JP2002179609A - Method for producing bis(4-oxocyclohexyl) compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a bis(4-oxocyclohexyl) compound in high yield and high selectivity from the corresponding bis(4- hydroxycyclohexyl) compound as the starting material under mild conditions easy to practice industrially. SOLUTION: This method comprises dehydrogenating a bis(4- hydroxycyclohexyl) compound of formula (I) [wherein, X is a single bond, a hydrocarbon group of formula (II) [wherein, R1 and R2 are each H, a 1-6C alkyl, a 5C or 6C cycloalkyl or phenyl], O or SO2] in a liquid phase comprising an unsaturated ketone solvent having a C=C double bond conjugated with a C=O double bond in the presence of a copper-based oxide catalyst to obtain the corresponding objective bis(4-oxocyclohexyl) compound of (III) (wherein, X, R1 and R2 are each the same as mentioned above).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing bis (4-oxocyclohexyl) s, and more particularly, to a method for producing a copper-based oxide in a liquid phase comprising an organic solvent in which bis (4-hydroxycyclohexyl) is particularly selected. (4-oxocyclohexyl) is obtained by dehydrogenating in the presence of a catalyst to obtain the corresponding bis (4-oxocyclohexyl) in high yield and high selectivity.

[0002]

2. Description of the Related Art Bis (4-oxocyclohexyl) s are compounds useful as intermediates for pharmaceutical raw materials, industrial chemical raw materials, display liquid crystal compound raw materials, polymer raw materials, antioxidant raw materials and the like.

As a method for producing bis (4-oxocyclohexyl) s, for example, Japanese Patent Application Laid-Open No. 4-59742 discloses a method in which 2,2-bis (4-hydroxycyclohexyl) propane is used in a solvent with hypochlorous acid or the like. A method is described which oxidizes to 2,2-bis (4-oxocyclohexyl) propane. However, according to this method, a large amount of difficult-to-treat waste is generated, so that industrial implementation is difficult.

On the other hand, JP-A-8-53386 discloses that
A method for producing a corresponding alicyclic diketone compound by dehydrogenating an alicyclic diol compound in a liquid phase with a pressurized system in the presence of a copper catalyst or a Raney catalyst is described. JP-A-11-199539 describes a method for producing a corresponding alicyclic diketone compound by subjecting an alicyclic diol compound to a dehydrogenation reaction under reduced pressure in a solvent in the presence of a copper catalyst. ing. However, according to these methods,
In any case, the reaction temperature is high, and it is necessary to carry out the reaction under pressure or under reduced pressure, and similarly, there is a problem in terms of equipment, reaction conditions, and the like for industrial implementation.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems in the production of conventional bis (4-oxocyclohexyl) s. As a starting material, bis (4-oxocyclohexyl) can be obtained in high yield and high selectivity to bis (4-oxocyclohexyl) under mild reaction conditions which are industrially easy to carry out.
It is an object of the present invention to provide a method for producing such a compound.

[0006]

According to the present invention, the compound represented by the general formula (I)

[0007]

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[Wherein, X is a single bond, general formula (II)

[0009]

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(Wherein R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 or 6 carbon atoms, or a phenyl group). group, -O- or -SO ₂ - shows a. A bis (4-hydroxycyclohexyl) compound represented by the formula (1) in a liquid phase comprising an unsaturated ketone solvent having a carbon-carbon double bond conjugated to a C = O double bond in the presence of a copper-based oxide catalyst. General formula (III) characterized by dehydrogenation to

[0011]

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(Wherein X, R ₁ and R ₂ are the same as above). A process for producing bis (4-oxocyclohexyl) s represented by the formula:

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a starting material represented by the general formula (I)

[0014]

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[Wherein, X is a single bond, general formula (II)

[0016]

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(Wherein R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 or 6 carbon atoms, or a phenyl group). group, -O- or -SO ₂ - shows a. ] (4-hydroxycyclohexyl) is used.

In such bis (4-hydroxycyclohexyl) s, when R ₁ or R ₂ is an alkyl group having 1 to 6 carbon atoms, specific examples thereof include a methyl group, an ethyl group and an n-propyl group. Group, isopropyl group, n-
Butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, n
-Hexyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, isohexyl group and the like. When R ₁ or R ₂ is a cycloalkyl group having 5 or 6 carbon atoms, specific examples thereof include a cyclopentyl group and a cyclohexyl group.

Accordingly, specific examples of the bis (4-hydroxycyclohexyl) represented by the above general formula (I) include, for example, bis (4-hydroxycyclohexyl),
Bis (4-hydroxycyclohexyl) methane, bis (4-hydroxycyclohexyl) -1-cyclohexylmethane, bis (4-hydroxycyclohexyl) ethane, bis (4-hydroxycyclohexyl) -1-methylethane, bis (4-hydroxycyclohexyl) -1
-Ethylethane, bis (4-hydroxycyclohexyl) -1-cyclohexylethane, bis (4-hydroxycyclohexyl) -1-phenylethane, bis (4-
(Hydroxycyclohexyl) propane, bis (4-hydroxycyclohexyl) -1-ethylpropane, bis (4-hydroxycyclohexyl) pentane, bis (4
-Hydroxycyclohexyl) -1-ethylpentane,
Bis (4-hydroxycyclohexyl) ether, bis (4-hydroxycyclohexyl) sulfone and the like can be mentioned.

According to the method of the present invention, such bis (4-hydroxycyclohexyl) s are dehydrogenated in a liquid phase comprising an unsaturated ketone solvent in the presence of a copper-based oxide catalyst. Bis (4-oxocyclohexyl) s can be obtained.

As the copper-based oxide catalyst, preferably, at least one selected from copper oxide, copper-chromium oxide, copper-zinc oxide, and copper-chromium-zinc oxide is used. According to the present invention, a co-catalyst such as barium oxide or manganese oxide may be used together with such a copper-based oxide catalyst, if necessary. Further, according to the present invention, the catalyst (and co-catalyst) is silica, alumina, activated clay,
It may be used by being supported on a carrier such as carbon or graphite. The form of these copper-based oxide catalysts is not particularly limited, but is preferably used in a powder form or in a slurry form dispersed in an organic solvent.

In the present invention, such a catalyst is used as a starting material for bis (4-hydroxycyclohexyl) s 1
0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, per 100 parts by weight.

According to the present invention, in the presence of such a catalyst, the dehydrogenation of bis (4-hydroxycyclohexyl) is carried out by reacting a carbon-carbon double bond conjugated with a C ＝ O double bond as a reaction solvent. The reaction is carried out using an unsaturated ketone solvent. That is, according to the present invention, the dehydrogenation of bis (4-hydroxycyclohexyl) s is performed in the unsaturated ketone solvent at a reaction temperature in the range of 150 to 280 ° C,
As the unsaturated ketone solvent, those having a boiling point higher than the reaction temperature are preferably used. That is,
According to the present invention, the reaction is performed in a liquid phase consisting of the unsaturated ketone solvent described above.

Examples of the unsaturated ketone solvent include, for example, methyl vinyl ketone, mesityl oxide,
Holon, isophorone and the like can be mentioned. These unsaturated ketone solvents are used alone or as a mixture of two or more. In the present invention, among these, holon, isophorone or a mixture thereof is particularly preferably used.

According to the present invention, by using such an unsaturated ketone solvent as a reaction solvent, bis (4
-Hydroxycyclohexyl) can be carried out under mild conditions at normal pressure in the presence of the catalyst,
Moreover, the desired product can be obtained with high yield and high selectivity.

The reason why the above effects can be obtained by using the above unsaturated ketone solvent as the reaction solvent in the method according to the present invention is not clear, and the present invention is not limited by the above. However, it is presumed that the unsaturated ketone solvent serves as a hydrogen acceptor during the dehydrogenation of bis (4-hydroxycyclohexyl) s to accelerate the reaction.

In the present invention, the reaction solvent comprising the above unsaturated ketone solvent is characterized in that the total number of moles of the carbon-carbon double bond in the molecule is such that the total number of hydrogen atoms generated by the dehydrogenation reaction of bis (4-hydroxycyclohexyl) s It is preferred to use more than the theoretical number of moles of molecule. Therefore, the amount of the reaction solvent to be used depends on the type of the bis (4-hydroxycyclohexyl) used as the starting material and the type of the solvent to be used, but it is usually based on 100 parts by weight of the bis (4-hydroxycyclohexyl). , 10 to 1000 parts by weight, preferably 50 to 500 parts by weight.

In the present invention, the dehydrogenation of bis (4-hydroxycyclohexyl) is carried out in the presence of the catalyst.
In the above reaction solvent, the reaction is carried out at a reaction temperature in the range of 150 to 280 ° C, preferably at a reaction temperature in the range of 160 to 220 ° C.

According to the present invention, as described above,
Under normal pressure, the reaction proceeds with high selectivity and high yield.
It is preferable to carry out the reaction under normal pressure from the viewpoint of industrial production. However, the reaction may be carried out under increased or reduced pressure, if necessary. According to the present invention, the reaction is usually completed in about 2 to 10 hours under such conditions.

In the method of the present invention, the mode of the reaction is not particularly limited. For example, bis (4-hydroxycyclohexyl), a reaction solvent and a catalyst are charged into a reaction vessel and stirred under a nitrogen stream. While 150-280
The temperature is raised to about ℃, and the reaction is carried out in the liquid phase. After completion of the reaction, the catalyst is separated from the obtained reaction mixture by filtration, and then, if necessary, distilled, crystallized, filtered, separated and dried to obtain a purified product.

According to the present invention, the starting material, bis (4-hydroxycyclohexyl), is represented by the general formula (III):

[0032]

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(Wherein X, R ₁ and R ₂ are the same as described above), and the desired bis (4-oxocyclohexyl) s represented by the formula ( ₁ ) can be obtained.

In such bis (4-oxocyclohexyl) s, when R ₁ or R ₂ is an alkyl group having 1 to 6 carbon atoms, specific examples thereof include a methyl group, an ethyl group and an n-propyl group. Group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, n-hexyl group, 1,3-dimethylbutyl group, 2,3-dimethyl Examples thereof include a butyl group and an isohexyl group. When R ₁ or R ₂ is a cycloalkyl group having 5 or 6 carbon atoms, specific examples thereof include a cyclopentyl group and a cyclohexyl group.

Accordingly, specific examples of the bis (4-oxocyclohexyl) s represented by the general formula (II) include, for example, bis (4-oxocyclohexyl) and bis (4-oxocyclohexyl).
Oxocyclohexyl) methane, bis (4-oxocyclohexyl) -1-cyclohexylmethane, bis (4-
Oxocyclohexyl) ethane, bis (4-oxocyclohexyl) -1-methylethane, bis (4-oxocyclohexyl) -1-ethylethane, bis (4-oxocyclohexyl) -1-cyclohexylethane, bis (4-oxocyclohexyl)- 1-phenylethane,
Bis (4-oxocyclohexyl) propane, bis (4
-Oxocyclohexyl) -1-ethylpropane, bis (4-oxocyclohexyl) pentane, bis (4-oxocyclohexyl) -1-ethylpentane, bis (4
-Oxocyclohexyl) ether, bis (4-oxocyclohexyl) sulfone, and the like.

[0036]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited by these examples. In the examples, the reaction yield and the selectivity of the target product were
After the completion of the reaction, the catalyst was filtered and separated from the reaction mixture, and the obtained reaction solution was analyzed by gas chromatography to calculate from the area percentage.

Example 1 A 1-L four-necked flask equipped with a thermometer, a backflow condenser, and a stirrer was purged with nitrogen gas at atmospheric pressure.
100 g (0.42 mol) of 2,2-bis (4-hydroxycyclohexyl) propane, 250 g of isophorone
(1.81 mol) and 3 g of a copper-chromium oxide catalyst (N203SD, manufactured by Nikki Chemical Co., Ltd.), and heated to 200 ° C. while stirring under a nitrogen stream.
A time reaction was performed.

After the completion of the reaction, the obtained reaction solution was analyzed by gas chromatography. As a result, the reaction yield of 2,2-bis (4-oxocyclohexyl) propane, which was the desired product, was 96.6%. The selectivity was 96.8%.

Example 2 A reaction was carried out in the same manner as in Example 1 except that 10 g of the copper-chromium oxide catalyst and 300 g (2.17 mol) of isophorone were used, and the reaction temperature was changed to 180 ° C. Was. As a result, the target substance, 2,2-bis (4-
The reaction yield of oxocyclohexyl) propane was 96.7.
%, And the selectivity of the target substance was 96.8%.

Example 3 In Example 1, 10 g of a copper-zinc oxide catalyst (X213 manufactured by Nikki Chemical Co., Ltd.) was used instead of the copper-chromium oxide catalyst.
And 300 g (2.17 mol) of isophorone
And the reaction was carried out in the same manner as in Example 1 except that the reaction time was changed to 6 hours. As a result, the reaction yield of the desired product, 2,2-bis (4-oxocyclohexyl) propane, was 91.1%, and the selectivity of the desired product was 91.1%.
%Met.

Example 4 In Example 1, holon 300 was used instead of isophorone.
g (2.17 mol) and the reaction temperature was 195
The reaction was carried out in the same manner as in Example 1 except that the temperature was changed to ° C. As a result, the reaction yield of 2,2-bis (4-oxocyclohexyl) propane, which was the target product, was 94.7%, and the selectivity for the target product was 94.8%.

Example 5 In Example 1, 100 g of bis (4-hydroxycyclohexyl) was used instead of 2,2-bis (4-hydroxycyclohexyl) propane, and 10 g of a copper-chromium oxide catalyst and 300 g of isophorone ( The reaction was carried out in the same manner as in Example 1 except that the reaction time was 7.5 hours. As a result, the reaction yield of bis (4-oxocyclohexyl), the target product, was 93.3%, and the selectivity for the target product was 94.0%.

Comparative Example 1 In Example 1, 3,3,5-
The reaction was carried out in the same manner as in Example 1 except that 300 g of trimethylcyclohexanone and 7 g of a copper-chromium oxide catalyst were used, the reaction temperature was 190 ° C., and the reaction time was 8 hours. As a result, the reaction yield to 2,2-bis (4-oxocyclohexyl) propane, which is the target product, was 39.3.
%, And the selectivity of the target substance was 44.7%.

Comparative Example 2 A reaction was performed in the same manner as in Example 1 except that 300 g of tetraethylene glycol dimethyl ether and 10 g of a copper-chromium oxide catalyst were used instead of isophorone, and the reaction time was changed to 8 hours. Was performed. As a result, the reaction yield of 2,2-bis (4-oxocyclohexyl) propane, which was the target, was 4.95%, and the selectivity of the target was 11.7%.

COMPARATIVE EXAMPLE 3 In a 1 L glass autoclave, 2,2-bis (4
-Hydroxycyclohexyl) propane 100 g, copper-
Chromium oxide catalyst (N203SD manufactured by Nikki Chemical Co., Ltd.) 5
g and 300 g of butyl acetate were charged, and the atmosphere in the flask was replaced with nitrogen gas at normal temperature and atmospheric pressure. Thereafter, the autoclave was sealed, heated to 200 ° C. with stirring, and reacted at this temperature under a pressure of 0.5 MPa for 8 hours. As a result, the reaction yield of the target product, 2,2-bis (4-oxocyclohexyl) propane, was 12.4%, and the selectivity of the target product was 19.6%.

Comparative Example 4 In Example 1, 300 g of diisopropylbenzene and 10 g of a copper-chromium oxide catalyst (N203SD manufactured by JGC Chemicals Co., Ltd.) were used instead of isophorone, and the reaction time was changed to 16 hours. The reaction was carried out in the same manner as in Example 1. As a result, the reaction yield of 2,2-bis (4-oxocyclohexyl) propane, which is the target product, was 25.4.
%, And the selectivity of the target substance was 32.8%.

Comparative Example 5 The reaction was carried out in the same manner as in Example 1 except that 250 g of cinnamaldehyde was used instead of isophorone and the reaction time was changed to 6 hours. 2,2-Bis (4-oxocyclohexyl) propane could not be obtained.

Comparative Example 6 A reaction was carried out in the same manner as in Example 1 except that 1,2-dihydronaphthalene 250 was used instead of isophorone and the reaction time was changed to 6 hours. As a result, the reaction yield of 2,2-bis (4-oxocyclohexyl) propane, which was the target, was 3.4%, and the selectivity of the target was 12.7%.

[0049]

As described above, according to the method of the present invention,
The dehydrogenation of bis (4-hydroxycyclohexyl) s can be performed under normal pressure under mild reaction conditions, and the desired product can be obtained in high yield and high selectivity.

Continued on the front page (72) Inventor Takeshi Egawa 2-115 Kozaiga, Wakayama-shi F-term in Honshu Kagaku Kogyo Co., Ltd. F-term (reference) 4H006 AA02 AC12 AC44 BA05 BA14 BA30 BA55 BA68 BB16 BC10 BC34 4H039 CA62 CC10

Claims (4)

[Claims] 1. A compound of the general formula (I) [Wherein, X is a single bond, general formula (II)] (Wherein, R ₁ and R ₂ each independently represent a hydrogen atom,
Represents an alkyl group having 6 to 6, a cycloalkyl group having 5 or 6 carbon atoms, or a phenyl group. ), A hydrocarbon group represented by
-O- or -SO ₂ - shows a. A bis (4-hydroxycyclohexyl) compound represented by the formula (1) in a liquid phase comprising an unsaturated ketone solvent having a carbon-carbon double bond conjugated to a C = O double bond in the presence of a copper-based oxide catalyst. General formula (III) characterized by dehydrogenation to (Wherein, X, R ₁ and R ₂ are the same as above). A process for producing bis (4-oxocyclohexyl) s represented by the formula: 2. The process for producing bis (4-oxocyclohexyl) s according to claim 1, wherein the dehydrogenation reaction is carried out in an unsaturated ketone solvent at a reaction temperature in the range of 150 to 280 ° C. 3. The process for producing bis (4-oxocyclohexyl) s according to claim 1, wherein the organic solvent has a boiling point higher than the reaction temperature. 4. The process for producing bis (4-oxocyclohexyl) s according to claim 1, wherein the unsaturated ketone solvent is phorone, isophorone or a mixture thereof.