JP2002255910A - Method for producing 1,1-bis(3-amino-4-hydroxyphenyl) cycloalkanes - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a new monomer allowing producing a high-performance polymer. SOLUTION: 1,1-Bis(3-nitro-4-hydroxyphenyl)cycloalkanes are reduced by hydrazines in the presence of a catalyst to produce 1,1-bis(3-amino-4- hydroxyphenyl)cycloalkanes.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a bis (3-amino-4-hydroxyphenyl) compound which is a monomer useful for producing a high-performance polymer.

[0002]

2. Description of the Related Art Bis-o-aminophenols are compounds required for producing polymers having high heat resistance, high strength and good electrical properties, such as polybenzoxazole and polyimides having hydroxyl groups or precursors thereof. Polybenzoxazole and polyhydroxyimide are particularly important as a surface protective film for semiconductors, interlayer insulating films, interlayer insulating films for multilayer wiring boards, cover coats for flexible wiring boards, and the like. In recent years, photosensitive polybenzoxazole and polyimide having the function of a photoresist have been particularly attracting attention. Polybenzoxazole is usually produced by obtaining polyhydroxyamide from dicarboxylic acid dichloride and bis-o-aminophenol, followed by heat treatment and dehydration ring closure. In addition, polyhydroxyimide is produced by obtaining a polyamic acid from tetracarboxylic dianhydride and bis-o-aminophenol, heat-treating this, and dehydrating and ring-closing the polyamic acid. Bis-o-aminophenols have a significant effect on the properties of the polymers made therefrom. That is, the heat resistance, mechanical properties, electrical properties, solubility, and the like of the polymer are greatly affected by the raw material bis-o-aminophenols. Specific examples of bis-o-aminophenols used in such applications include 2,2-bis (3-amino-4-hydroxyphenyl) propane and 2,2-bis (3-amino-4-hydroxyphenyl) Hexafluoropropane, 4,4'-sulfonylbis (2-aminophenol), 3,3'-diamino-4,4'-dihydroxybiphenyl and the like are known.

As described above, polybenzoxazoles and polyhydroxyimides produced from bis-o-aminophenols that are currently used industrially have characteristic properties such as heat resistance, mechanical properties, and electrical properties. It is known to have However, these conventional bis-o-aminophenols are becoming more and more advanced in the field of semiconductors, and have high heat resistance for surface mounting and high-frequency transmission.
Bis-o-aminophenols that can produce polymers satisfying high performance requirements such as low thermal expansion and low dielectric property are not enough. Therefore, there is a demand for the development of a monomer useful for producing a polymer that satisfies the high performance requirements required in the semiconductor field and a method for producing the same.

[0004] 1,1-bis (3-amino-4-hydroxyphenyl) cycloalkane is considered to be useful as a monomer of a polymer satisfying high performance requirements in the semiconductor field. Hydroxyphenyl) cyclohexane and 1,1-bis (3-amino-4
Only a synthesis example of (-hydroxy-5-methylphenyl) cyclohexane is known. Tr.Voronezh.Gos.Un
iv. According to (1969), 73 (2), 58, 1,1-bis (4-
Hydroxyphenyl) cyclohexane or 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane is nitrated in acetic acid with fuming nitric acid (d1.5) to give 1,1-bis (3-nitro-4-hydroxyphenyl). Cyclohexane or 1,1-bis (3-nitro-4-hydroxy-5-methylphenyl) cyclohexane was obtained and then reduced with stannous chloride and hydrochloric acid or hydrogen reduction under Raney nickel catalyst to give 1,1-bis (3
-Amino-4-hydroxyphenyl) cyclohexane or 1,1-bis (3-amino-4-hydroxy-5-
Methylphenyl) cyclohexane has been synthesized. In chemical reduction, there is a problem in separation and treatment of a by-product tin compound, and in hydrogen reduction, a pressure-resistant reactor (autoclave) or the like is required, and there is a problem in safety of the reaction operation. In addition, the present inventors have proposed a method for producing bis (3-amino-4-hydroxyphenyl) in Japanese Patent Application Laid-Open No. H11-106367. However, 1,1-bis (3 −
No mention is made of amino-4-hydroxyphenyl) cycloalkanes.

[0005]

A conventional method for producing 1,1-bis (3-amino-4-hydroxyphenyl) cycloalkanes useful as a raw material for a polymer satisfying high performance requirements in the field of semiconductors involves by-products and There is a problem in the treatment of the waste liquid, and there is a problem in the reaction operation because special equipment is required.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that 1,1-bis (3-amino-4-hydroxyphenyl) cycloalkane, which is useful as a raw material for high-performance polymers, The present invention was completed by finding a production method with high purity and high yield. That is, the present invention
(1) 1,1-bis (3-nitro-4-hydroxyphenyl) cycloalkanes are reduced using hydrazines in the presence of a catalyst, and 1,1-bis (3
-Amino-4-hydroxyphenyl) cyclohexanes, (2) 1,1-bis (3-amino-4) according to (1), wherein the catalyst is a nickel catalyst or a noble metal catalyst.
-Hydroxyphenyl) cycloalkanes,
(3) the method for producing 1,1-bis (3-amino-4-hydroxyphenyl) cycloalkanes according to (2), wherein the noble metal catalyst is a platinum and / or palladium catalyst dispersed in a carrier, (4) a catalyst Is a combination of an iron salt and activated carbon, (1) the method for producing 1,1-bis (3-amino-4-hydroxyphenyl) cycloalkanes, (5) lower aliphatic alcohols for reduction, The method for producing 1,1-bis (3-amino-4-hydroxyphenyl) cycloalkane according to any one of (1) to (4), wherein the method is carried out with a solvent of a cyclic or acyclic ether, (6)
1,1-bis (3-amino-4-hydroxyphenyl)
When the cycloalkane is 1,1-bis (3-amino-4-hydroxyphenyl) cyclohexane, 1,1-bis (3
-Amino-5-fluoro-4-hydroxyphenyl) cyclohexane or 1,1-bis (3-amino-4-hydroxy-5-trifluoromethylphenyl) cyclohexane according to any one of (1) to (5), About.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The 1,1-bis (3-amino-4-hydroxyphenyl) cycloalkane produced by the method of the present invention has two 3-amino-4-hydroxyphenyl moieties at the 1-position of the cycloalkane moieties. And a substituent may be optionally present in both the cycloalkane moiety and the 3-amino-4-hydroxyphenyl moiety. The cycloalkane moiety is a cycloalkane-like cyclic structure such as cyclohexane, and has a cyclic skeleton composed of at least only carbon atoms. The ring size of the cycloalkane moiety is 3 or more, preferably 15 or less, more preferably 3 to 10, and preferably 5 to 8. Further, two or more substituents substituted at positions other than the 1-position of the cycloalkane moiety may be mutually bonded to form a bicyclo ring, a spiro ring, a peri ring, or a benzene ring such as indane or tetralin. An aromatic ring (including a heterocyclic ring) may be condensed. Specific examples of the cycloalkane moiety include cyclopentane, cyclohexane, cycloheptane, cyclooctane and the like, with cyclohexane being preferred. The substituent bonded to the cycloalkane moiety may be any group that is stable under a reduction reaction environment using hydrazine, and specific examples thereof include methyl, ethyl, n-propyl, iso-propyl, and tert-butyl. Examples include an alkyl group and a phenyl group. 3
The substituent of the -amino-4-hydroxyphenyl moiety may be any as long as it is stable in a reduction reaction environment using hydrazine, and the substitution position is any of the 2, 5, and 6 positions, but is preferably 2-mono substitution, 5-mono substitution, 6
Mono-substituted, 2,5-di-substituted. Specific examples of the substituent include a lower alkyl group, a phenyl group, a halogen-substituted lower alkyl group, a lower alkoxy group, a halogen-substituted lower alkoxy group, a lower thioalkyl group, and a halogen atom. Specific examples of the lower alkyl group include methyl, ethyl, n-propyl, iso-propyl, and tert-butyl. Specific examples of the halogen-substituted lower alkyl group include trifluoromethyl, trichloromethyl, perfluoroethyl, and hexafluoropropyl, with trifluoromethyl being preferred.
Specific examples of the lower alkoxy group include methoxy, ethoxy, and n-propoxy. Specific examples of the halogen-substituted lower alkoxy group include trifluoromethoxy,
Perfluoroethoxy and hexafluoropropoxy are exemplified. Specific examples of the lower thioalkyl group include methylthio, ethylthio, and n-propylthio.
Specific examples of the halogen atom include fluorine, chlorine, bromine and iodine, and fluorine is preferable.

Specific examples of 1,1-bis (3-amino-4-hydroxyphenyl) cycloalkanes include 1,1
1-bis (3-amino-4-hydroxyphenyl) cyclopentane, 1,1-bis (3-amino-4-hydroxy-5-fluorophenyl) cyclopentane, 1,1-
Bis (3-amino-4-hydroxy-5-methyl) cyclopentane, 1,1-bis (3-amino-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-amino-4-hydroxyphenyl) -2-methylcyclohexane 1,1-bis (3-amino-4-hydroxyphenyl) -3-methylcyclohexane, 1,1-bis (3
-Amino-4-hydroxyphenyl) -4-methylcyclohexane, 1,1-bis (3-amino-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-amino-4-hydroxyphenyl ) -4-tert-Butylcyclohexane, 1,1-
Bis (3-amino-4-hydroxyphenyl) -4-phenylcyclohexane, 1,1-bis (3-amino-4
-Hydroxy-5-methylphenyl) cyclohexane,
1,1-bis (3-amino-4-hydroxy-2,5-
Dimethylphenyl) cyclohexane, 1,1-bis (3
-Amino-4-hydroxy-5-trifluoromethylphenyl) cyclohexane, 1,1-bis (3-amino-4-hydroxy-5-methoxyphenyl) cyclohexane, 1,1-bis (3-amino-4-hydroxy-5-
Perfluoroethoxyphenyl) cyclohexane, 1,
1-bis (3-amino-4-hydroxy-5-methylthio) cyclohexane, 1,1-bis (3-amino-4-
(Hydroxy-5-fluorophenyl) cyclohexane,
1,1-bis (3-amino-4-hydroxy-2,5-
Difluorophenyl) cyclohexane, 1,1-bis (3-amino-4-hydroxyphenyl) cycloheptane, 1,1-bis (3-amino-4-hydroxyphenyl) cycloheptane, 1,1-bis (3-amino-4-
(Hydroxyphenyl) cyclooctane. Of these, 1,1-bis (3-amino-4-hydroxyphenyl) cyclohexane and 1,1-bis (3-amino-5-fluoro-4-hydroxyphenyl) cyclohexane are preferred.

1,1-bis (3-nitro-4-hydroxyphenyl) used as a raw material in the production method of the present invention
Cycloalkanes are produced by nitrating 1,1-bis (4-hydroxyphenyl) cycloalkanes produced by heating cycloalkyl ketones and phenols in the presence of an acid catalyst such as hydrochloric acid. Is done.
In addition, 1,1-bis (3-nitro-4-hydroxyphenyl) cycloalkanes have the same structure as that of 1,1-bis (3-amino-4
-Hydroxyphenyl) cycloalkanes have almost the same structure, so detailed description is omitted. However, when 1,1-bis (3-amino-4-hydroxyphenyl) cycloalkanes have a substituent, the present invention A precursor substituent capable of forming the substituent under the reaction conditions (for example, forming a hydrazide group such as an ester group when the target 1,1-bis (4-hydroxyphenyl) cycloalkane has a hydrazide group); Which may have a substituent such as a protecting group which is eliminated under the reaction conditions.
The target product, 1,1-bis (3-amino-4)
-Hydroxyphenyl) cycloalkanes and 1,1-bis (3-nitro-4-hydroxyphenyl) as a raw material
Cycloalkanes do not require exact structural similarity.

The reduction catalyst may be any catalyst used for the reduction reaction using hydrazine, but it is preferable to use a nickel catalyst or a noble metal catalyst. As the nickel catalyst, nickel, nickel boride, Raney nickel or the like dispersed in a carrier such as diatomaceous earth or activated carbon can be used. Of these, Raney nickel is preferably used. Further, as a noble metal catalyst, a platinum, palladium, ruthenium, rhodium catalyst or the like can be used. As the noble metal catalyst, in addition to a simple substance of such a noble metal, an oxide of the metal or a dispersion of the metal in a carrier such as activated carbon silica, alumina, zeolite or calcium carbonate can be used as the catalyst. Among these, a catalyst in which platinum and palladium are dispersed in activated carbon is preferable as the noble metal catalyst. In this case, the ratio of the noble metal dispersed in the carrier is preferably 1.0 to 5.0% by weight. Further, as the reduction catalyst, a combination of an iron salt and activated carbon can be used as the catalyst. As iron salts,
For example, hydrates and anhydrides of ferrous chloride and ferric chloride can be used. The amount of catalyst used is 1,1-bis (3
It is preferable to use 5 to 20% by weight of Raney nickel, 1 to 10% by weight of platinum-charcoal or palladium-carbon, and 5 to 20% by weight of iron salt based on -nitro-4-hydroxyphenyl) cyclohexanes. The catalyst may be a new catalyst or a recovered and recycled catalyst.

As the hydrazine used as a reducing agent, any hydrazine having a reducing power can be used.
For example, hydrazine monohydrate, methylhydrazine, hydrazinium chloride, hydrazinium sulfate can be used. Preferably 60 to 8 hydrazine monohydrate
A 0% by weight aqueous solution is used. Hydrazines are 1,1-
The amount is usually 2.0 to 6.0 mol, preferably 2.5 to 4.0 mol, per 1.0 mol of bis (3-nitro-4-hydroxyphenyl) cycloalkane. The reaction temperature is usually 1
The reaction is performed at 0 to 100 ° C, preferably 40 to 80 ° C. The reaction time varies depending on the reaction temperature, the type of catalyst and the amount used, but is usually 1 to 20 hours.

The reduction reaction is usually carried out in an organic solvent such as a lower aliphatic alcohol, a cyclic or acyclic ether. As lower aliphatic alcohols that can be used,
Methanol, ethanol, iso-propanol and the like can be mentioned. Similarly, examples of the ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dioxane, and tetrahydrofuran. Also, a mixed solvent composed of a mixture of these organic solvents and water can be used as the solvent. The ratio of water in the mixed solvent is preferably 50% by volume or less. The amount of the solvent used is usually 1 to 1 part by weight of 1,1-bis (3-nitro-4-hydroxyphenyl) cyclohexane.
It is 10 parts by weight, preferably 1.5 to 5 parts by weight.

In the operation method of the present invention, after replacing the air in the reactor with nitrogen, predetermined amounts of a solvent, 1,1-bis (3-nitro-4-hydroxyphenyl) cycloalkane and a catalyst are charged, Heat to near reaction temperature with stirring. Then, while maintaining the reaction temperature, a predetermined amount of a hydrazine aqueous solution is divided or continuously added to react. Alternatively, a solvent and a catalyst are charged and 1,1
A solution or slurry obtained by dissolving -bis (3-nitro-4-hydroxyphenyl) cycloalkane in a reaction solvent and an aqueous hydrazine solution are simultaneously added and reacted. After completion of the reaction, the reaction product is cooled to near room temperature, and the reaction product is taken out. The catalyst is removed by filtration. The solvent and water are distilled off from the filtrate to obtain 1,1-bis (3-amino-4-hydroxyphenyl) cycloalkanes.

The 1,1-bis (3-amino-4-hydroxyphenyl) cycloalkanes obtained as described above have a sufficiently high purity, but can be purified by a recrystallization method or the like, if necessary. . Examples of the recrystallization solvent include alcohols such as methanol, ethanol, and iso-propanol; ethers such as ethylene glycol monoethyl ether, ethylene glycol diethyl ether, dioxane, and tetrahydrofuran; and aromatic hydrocarbons such as toluene and xylene. ,Ethyl acetate,
Carboxylic esters such as butyl acetate can be used. As the recrystallization solvent, one kind of solvent may be used alone, or two or more kinds may be used in combination. The recrystallization can be performed, for example, by using 1 to 10 parts by weight of a recrystallization solvent with respect to 1 part by weight of crude 1,1-bis (3-amino-4-hydroxyphenyl) cycloalkane.

1,1- produced by the method of the present invention
Bis (3-amino-4-hydroxyphenyl) cycloalkanes are derivatized to polybenzoxazole by polycondensation with dicarboxylic acid and dehydration and ring closure, and to polyhydroxyimide by polycondensation with tetracarboxylic dianhydride and dehydration ring closure. You. As an example of the synthesis of polybenzoxazole, 1,1-bis (3-amino-4-hydroxyphenyl) cycloalkane is dissolved in an aprotic polar solvent such as N-methyl-2-pyrrolidone, and an acid acceptor such as pyridine is used. Is reacted with a dicarboxylic acid dichloride such as terephthalic acid dichloride at −20 ° C. to room temperature in the presence of to obtain a polybenzoxazole precursor. By heating the polybenzoxazole precursor thus obtained or treating it with a dehydrating agent such as polyphosphoric acid,
Dehydration and ring closure can give polybenzoxazole.

[0017]

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these specific examples.

Reference Example 1,1-bis (3-nitro-4-
Production of hydroxyphenyl) cyclohexane In a 1 L 4-neck flask equipped with a thermometer and a stirrer, 600 ml of dichloromethane and 81 g (0.30 mol) of 1,1-bis (4-hydroxyphenyl) cyclohexane were added.
While cooling and keeping the reaction temperature at -5 to 0 ° C, 607 g (0.66 mol) of 70% by weight nitric acid (d = 1.42) was added dropwise over 3 hours. The reaction was further completed by stirring at the same temperature for 1 hour. The reaction solution was washed with a dilute aqueous sodium hydrogen carbonate solution and then with water, and then the dichloromethane solution phase was separated. Dichloromethane was almost distilled off to obtain 130 g of crude 1,1-bis (3-nitro-4-hydroxyphenyl) cyclohequine as a brown viscous oil. HPLC analysis (area%) 92.0%. After methanol was added to the oil and dissolved by heating, the mixture was gradually cooled to precipitate crystals and filtered at 5 ° C. After drying, 86 g of pure 1,1-bis (3-nitro-4-hydroxyphenyl) cyclohexane was obtained. Yield 80
%. HPLC analysis (area%) 99.0%. 1,1-bis (3-nitro-4-hydroxyphenyl)
Characteristic value of cyclohexane Melting point (DSC) 92 ° C ¹ H-NMR (CDCl ₃ ) δ 1.55 ppm (6H, m), 2.45 (4H, m),
7.07 (2H, d), 7.40 (2H, dd), 8.0
5 (2H, d), 10.48 (2H, s)

Example 1 1,1-bis (3-amino-4
Preparation of -Hydroxyphenyl) cyclohexane To a 500 ml flask equipped with a thermometer, a stirrer and a condenser, 36 g (0.10 mol) of 1,1-bis (3-nitro-4-hydroxyphenyl) cyclohexane and 200 ml of ethylene glycol monoethyl ether were added. The air was replaced with nitrogen. Next, 2.5 g of a 5% Pd-carbon catalyst was added, and after heating to 60 ° C., 33 g (0.40 mol) of 60% hydrazine monohydrate was added dropwise over 3 hours. During this time, cooling was performed so as to maintain the reaction temperature at 60 to 65 ° C. After further aging at 60 to 65 ° C. for 1 hour, the mixture was cooled to room temperature. The reaction product was taken out, and most of the solvent and water were distilled off under reduced pressure from the filtrate from which the catalyst was removed by filtration. Methanol was added and the mixture was stirred to precipitate a white solid, and the solid was filtered. After drying in a vacuum dryer,
25.5 g of bis (3-amino-4-hydroxyphenyl) cyclohexane were obtained. 85.6% yield. HPLC analysis (area%) 99.5%. 1,1-bis (3-amino-4-hydroxyphenyl)
Characteristic value of cyclohexane Melting point (DSC) 227 ° C ¹ H-NMR ((CD ₃ ) ₂ SO) δ 1.43 ppm (6H, m), 2.02 (4H, m),
4.30 (4H, s), 6.28 (2H, dd), 6.4
8 (2H, d), 6.49 (2H, d), 8.64 (2
H, s)

[0020]

EFFECT OF THE INVENTION 1,1 useful as a raw material for a high-performance polymer
1-bis (3-amino-4-hydroxyphenyl) cycloalkanes can be obtained efficiently.

Claims (6)

[Claims] 1. A method for reducing 1,1-bis (3-nitro-4-hydroxyphenyl) cycloalkanes with hydrazines in the presence of a catalyst. Method for producing 4-hydroxyphenyl) cycloalkanes. 2. The method for producing 1,1-bis (3-amino-4-hydroxyphenyl) cycloalkane according to claim 1, wherein the catalyst is a nickel catalyst or a noble metal catalyst. 3. The 1,1 according to claim 2, wherein the noble metal catalyst is a platinum and / or palladium catalyst dispersed on a carrier.
A method for producing bis (3-amino-4-hydroxyphenyl) cycloalkanes. 4. The 1,1-bis (3-amino-4) according to claim 1, wherein the catalyst is a combination of an iron salt and activated carbon.
-Hydroxyphenyl) cycloalkanes. 5. The 1,1-bis (3-amino-4-hydroxyphenyl) according to claim 1, wherein the reduction is carried out with a solvent of a lower aliphatic alcohol, a cyclic or acyclic ether. A method for producing cycloalkanes. 6. A method according to claim 1, wherein the 1,1-bis (3-amino-4-hydroxyphenyl) cycloalkane is 1,1-bis (3-amino-4-hydroxyphenyl) cyclohexane,
The method according to any one of claims 1 to 5, which is 1-bis (3-amino-5-fluoro-4-hydroxyphenyl) cyclohexane or 1,1-bis (3-amino-4-hydroxy-5-trifluoromethylphenyl) cyclohexane. Production method.