JP2007210936A - Method for producing alicyclic diamine compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for inexpensively, simply and safely producing an alicyclic diamine compound (bicyclohexane diamines) in good yield without handling an aromatic diamine causing toxicity problems and generating the amine as an intermediate. <P>SOLUTION: The method for producing the alicyclic diamine compound is to react a diketone compound having a specific structure with a compound expressed by general formula (2): R<SP>1</SP>NH<SB>2</SB>(wherein R<SP>1</SP>expresses a benzyl group which may have a substituent) and hydrogenzize the reaction product in the presence of a hydrogenation catalyst and hydrogen. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a method for producing an alicyclic diamine compound.

Diamine compounds are useful as raw materials for, for example, polyamides, polybenzoxazoles, polyamideimides, and epoxy resins for electronic materials and optical materials.

Conventionally, aromatic compounds have been used in such applications, but compounds having an aromatic ring generally have a high electron density, and as a result, there are disadvantages such as a high dielectric constant particularly in the high frequency range, and aromatic rings. There are drawbacks such as strong intermolecular packing and low light transmittance. Thus, for example, alicyclic diamine compounds having no aromatic ring (for example, bicyclohexanediamine) are attracting attention.

In producing bicyclohexanediamine, a method of hydrogenating benzidine and a method of reacting bicyclohexanediol with ammonia are conceivable. The former is not preferable from the viewpoint of the toxicity of benzidine as a raw material, and the latter is not preferable because high temperature and high pressure are required for the reaction.

The present invention is a method for producing an alicyclic diamine compound (bicyclohexanediamine) inexpensively, easily, safely without producing an aromatic diamine having a problem of toxicity in high yield, and without causing intermediates. The purpose is to provide.

As a result of intensive studies to solve the above problems, the present inventors have conducted a hydrocracking reaction of a biimino compound obtained by a dehydration condensation reaction from an alicyclic diketone and a specific amine in a hydrogen atmosphere in the presence of a hydrogenation catalyst. As a result, it was found that an alicyclic diamine compound can be quantitatively produced, and the present invention was completed.

  That is, the present invention relates to the general formula (1):

(Wherein R represents an alkyl group having 1 to 4 carbon atoms, R ′ represents an alkyl group having 1 to 4 carbon atoms, n represents an integer of 0 to 4, and n ′ represents an integer of 0 to 4). And a compound represented by the general formula (2): R ¹ NH ₂ (wherein R ¹ represents a benzyl group which may have a substituent), a hydrogenation catalyst, General formula (3) characterized by hydrogenation in the presence of hydrogen:

(Wherein R represents an alkyl group having 1 to 4 carbon atoms, R ′ represents an alkyl group having 1 to 4 carbon atoms, n represents an integer of 0 to 4, and n ′ represents an integer of 0 to 4). A process for producing an alicyclic diamine compound; general formula (4):

で表される化合物を、水素化触媒、水素の存在下、一般式（２）：Ｒ^１ＮＨ_２（式中、Ｒ^１は、水酸基または置換基を有していてもよいベンジル基を表す。）で表される化合物と反応させることを特徴とする一般式（５）：

In the presence of hydrogenation catalyst and hydrogen, general formula (2): R ¹ NH ₂ (wherein R ¹ represents a hydroxyl group or a benzyl group which may have a substituent. And a compound represented by the general formula (5):

It relates to the manufacturing method of the alicyclic diamine compound represented by these.

According to the present invention, a novel alicyclic diamine compound (bicyclohexanediamine) can be provided. Moreover, according to the manufacturing method of this invention, an alicyclic diamine compound can be manufactured with sufficient yield. Furthermore, according to the present invention, it is not necessary to use a toxic substance having a carcinogenic potential such as an aromatic diamine typified by benzidine, so that environmental burden can be reduced.

  In the present invention, the general formula (1):

(Wherein R represents an alkyl group having 1 to 4 carbon atoms, R ′ represents an alkyl group having 1 to 4 carbon atoms, n represents an integer of 0 to 4, and n ′ represents an integer of 0 to 4). The compound (hereinafter referred to as diketone compound (A)) in the presence of hydrogenation catalyst and hydrogen is represented by the general formula (2): R ¹ NH ₂ (wherein R ¹ has a hydroxyl group or a substituent). And a hydrogenated catalyst in the presence of hydrogen to give a hydrogen atom in the general formula (3):

(Wherein R represents an alkyl group having 1 to 4 carbon atoms, R ′ represents an alkyl group having 1 to 4 carbon atoms, n represents an integer of 0 to 4, and n ′ represents an integer of 0 to 4). (Hereinafter referred to as alicyclic diamine compound (D)).

  As a diketone compound (A) used for this invention, what is represented by the said General formula (1) is used. Specifically, for example, 4,4′-bicyclohexanedione, 2-methyl-4,4′-bicyclohexanedione, 3-methyl-4,4′-bicyclohexanedione, 2,2′-dimethyl-4 4,4′-bicyclohexanedione, 2,3′-dimethyl-4,4′-bicyclohexanedione, 3,3′-dimethyl-4,4′-bicyclohexanedione, and the like. As these compounds, commercially available products may be used as they are, or they can be produced by hydrogenating and oxidizing a biphenol derivative. Specifically, for example, a method described in Japanese Patent No. 2743390 or Japanese Patent No. 3555201 may be employed. The amine compound (B) used in the present invention is represented by the general formula (2), and specific examples include hydroxylamine and benzylamine which may have a substituent. The benzylamine which may have a substituent is not particularly limited, and known ones can be used. Specific examples include benzylamine, o-methylbenzylamine, m-methylbenzylamine. , P-methylbenzylamine, o-fluorobenzylamine, m-fluorobenzylamine, p-fluorobenzylamine, o-chlorobenzylamine, m-chlorobenzylamine, p-chlorobenzylamine and the like. . Among these, benzylamine which may have a substituent is preferable from the viewpoint of workability, and benzylamine is particularly preferable from the viewpoint of easy availability.

In the reaction of the present invention, a diketone compound (A) and an amine compound (B) are reacted to form a general formula (6):

(In the formula, R is an alkyl group having 1 to 4 carbon atoms, R ′ is an alkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 4, n ′ is an integer of 0 to 4, and R ¹ is A compound represented by a hydroxyl group or an optionally substituted benzyl group) (hereinafter referred to as an imine compound (C)), the imine compound (C) is hydrogenated, and an alicyclic diamine compound ( D).

  The reaction between the diketone compound (A) and the amine compound (B) is an equilibrium reaction, and the imine compound (C) is reduced by hydrogenation of the imine compound (C). The imine compound (C) is generated, and thereby the alicyclic diamine compound (D) can be obtained with a high yield.

  The reaction between the diketone compound (A) and the amine compound (B) proceeds easily, and the reaction proceeds only by mixing the diketone compound (A) and the amine compound (B), and the imine compound (C). Produces. Usually, it is made to react at about 0-120 degreeC. If the temperature exceeds 120 ° C., the product may decompose, and the yield may decrease.

  In the present invention, the produced imine compound (C) is hydrogenated to change the equilibrium state and produce the alicyclic diamine compound (D) with good yield.

  The hydrogenation is usually performed in the presence of a hydrogenation catalyst and hydrogen. The hydrogenation catalyst and hydrogen may be added when the diketone compound (A) and the amine compound (B) are mixed, or may be added after the diketone compound (A) and the amine compound (B) are mixed and reacted. Good.

The hydrogenation catalyst used in the hydrogenation of the present invention is at least one selected from the group consisting of palladium catalysts, platinum catalysts, ruthenium catalysts, rhodium catalysts, iridium catalysts, nickel catalysts and cobalt catalysts. Can be used. The ruthenium-based catalyst is not particularly limited as long as it contains ruthenium as an active metal species, and a known catalyst can be used. However, if a ruthenium-supported catalyst supported on an inert carrier is used, handling is easy. The rhodium-based catalyst is not particularly limited as long as it contains rhodium as an active metal species, and a known catalyst can be used. However, if a rhodium-supported catalyst supported on an inert carrier is used, handling is easy. The palladium-based catalyst is not particularly limited as long as it contains palladium as an active metal species, and any known catalyst can be used. However, if a palladium-supported catalyst supported on an inert carrier is used, handling is easy. The iridium catalyst is not particularly limited as long as it contains iridium as an active metal species, and a known catalyst can be used. However, if an iridium supported catalyst supported on an inert carrier is used, handling is easy. The platinum-based catalyst is not particularly limited as long as it contains platinum as an active metal species, and a known catalyst can be used. However, if a platinum-supported catalyst supported on an inert carrier is used, handling is easy. The nickel-based catalyst is not particularly limited as long as it contains nickel as an active metal species, including sponge nickel, but a known catalyst can be used, but if a nickel-based catalyst supported on an inert carrier is used, the handleability is improved. Is easy. The cobalt-based catalyst is not particularly limited as long as it contains sponge cobalt and cobalt as the active metal species, and any known catalyst can be used. However, if a cobalt-based catalyst supported on an inert carrier is used, the handling property is improved. Is easy. As the inert carrier, for example, carbon, silica, alumina, silica alumina, magnesia and the like are preferable, and carbon or alumina is particularly preferable. Supporting a metal such as ruthenium on the support can be performed by a known method such as an impregnation method or a precipitation method. The amount of metal such as ruthenium supported is not particularly limited, but it is usually preferably about 0.5 to 10% by weight. As these hydrogenation catalysts, commercially available supported catalysts may be used as they are. Among these hydrogenation catalysts, it is preferable to use a palladium supported catalyst, a platinum supported catalyst, a ruthenium supported catalyst, or a rhodium supported catalyst.

Although the usage-amount of a hydrogenation catalyst is not specifically limited, Usually, it is preferable to set it as about 0.01-10 weight% as an active metal seed | species with respect to the weight of a raw material, and 0.05-2 weight% is especially preferable.
The reaction charge molar ratio of the diketone compound (A) and the amine compound (B) in the present invention is such that the theoretical amount ratio is (A) :( B) = 1: 2, and the amount of the amine compound (B) is 2 or more. The molar ratio of (A) :( B) is preferably 1.0: 2.0 to 1.0: 4.0, and 1.0: 2.0 to 1.0: 2.4 is particularly preferred.

  In the present invention, a reaction solvent may be used as necessary. As the reaction solvent, a known solvent that does not react with a raw material compound or a catalyst can be used. Specific examples include alcohol solvents, ether solvents, ester solvents, hydrocarbon solvents, and the like. Examples of the alcohol solvent include methanol, ethanol, n-propyl alcohol, 2-propanol, n-butanol, cyclohexanol and the like, and examples of the ether solvent include methyl tertiary butyl ether, dipropyl ether, dibutyl ether, Examples include methylal, dimethoxyethane, diethoxyethane, tetrahydrofuran, tetrahydropyran, dioxane, dioxolane and the like, and ester solvents include, for example, ethyl acetate, propyl acetate, butyl acetate and the like, and hydrocarbon solvents include, for example, Examples thereof include n-hexane, cyclohexane, n-pentane, toluene, xylene and the like. Among these, alcohol solvents and ether solvents are preferable, and methanol, ethanol, 2-propanol, and tetrahydrofuran are particularly preferable.

The amount used in the case of using a reaction solvent is not particularly limited, but it is usually preferable to use about 0.5 to 20 parts by weight with respect to 1 part by weight of the starting diketone compound (A), and 1 part by weight of the diketone compound (A). It is more preferable to use 2 to 10 parts by weight with respect to parts.

  The reaction temperature and reaction pressure (hydrogen pressure) during the hydrogenation in the present invention are not particularly limited and can be appropriately determined. Usually, the reaction temperature is about 0 ° C to 120 ° C, preferably 20 to 100 ° C. The hydrogen pressure is about 2 to 20 MPa, preferably 7 to 18 MPa. The reaction time is not particularly limited, but is usually about 2 to 20 hours.

  By hydrogenating under the above hydrogenation conditions, a reaction liquid containing the alicyclic diamine compound (D) at a high concentration is obtained, and the target compound can be easily obtained by separating the catalyst and the solvent from the reaction liquid. Can be obtained. In addition, when using a hydroxylamine as an amine compound (B), it is preferable from points, such as purity and a yield, to hydrogenate after isolating as an oxime body. Moreover, when using the benzylamine which may have a substituent as an amine compound (B), diketone compound (A), an amine compound (B), and a hydrogenation catalyst should be mixed and made to react. Can hydrogenate the produced imine compound (C) as it is, shift the equilibrium, and promote the production of the imine compound (C), thereby reducing the reaction time and the number of reaction steps.

According to the present invention, the desired alicyclic diamine compound is usually obtained with a selectivity of 80% or more from the raw material. In addition, since the reaction product contains a small amount of reaction intermediates, these can be purified by means such as ordinary distillation or recrystallization as necessary to obtain a higher purity alicyclic diamine compound. Can do.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples.

Example 1
In a 200 ml autoclave, 19.4 g (0.10 mol) of 4,4′-bicyclohexanedione, 23.6 g (0.22 mol) of benzylamine, 100 ml of ethanol, a 10% palladium-carbon supported catalyst (N Chemcat ( Co., Ltd., PE type 50% water-containing product) 1.0 g was charged, and the system was replaced with hydrogen. The hydrogen pressure was 12 MPa at room temperature and the reaction was continued for 4 hours with stirring. The hydrogen pressure was 6.6 MPa. Next, the temperature was set to 120 ° C., the hydrogen pressure was maintained at 12 MPa, and the reaction was further continued for 8 hours. The obtained reaction solution was filtered to remove the catalyst, and the reaction solution was subjected to gas chromatography (manufactured by Shimadzu Corporation, GC-17A (FID detector), GL Sciences, Inc., using TC-1 capillary column). Hereinafter the same and abbreviated as GC). The composition ratio according to the GC area ratio of the reaction solution was 59.7% toluene, 0.4% benzylamine, 39.2% 4,4'-bicyclohexyldiamine, 4,4'-bicyclohexane excluding the ethanol solvent. Dione was 0.0%, and others were 0.7%.
The solvent was distilled off under reduced pressure to obtain 18.7 g of 4,4′-bicyclohexyldiamine as a waxy solid having a purity by GC area ratio (hereinafter abbreviated as GC purity) of 97.5%. 15.0 g of the obtained solid was recrystallized from toluene to obtain 12.6 g of white crystals having a GC purity of 99.6%. As a result of GC-MS (mass spectrometry), it was confirmed that the molecular weight of this crystal was 196.

Example 2
In a 200 ml autoclave, 9.7 g (0.05 mol) of 4,4′-bicyclohexanedione, 11.8 g (0.11 mol) of benzylamine, 100 ml of ethanol, a 10% palladium-carbon supported catalyst (N Chemcat ( Co., Ltd., PE type 50% water-containing product) 0.5 g was charged, and the system was replaced with hydrogen. Then, the temperature was set to 100 ° C., and the reaction was stirred for 8 hours while adding hydrogen to maintain the hydrogen pressure at 5 MPa. . The obtained reaction solution was filtered to remove the catalyst, and GC composition analysis was performed. As a result, the composition ratio excluding ethanol was 58.2% toluene, 1.3% benzylamine, and 4,4′-bicyclohexyl. Diamine 37.4%, 4,4'-bicyclohexanedione 0.0%, and others 3.1%. The solvent was distilled off under reduced pressure to obtain 8.9 g of a waxy solid. The GC purity was 90.8% (benzylamine 1.4%, 4,4′-bicyclohexanedione 0.0%, others 7.8%).

Comparative Example 1
In a 200 ml four-necked flask equipped with a thermometer, a cooling pipe, a hydrogen introduction pipe and a stirrer, 9.7 g (0.05 mol) of 4,4′-bicyclohexanedione and 11.8 g (0.11 mol) of benzylamine Then, 100 ml of ethanol was charged, the temperature was adjusted to 60 ° C. under a nitrogen atmosphere, the imination reaction was sampled, and GC analysis was performed (see the table below). Next, 0.5 g of 4.2% palladium-0.5% platinum-carbon supported catalyst (manufactured by N Chemcat Co., Ltd., ASCA-2 type 50% water-containing product) was added, and vacuum degassing-hydrogen introduction was performed three times. The inside of the closed flask was repeatedly replaced with hydrogen. The reaction was carried out for 12 hours under a hydrogen atmosphere at normal pressure with vigorous stirring, and further 50 ml of ethanol was added to the flask contents and dissolved. The resulting solution was charged into a 200 ml autoclave, and the system was filled with hydrogen. Then, the temperature was set to 100 ° C., and the reaction was performed for 4 hours while maintaining the hydrogen pressure at 10 MPa. The obtained reaction solution was filtered to remove the catalyst, and GC composition analysis was performed. The composition ratio excluding ethanol was as follows: toluene 33.1%, benzylamine 5.0%, 4,4′-bicyclohexyl. Diamine was 7.4%, 4,4′-bicyclohexanedione 0.0%, and other 54.5%.

Claims (3)

General formula (1):

(Wherein R represents an alkyl group having 1 to 4 carbon atoms, R ′ represents an alkyl group having 1 to 4 carbon atoms, n represents an integer of 0 to 4, and n ′ represents an integer of 0 to 4). And a compound represented by the general formula (2): R ¹ NH ₂ (wherein R ¹ represents a benzyl group which may have a substituent), a hydrogenation catalyst, General formula (3) characterized by hydrogenation in the presence of hydrogen:

(Wherein R represents an alkyl group having 1 to 4 carbon atoms, R ′ represents an alkyl group having 1 to 4 carbon atoms, n represents an integer of 0 to 4, and n ′ represents an integer of 0 to 4). A method for producing an alicyclic diamine compound. 2. The alicyclic catalyst according to claim 1, wherein the hydrogenation catalyst is at least one selected from a palladium catalyst, a platinum catalyst, a ruthenium catalyst, a rhodium catalyst, an iridium catalyst, a nickel catalyst, and a cobalt catalyst. A method for producing a diamine compound. General formula (4):

In the presence of hydrogenation catalyst and hydrogen, general formula (2): R ¹ NH ₂ (wherein R ¹ represents a hydroxyl group or a benzyl group which may have a substituent. And a compound represented by the general formula (5):

The manufacturing method of the alicyclic diamine compound represented by these.