in acetone, and the solvent was distilled off to obtain 6.2 g of 1,3-bis (2-methyl-4-nitrophenoxy) -5-methylbenzene. It was The purity measured by HPLC is 97.5%, mp. Was 104-108 ° C.
The ¹ H-NMR spectrum chart of the compound produced in Example 7 is shown in FIG. 13, and the ¹³ C-NMR spectrum chart is shown in FIG. The results of IR and GC-MS are as follows.
IR (KBr, cm < ^-1 >): 3434, 3077, 2961, 1615, 1576, 1515, 487, 1458, 1342, 1297, 1239, 1092, 969, 882, 746, 647.
GC-MS: m / z = 394 (M ⁺ ).

[Example 8]
Synthesis of 1,3-bis (4-amino-2-methylphenoxy) -5-methylbenzene 1,3-bis (2-methyl-4-) obtained in Example 7 in a 30 mL two-necked flask equipped with a cooling tube. Nitrophenoxy) -5-methylbenzene (2.0 g) and 2-methoxyethanol (10 mL) and 5% Pd / C (0.22 g) were charged and the temperature was raised to 80 ° C. 2.5 mL of an aqueous hydrazine solution was added, and the mixture was kept warm for 4 hours for reaction. After removing the catalyst, the solvent was evaporated and the residue was dried to obtain a crude product of 1,3-bis (4-amino-2-methylphenoxy) -5-methylbenzene. This was dissolved in ethyl acetate, hydrochloric acid was added to cause acid precipitation, and the precipitated solid was separated by filtration. This solid was added to ethyl acetate, an aqueous alkaline solution was further added, and the aqueous layer was removed. Activated carbon was added to the obtained oil layer for decolorization, filtration, the filtrate was concentrated, and 1.6 g of 1,3-bis (4-amino-2-methylphenoxy) -5-methylbenzene purified by drying under reduced pressure was added. Obtained. The purity measured by HPLC was 97.7%.
The ¹ H-NMR spectrum chart of the compound produced in Example 8 is shown in FIG. 15, and the ¹³ C-NMR spectrum chart is shown in FIG. 16. The results of IR, GC-MS, and HRMS are as follows.
IR (KBr, cm < ^-1 >): 3436, 3367, 3220, 2920, 1614, 1594, 1498, 1463, 1211, 1129, 976, 822.
GC-MS: m / z = 334 (M ⁺ ).
HRMS (ESI): 335.1724 (M + H) ⁺

  INDUSTRIAL APPLICABILITY The bis (aminophenoxy) benzene compound of the present invention can be suitably used as a novel diamine compound, greatly expands the potential of the polyimide field derived from the compound, and has excellent high heat resistance and electrical characteristics. It can be expected as a material. Further, the bis (nitrophenoxy) benzene compound and the (aminophenoxy) (nitrophenoxy) benzene compound serve as precursors of the above bis (aminophenoxy) benzene compound, and like the diamine compound, can greatly expand the potential of the polyimide field. Can be expected.

Claims (14)

Compound represented by the following formula (1)
(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ^{1 ′} , R ^{2 ′} , R ^{3 ′} , R ^{4 ′} , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently hydrogen. An atom or a substituent selected from an optionally substituted alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 3 carbon atoms, and at least one of R ¹ , R ² , R ³ and R ⁴ . One is the substituent, at least one of R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and R ^{4 ′} is the substituent, and at least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ Is a substituent, and A and B are each independently a nitro group or an amino group.)
However, 1,4-bis (4-amino-2-methylphenoxy) -2,3,5-trimethylbenzene is excluded. In the formula (1), one or two of R ⁵ , R ⁶ , R ⁷ and R ⁸ are the substituents, and the rest of R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen atoms. The compound according to claim 1. The compound according to claim 2, which is represented by the following formula (1a ′) or (1b ′).
(In the above formulas, R, R ′ and R ″ are each independently an optionally substituted alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and A and B Is as above). Three of R ⁵ , R ⁶ , R ⁷ and R ⁸ are the substituents, the remaining one is a hydrogen atom, and among the substituents represented by R ¹ , R ² , R ³ or R ^4. At least one is in the ortho position with respect to the group represented by A, and at least one of the substituents represented by R ^{1 ′} , R ^{2 ′} , R ^{3 ′} , or R ^{4 ′} is a group represented by B. The compound of claim 1 in the ortho position relative to. The compound according to claim 4, which is represented by the following formula (1c).
(In the above, R, R ′, and R ″ are, independently of each other, an optionally substituted alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and A and B are as described above. And R'is in the ortho position to the group represented by A and R '' is in the ortho position to the group represented by B).   The compound according to any one of claims 1 to 5, wherein both A and B are amino groups. A method for producing a compound represented by the following formula (1-a),
[Wherein R ¹ , R ² , R ³ , R ⁴ , R ^{1 ′} , R ^{2 ′} , R ^{3 ′} , R ^{4 ′} , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently, A hydrogen atom or a substituent selected from an optionally substituted alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 3 carbon atoms, at least R ¹ , R ² , R ³ and R ⁴ ; One is the substituent, at least one of R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and R ^{4 ′} is the substituent, and at least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ One is the above substituent)
However, 1,4-bis (4-amino-2-methylphenoxy) -2,3,5-trimethylbenzene is excluded]
A compound represented by the following formula (1-b) or formula (1-c)
(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ^{1 ′} , R ^{2 ′} , R ^{3 ′} , R ^{4 ′} , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as described above. )
The method for producing as described above, comprising the step of reducing the nitro group to obtain the compound represented by the formula (1-a). A method for producing a compound represented by the following formula (1-b),
(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ^{1 ′} , R ^{2 ′} , R ^{3 ′} , R ^{4 ′} , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently hydrogen. An atom or a substituent selected from an optionally substituted alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 3 carbon atoms, and at least one of R ¹ , R ² , R ³ and R ⁴ . One is the substituent, at least one of R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and R ^{4 ′} is the substituent, and at least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ Is the above substituent)
One or more compounds represented by the following formula (2)
(In the formula, R ¹ , R ² , R ³ and R ⁴ are as described above, and X is a halogen atom.)
And one or more compounds represented by the following formula (3):
(In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ are as described above, and Y is a hydrogen atom, an alkali metal or an alkaline earth metal.)
The said manufacturing method including the process of reacting with and obtaining the compound represented by said Formula (1-b). A method for producing a compound represented by the following formula (1-b),
(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ^{1 ′} , R ^{2 ′} , R ^{3 ′} , R ^{4 ′} , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently hydrogen. An atom or a substituent selected from an optionally substituted alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 3 carbon atoms, and at least one of R ¹ , R ² , R ³ and R ⁴ . One is the substituent, at least one of R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and R ^{4 ′} is the substituent, and at least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ Is the above substituent)
One or more compounds represented by the following formula (4)
(In the formula, R ¹ , R ² , R ³ and R ⁴ are as described above, and Y is a hydrogen atom, an alkali metal or an alkaline earth metal.)
And one or more compounds represented by the following formula (5):
(In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ are as described above, and X is a halogen atom), and a step of obtaining a compound represented by the above formula (1-b) The manufacturing method, including:   A polyimide compound, which is a reaction product of the diamine compound according to claim 6 and an acid anhydride.   The acid anhydride is pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, benzophenone-3,4,3 ′, 4′-tetracarboxylic dianhydride, 4,4 ′-(2,2-hexafluoroisopropylidene) diphthalic acid dianhydride, 2,2-bis [3- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride and oxy-4,4′-diphthalic dianhydride The polyimide compound according to claim 10, which is at least one selected from the group consisting of:   The polyimide compound according to claim 10 or 11, which has a number average molecular weight of 2,000 to 200,000.   A polyimide compound, which is a reaction product of the compound according to claim 6, an acid anhydride, and any diamine compound other than the compound according to claim 6, wherein the compound according to claim 6 and the optional diamine compound. The polyimide compound according to any one of claims 10 to 12, wherein the ratio of the compound according to claim 6 to the total moles is 10 mol% to 100 mol%.   A molded article comprising the polyimide compound according to claim 10.