JP7621095B2 - Method for producing alicyclic compound and alicyclic compound - Google Patents

Description

The present invention relates to a method for selectively producing an alicyclic compound having a norbornane ring, and to the alicyclic compound.

Alicyclic compounds, particularly alicyclic diols, are used as raw materials for polymers such as polyester resins, polycarbonate resins, and urethane (meth)acrylate resins, and the polymers are used in applications such as optical materials, electronic information materials, coating materials, and adhesive materials. For example, polycarbonate resins using pentacyclopentadecanedimethanol as the alicyclic diol and modified polyester resins using pentacyclopentadecanedimethanol are known (Patent Documents 1 and 2).

A commonly known method for producing pentacyclopentadecanedimethanol is to synthesize pentacyclopentadecanedicarbaldehyde by hydroformylation of tricyclopentadiene, and then subject the dialdehyde to catalytic hydrogenation (Patent Document 3).

The tricyclopentadiene used as the raw material in the above manufacturing method is obtained as a mixture of two structural isomers represented by formulas (A1) and (B1) through the Diels-Alder reaction of dicyclopentadiene, and it is known that the compound represented by formula (A1) is the main component (Patent Document 4).

Therefore, when pentacyclopentadecanedicarbaldehyde is produced by the above-mentioned production method, the dicarbaldehyde is obtained as a mixture of two structural isomers with different ring structures represented by formula (A2) and formula (B2), and the main component in this case is the compound represented by formula (A2).

Similarly, when pentacyclopentadecanedimethanol is produced by the above-mentioned production method, the dimethanol is obtained as a mixture of two structural isomers represented by formulas (A3) and (B3), and the main component is the compound represented by formula (A3).

In other words, the conventionally known production methods cannot selectively produce only the compound represented by formula (B3). In addition, there are no known examples of isolating a high-purity compound represented by formula (B3) from an isomer mixture represented by formulas (A3) and (B3). Similarly, there are no known examples of isolating a compound represented by formula (B1) and a compound represented by formula (B2), which are raw materials for the compound represented by formula (B3), from an isomer mixture containing the compound represented by formula (B1) and the compound represented by formula (B2), with high purity.

JP 2000-302860 A Patent No. 5849967 Patent No. 4573003 Patent No. 5742853

The object of the present invention is to provide a method for selectively producing an alicyclic compound having a norbornane ring, and the alicyclic compound.

The present invention provides the following [1] to [10].
[1] General formula (1)

(In the formula, one of R ¹¹ and R ¹² represents a formyl group or a hydroxymethyl group, and the other represents a hydrogen atom.)
and cyclopentadiene by Diels-Alder reaction.

(In the formula, R ¹¹ and R ¹² are defined as above.)
A method for producing an alicyclic compound represented by the formula:

[2] General formula (1)

(In the formula, one of R ¹¹ and R ¹² represents a formyl group or a hydroxymethyl group, and the other represents a hydrogen atom.)
and cyclopentadiene by Diels-Alder reaction to obtain a compound represented by the general formula (2)

(In the formula, R ¹¹ and R ¹² are defined as above.)
The method includes a step of obtaining an alicyclic compound represented by the general formula (4):

(In the formula, one of R ⁴¹ and R ⁴² represents a hydroxymethyl group, and the other represents a hydrogen atom; and one of R ⁴³ and R ⁴⁴ represents a hydroxymethyl group, and the other represents a hydrogen atom.)
A method for producing an alicyclic compound represented by the formula:

[3] The alicyclic compound represented by the general formula (2) is subjected to a hydroformylation reaction to obtain a compound represented by the general formula (3)

(In the formula, R ¹¹ and R ¹² are defined as above, and one of R ³³ and R ³⁴ represents a formyl group, and the other represents a hydrogen atom.)
and subjecting the alicyclic compound represented by general formula (3) to a reduction reaction to obtain the alicyclic compound represented by general formula (4).

[4] Equation (5)

The method for producing an alicyclic compound according to any one of [1] to [3] further includes a step of obtaining a compound represented by the general formula (1), which includes a step of subjecting a compound represented by the general formula (1) to a hydroformylation reaction.

[5] The method for producing an alicyclic compound according to any one of [1] to [4], wherein one of R ¹¹ and R ¹² in general formula (1) is a formyl group, and the other is a hydrogen atom.

[6] A method for producing an alicyclic compound according to any one of [1] to [5], wherein in the step of obtaining an alicyclic compound represented by general formula (2), the amount of cyclopentadiene used is 0.05 to 2.0 moles per mole of the compound represented by general formula (1).

[7] A method for producing an alicyclic compound according to any one of [1] to [6], in the step of obtaining an alicyclic compound represented by general formula (2), cyclopentadiene is supplied at a temperature of 100 to 250°C to a reactor that has already been charged with a compound represented by general formula (1).

[8] A method for producing an alicyclic compound according to any one of [3] to [7], in which a rhodium compound and an organic phosphorus compound are used as catalysts when subjecting an alicyclic compound represented by general formula (2) to a hydroformylation reaction.

[9] The method for producing an alicyclic compound according to any one of [3] to [8], wherein the reduction reaction is a step of subjecting the alicyclic compound represented by the general formula (3) to a hydrogenation reaction in the presence of a metal catalyst.

[10] An alicyclic compound represented by general formula (2).

(In the formula, one of R ¹¹ and R ¹² represents a formyl group or a hydroxymethyl group, and the other represents a hydrogen atom.)

The present invention provides a method for selectively producing an alicyclic compound having a norbornane ring, and the alicyclic compound.

1 is a ¹ H-NMR spectrum of the compound (4) obtained in Example 2.

A preferred embodiment of the present invention (hereinafter, sometimes referred to as the present embodiment) will be described in detail below.
The method for producing the alicyclic compound represented by the general formula (2) of the present invention requires subjecting the compound represented by the general formula (1) to a Diels-Alder reaction with cyclopentadiene. By using the compound represented by the general formula (1) as a raw material in this manner, the alicyclic compound represented by the general formula (2) can be selectively obtained, which is preferable.

The method for producing an alicyclic compound represented by the general formula (4), which includes a step of obtaining an alicyclic compound represented by the general formula (2), is preferable in that it can selectively produce an alicyclic compound represented by the general formula (4) that is useful as a raw material for optical materials, etc., as described above.

It is preferable that the method further includes a step of subjecting the alicyclic compound represented by the general formula (2) to a hydroformylation reaction to obtain an alicyclic compound represented by the general formula (3), and a step of subjecting the alicyclic compound represented by the general formula (3) to a reduction reaction to obtain an alicyclic compound represented by the general formula (4).

That is, the compound represented by the general formula (1) and cyclopentadiene are subjected to a Diels-Alder reaction to produce an alicyclic compound represented by the general formula (2), which is then subjected to a hydroformylation reaction to produce an alicyclic compound represented by the general formula (3), which is then subjected to a reduction reaction to produce an alicyclic compound represented by the general formula (4) (pentacyclopentadecanedimethanol). This is preferable in that the alicyclic compound represented by the general formula (4) can be selectively produced from the compound represented by the general formula (1).

(In the formula, R ¹¹ , R ¹² , R ³³ , R ³⁴ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are each as defined above.)
As the reduction reaction, it is more preferable to subject the alicyclic compound represented by the general formula (3) to a hydrogenation reaction in the presence of a metal catalyst.

Hereinafter, the compound represented by general formula (1) will be referred to as compound (1). The same applies to compounds with other formula numbers.

Step 1 (Diels-Alder reaction)
In step 1 of this embodiment, compound (2) can be produced by subjecting compound (1) and cyclopentadiene to a Diels-Alder reaction.
Compound (1) may be compound (11) or compound (12), or a mixture thereof.

(In the formula, one of R ¹³ and R ¹⁴ represents a formyl group, and the other represents a hydrogen atom; and one of R ¹⁵ and R ¹⁶ represents a hydroxymethyl group, and the other represents a hydrogen atom.)

Compound (11) can be produced by subjecting dicyclopentadiene (corresponding to compound (5)) to a hydroformylation reaction according to the method described in, for example, JP-A-2005-139179. The hydroformylation can be carried out in the same manner as the hydroformylation method described below.

(In the formula, R ¹³ and R ¹⁴ are defined as above.)

Compound (12) can also be produced by subjecting compound (11) to a reduction reaction, for example, according to the method described in JP-A-2001-139638.

(In the formula, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each defined as above.)
The compound obtained by subjecting the compound (5) to a hydroformylation reaction is the compound (11) in which at least one of R ¹¹ and R ¹² of the compound (1) is a formyl group, and the other is obtained as a hydrogen atom. Therefore, the compound (11) is obtained as a structural isomer in which the substitution positions of the hydrogen atoms of R ¹³ and R ¹⁴ are different. The structural isomer may be a single one or a mixture. The compound (12) is also obtained as a similar structural isomer, and may be a single one or a mixture. In this embodiment, the hydroformylation reaction proceeds with respect to the carbon-carbon double bond at a specific position of the compound (5), and the other carbon-carbon double bond remains, so that the compound (2) which is the result of the Diels-Alder reaction in step 1 becomes the specific ring structure, which is preferable.

When the subsequent steps are carried out using a compound in which R ¹¹ is a hydrogen atom as compound (1), an alicyclic compound in which the substituent corresponding to R ¹¹ is a hydrogen atom is obtained, and when the subsequent steps are carried out using a compound in which R ¹² is a hydrogen atom, an alicyclic compound in which the substituent corresponding to R ¹² is a hydrogen atom is obtained. Note that in the present application, the purity of each compound is calculated based on the sum of structural isomers having different substitution positions of hydrogen atoms.

In step 1 of this embodiment, compound (1) is reacted with cyclopentadiene, which usually exists as a mixture with a Diels-Alder reaction product of cyclopentadiene such as dicyclopentadiene. Dicyclopentadiene, etc. means a dimer or higher of cyclopentadiene.

The cyclopentadiene of this embodiment may be substantially cyclopentadiene alone, may be a mixture of cyclopentadiene and dicyclopentadiene, or may be a mixture of dicyclopentadiene. "Substantially" means that the purity is 98% by mass or more. In the following, "%" means "% by mass" unless otherwise specified.

Dicyclopentadiene etc. easily becomes cyclopentadiene when heated etc., so in the Diels-Alder reaction of compound (1) with dicyclopentadiene etc., cyclopentadiene is generated in the reaction system, so it can be added to the reaction system as dicyclopentadiene etc., or it can be added to the reaction system as a mixture of cyclopentadiene and dicyclopentadiene etc. In the following explanation of the embodiment, cyclopentadiene and dicyclopentadiene etc. are collectively referred to as cyclopentadiene, and the amounts used etc. are described assuming that all are cyclopentadiene.

Compound (2) may be compound (21), compound (22), or a mixture thereof.

(In the formula, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each defined as above.)
In step 1 of this embodiment, compound (12) may be subjected to a Diels-Alder reaction to obtain compound (22), or compound (11) may be subjected to a Diels-Alder reaction, and then the resulting compound (21) may be subjected to a reduction reaction similar to that described above to obtain compound (22).

(In the formula, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each defined as above.)
The purity of the cyclopentadiene used in step 1 of the present embodiment is preferably 90% or more, more preferably 95% or more, and even more preferably 98% or more, from the viewpoint of obtaining an alicyclic compound with high purity.
The amount of cyclopentadiene used is preferably 0.05 to 2.0 moles, more preferably 0.1 to 1.8 moles, and even more preferably 0.2 to 1.5 moles, per mole of compound (1). An amount of 0.05 moles or more is preferred because the amount of compound (2) produced increases. An amount of 2.0 moles or less is preferred because the amount of by-products decreases.

Although step 1 of this embodiment can be performed without using a solvent, a solvent can also be used. The solvent is not particularly limited as long as it dissolves compound (1) and cyclopentadiene. Specific examples include alcohols such as ethanol, 2-propanol, and 1-butanol; esters such as ethyl acetate and butyl acetate; saturated aliphatic hydrocarbons such as pentane, hexane, heptane, octane, isooctane, and isononane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; and aromatic hydrocarbons such as benzene, toluene, and xylene. These solvents may be used alone or in combination of two or more.

Step 1 of the present embodiment is preferably carried out in an inert gas atmosphere, specific examples of which include nitrogen and argon.
The temperature in step 1 of this embodiment is preferably 100 to 250° C., more preferably 120 to 240° C., and even more preferably 140 to 230° C. A temperature of 100° C. or higher is preferable because the reaction efficiency increases. A temperature of 250° C. or lower is preferable because by-products such as high boiling point components are reduced.

Various reaction methods can be used for step 1 of this embodiment, such as a batch method using a tank reactor, a semi-batch method in which the substrate and solvent are supplied to a tank reactor under reaction conditions, and a continuous flow method in which the substrate and solvent are circulated in a tubular reactor under reaction conditions. A semi-batch method in which compound (1) is placed in a reactor in advance and cyclopentadiene is supplied to a reactor under reaction conditions is preferred because it reduces by-products such as high boiling point components. The supply temperature of cyclopentadiene is more preferably 100 to 250°C.

The compound (2) obtained in step 1 of this embodiment can be used as it is as a raw material in the next step, but it may also be purified by a method such as distillation, extraction, crystallization, column chromatography, or a combination of these methods before being used in the next step. In addition, the compound (1) and cyclopentadiene recovered during purification can be reused in step 1 to improve the yield.

Step 2 (hydroformylation reaction)
In step 2 of this embodiment, compound (3) can be produced by subjecting a mixed gas (hereinafter referred to as synthesis gas) of compound (2), carbon monoxide (hereinafter also referred to as "CO") and hydrogen (hereinafter also referred to as " _H2 ") to a hydroformylation reaction in the presence of a catalyst and, if necessary, a solvent.
Compound (3) may be compound (31), compound (32), or a mixture thereof.

(In the formula, R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ³³ and R ³⁴ are each defined as above.)
In step 2 of this embodiment, compound (21) may be subjected to a hydroformylation reaction to give compound (31), or compound (22) may be subjected to a hydroformylation reaction to give compound (32).

(In the formula, R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ³³ and R ³⁴ are each defined as above.)
The catalyst used in step 2 of this embodiment may be a catalyst used in a general hydroformylation reaction, such as a known metal catalyst, for example, a cobalt-based catalyst, a rhodium-based catalyst, or a platinum-based catalyst. Among these, a rhodium-based catalyst is preferred in terms of reaction rate, yield, etc. It is more preferable to use a rhodium-based catalyst in combination with a rhodium compound and an organophosphorus compound.

When a rhodium compound and an organic phosphorus compound are used in combination, the rhodium compound is not particularly limited as long as it forms a complex with the organic phosphorus compound and exhibits catalytic activity for hydroformylation. Specific examples include _Rh4 (CO) ₁₂ , _Rh6 (CO) ₁₆ , rhodium acetate, Rh(acac) ₃ (wherein acac represents an acetylacetonate group, the same applies below), Rh(acac)(CO) ₂ , Rh(acac)(cod) (wherein cod represents a 1,5-cyclooctadienyl group), _RhCl3 , RhCl( _PPh3 ) ₃ (wherein Ph represents a phenyl group, the same applies below), RhH(CO)( _PPh3 ) ₃ , etc.

The concentration of the rhodium compound in this embodiment is preferably 0.1 to 100 ppm, more preferably 0.5 to 50 ppm, and even more preferably 1 to 20 ppm, as the weight concentration of rhodium atoms in the reaction mixture. A concentration of 0.1 ppm or more is preferable because it increases the reaction efficiency. Also, a concentration of 100 ppm or less is preferable because it reduces the cost of the rhodium catalyst.

The organic phosphorus compound is not particularly limited as long as it forms a complex with a rhodium compound and exhibits catalytic activity for hydroformylation. Specific examples include phosphines represented by the general formula R ¹ ₃ P and phosphites represented by the general formula (R ² O) ₃ P. The three R ^1s and the three R ^2s may be the same or different, and examples include aromatic hydrocarbon groups and aliphatic hydrocarbon groups. Specific examples include, but are not limited to, alkyl groups having 1 to 12 carbon atoms; phenyl groups which may be substituted with alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or sulfone groups; alicyclic alkyl groups which may be substituted with alkyl groups having 1 to 8 carbon atoms or alkoxy groups having 1 to 8 carbon atoms, and the like. Examples of the alicyclic alkyl groups include cyclohexyl groups. Bicyclic heterocyclic phosphines can also be used. Specific examples include triphenylphosphine, tritolylphosphine, tris(2-methylphenyl)phosphine, sodium triphenylphosphine trisulfonate, tricyclohexylphosphine, triphenylphosphite, tris(nonylphenyl)phosphite, tris(2-tert-butylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2-methylphenyl)phosphite, tris(3-methyl-6-tert-butylphenyl)phosphite, etc., and among these, triphenylphosphine or triphenylphosphite is preferred. These organic phosphorus compounds may be used alone or in combination of two or more.

The amount of the organic phosphorus compound used is preferably 5 to 2000 times by mole relative to the amount of rhodium, more preferably 10 to 1000 times by mole, and even more preferably 20 to 500 times by mole. An amount of 5 times or more is preferred because it improves the stability of the rhodium catalyst. Also, an amount of 2000 times or less by mole is preferred because it reduces the cost of the organic phosphorus compound.

Although step 2 of this embodiment can be performed without using a solvent, a solvent can also be used. The solvent is not particularly limited as long as it dissolves compound (2), the rhodium compound, and the organic phosphorus compound. Specific examples include alcohols such as ethanol, 2-propanol, and 1-butanol; esters such as ethyl acetate and butyl acetate; saturated aliphatic hydrocarbons such as pentane, hexane, heptane, octane, isooctane, and isononane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; and aromatic hydrocarbons such as benzene, toluene, and xylene. These solvents may be used alone or in combination of two or more.

The temperature in step 2 of this embodiment is preferably 60 to 160°C, more preferably 70 to 130°C, and even more preferably 80 to 100°C. A temperature of 60°C or higher is preferred because it increases the reaction efficiency. Also, a temperature of 160°C or lower is preferred because it reduces by-products such as high boiling point components.

Step 2 of this embodiment is preferably carried out under pressure with a synthesis gas containing a mixture of carbon monoxide and hydrogen. In this case, carbon monoxide and hydrogen can be introduced into the reaction system independently, or a synthesis gas can be prepared in advance and introduced into the reaction system. The molar ratio of the synthesis gas (=CO/H ₂ ) introduced into the reaction system is preferably 0.4 to 2.5, more preferably 0.6 to 1.7, and even more preferably 0.8 to 1.3. If the molar ratio of the synthesis gas is within the above range, problems such as a decrease in reaction activity and a decrease in selectivity for compound (3) are unlikely to occur, and this is preferable. Note that a gas inert to the hydroformylation reaction, such as methane, ethane, propane, nitrogen, helium, argon, carbon dioxide, etc., may coexist in the reaction system.

The pressure in step 2 of this embodiment is preferably 0.6 to 20 MPa (hereinafter, "Pa" means gauge pressure unless otherwise specified), more preferably 0.8 to 15 MPa, and even more preferably 1.0 to 10 MPa. A pressure of 0.6 MPa or more is preferable because it increases the reaction efficiency. Also, a pressure of 20 MPa or less is preferable because it reduces the cost of equipment with excellent pressure resistance.

A variety of reaction methods can be used for step 2 in this embodiment, including a batch method using a tank reactor, a semi-batch method in which the substrate, catalyst, solvent, etc. are supplied to a tank reactor under reaction conditions, and a continuous flow method in which the substrate, catalyst, solvent, etc. are circulated through a tubular reactor under reaction conditions.

The compound (3) obtained by step 2 of this embodiment can be used as it is as a raw material for the next step 3, but it may be purified by a method such as distillation, extraction, crystallization, column chromatography, or a combination of these, and then subjected to step 3. The formyl groups contained in the compound (3) obtained by step 2 of this embodiment may be partially reduced to hydroxymethyl groups, and these groups may be subjected to step 3 as a mixture.

Step 3 (reduction reaction)
In step 3 of this embodiment, compound (4) is preferably produced by subjecting compound (3) to a reduction reaction. The reduction reaction may be carried out by reacting compound (3) with a reducing agent that generates a hydride, such as sodium borohydride (hydride reduction reaction), but it is industrially advantageous to react compound (3) with hydrogen gas in the presence of a metal catalyst (hydrogenation reaction).

In the hydrogenation reaction, the metal catalyst used in reacting hydrogen gas with compound (3) is not particularly limited, but known catalysts can be used. For example, catalysts containing one or more elements selected from the transition metals of Groups 6 to 12 in the periodic table are preferred, and specific examples include Raney metals such as Raney nickel, Raney cobalt, and Raney copper, reduced nickel-supported catalysts, reduced cobalt-supported catalysts, copper-chromium oxide catalysts, copper-zinc oxide catalysts, copper-iron oxide catalysts, precious metal-supported catalysts such as palladium black, platinum black, ruthenium black, palladium-supported silica, palladium-supported alumina, palladium-supported activated carbon, platinum-supported silica, platinum-supported alumina, platinum-supported activated carbon, ruthenium-supported silica, ruthenium-supported alumina, ruthenium-supported activated carbon, rhodium-supported activated carbon, iridium-supported activated carbon, and rhenium-supported activated carbon. The amount of catalyst used when reacting hydrogen gas with compound (3) is not particularly limited, but can be selected appropriately depending on the type of catalyst, reaction format, etc.

The hydrogenation reaction can be carried out without using a solvent, but a solvent can also be used. The solvent is not particularly limited as long as it dissolves compound (3). Specific examples include alcohols such as ethanol, 2-propanol, and 1-butanol; esters such as ethyl acetate and butyl acetate; saturated aliphatic hydrocarbons such as pentane, hexane, heptane, octane, isooctane, and isononane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; and aromatic hydrocarbons such as benzene, toluene, and xylene. These solvents may be used alone or in combination of two or more. When using alcohols, water may be added.

The temperature of the hydrogenation reaction can be set appropriately taking into consideration the reaction rate, yield, etc. depending on the type and amount of catalyst used, but is preferably 80 to 250°C, more preferably 90 to 200°C, and even more preferably 100 to 170°C. Temperatures of 80°C or higher are preferred because they increase the reaction efficiency. Temperatures of 250°C or lower are also preferred because they reduce by-products such as high boiling point components.

The pressure of the hydrogenation reaction is preferably 1.0 to 20 MPa, more preferably 1.5 to 15 MPa, and even more preferably 2.0 to 10 MPa. A pressure of 1.0 MPa or more is preferable because it increases the reaction efficiency. A pressure of 20 MPa or less is also preferable because it reduces the cost of equipment with excellent pressure resistance. Gases inert to the hydrogenation reaction, such as methane, ethane, propane, nitrogen, helium, argon, and carbon dioxide, may also be present in the reaction system.

A variety of reaction methods can be used for the hydrogenation reaction, including a batch method using a tank reactor, a semi-batch method in which the substrate, catalyst, solvent, etc. are supplied to a tank reactor under reaction conditions, and a continuous flow method in which the substrate, catalyst, solvent, etc. are circulated through a tubular reactor under reaction conditions.

The compound (4) obtained in step 3 of this embodiment can be purified by a method such as distillation, extraction, crystallization, column chromatography, or a combination of these.
Compound (1), compound (2), compound (3) and compound (4) may each have any stereostructure, may have a single stereostructure or may be a mixture thereof.
In finally obtaining compound (4), the reduction of the formyl group of R ¹¹ or R ¹² to a hydroxymethyl group may be carried out at any stage of compound (1), compound (2) or compound (3).

When reducing a formyl group of a molecule having an olefin, it is preferable to use a hydride reduction reaction. More specifically, it is preferable to use a hydride reduction reaction for the reduction of the compound (11) to the compound (12) and the reduction of the compound (21) to the compound (22).

The reducing reagent used in the hydride reduction reaction to generate hydride includes metal hydrides or metal hydrogen complex compounds. As metal hydrides or metal hydrogen complex compounds, sodium borohydride, lithium borohydride, lithium aluminum hydride, sodium hydride, diisobutylaluminum hydride, sodium cyanoborohydride, lithium borohydride, borane dimethylsulfide, and borane tetrahydrofuran are preferred, with sodium borohydride being preferred from the standpoint of ease of handling and the yield of the target product.

The hydride reduction reaction can be carried out without using a solvent, but a solvent can also be used. The solvent is not particularly limited as long as it dissolves compound (11) and compound (21). Specific examples include alcohols such as ethanol, 2-propanol, and 1-butanol; esters such as ethyl acetate and butyl acetate; saturated aliphatic hydrocarbons such as pentane, hexane, heptane, octane, isooctane, and isononane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; and aromatic hydrocarbons such as benzene, toluene, and xylene. The solvent used in the previous step can also be used as it is. These solvents may be used alone or in combination of two or more.
The temperature of the hydride reduction reaction is preferably 0 to 160° C., more preferably 10 to 130° C., and even more preferably 15 to 100° C., and the reaction may be carried out without external heating or cooling.

The hydride reduction reaction is preferably carried out under an inert gas atmosphere, and is preferably carried out under a nitrogen gas atmosphere or an argon gas atmosphere.
The reaction apparatus is not particularly limited and can be appropriately selected.

The resulting compound (4) can be used as a raw material for polymers such as polyester resins, polycarbonate resins, and urethane (meth)acrylate resins.

The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to the following examples.

The purity of the compounds (1) to (4) obtained in the examples was analyzed by gas chromatography equipped with a hydrogen flame ionization detector.
[Gas chromatography with hydrogen flame ionization detector]
<Measurement conditions>
・ Apparatus: Shimadzu Gas Chromatograph GC-2014
Column: Agilent Technologies DB-1 (column length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm)

Temperature rise conditions: After holding at 50° C. for 5 minutes, the temperature was raised to 320° C. at a rate of 10° C. per minute, and then held for 28 minutes.
Sample injection temperature: 320°C
Detector temperature: 330°C

[Calculation method]
The purity of the compounds (1) to (4) was calculated from the GC peak area according to the following formula.
Purity (%) = (A/B) x 100
Here, A represents the peak area of the target product, and B represents the sum of all peak areas.
The yield was calculated according to the following formula.

Yield (%) = (C/D) x 100
Here, C represents the number of moles of the target product (calculated by multiplying the weight of the target product including impurities by its purity and dividing the result by the molecular weight of the target product), and D represents the number of moles of the reference raw material.

Compound (2) and compound (3) were identified by gas chromatography-mass spectrometry, and compound (4) was identified by ¹ H-NMR and gas chromatography-mass spectrometry.

[Gas chromatography mass spectrometry]
<Measurement conditions>
・ Apparatus: Gas chromatograph 6890N manufactured by Agilent Technologies
・ Equipment: JEOL mass spectrometer JMS-K9
Column: Agilent Technologies DB-1 (column length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm)

Temperature rise conditions: After maintaining at 50° C. for 5 minutes, the temperature was raised to 300° C. at a rate of 7° C. per minute, and then maintained for 20 minutes.
Sample injection temperature: 320°C
Ion source: CI or EI
Ionization section temperature: CI 150°C, EI 200°C

[ ^1H -NMR]
<Measurement conditions>
・ Equipment: JNM-ECA500 manufactured by JEOL Ltd.
Measurement solvent: chloroform-d 99.8% containing 0.05 Vol% tetramethylsilane Resonance frequency: 500 MHz

[Example 1]
[Production of compound (11)]
In a 1000 ml autoclave, 200 g (1.51 mol) of dicyclopentadiene (Tokyo Chemical Industry Co., Ltd.), 0.47 g (1.51 mmol) of triphenyl phosphite (Kanto Chemical Co., Ltd.), and 0.0039 g (0.0151 mmol) of Rh(acac)(CO) ₂ (N.E. Chemcat Co., Ltd.) were placed at room temperature, and the system was replaced with nitrogen. The system was heated to 50° C. and stirred for 10 minutes while maintaining this temperature. The system was then replaced with synthesis gas (CO/H ₂ molar ratio = 0.8) and the pressure was increased to 7.0 MPa, after which the temperature in the system was adjusted to 90° C. and the internal pressure to 8.0 MPa. The reaction was stopped after 2 hours while maintaining this temperature and pressure, and 233.8 g of a crude product containing the compound (11) was obtained.

Analysis by gas chromatography showed that the purity of the obtained compound (11) was 96.5% and the yield based on dicyclopentadiene was 92.1%.

[Step 1: Preparation of compound (21)]

245.5 g of crude product containing compound (11) (content of compound (11) 236.9 g, 1.46 mol) obtained in the same manner as in [Production of compound (11)] was placed in a 1000 ml autoclave at room temperature, and the system was replaced with nitrogen. The system was pressurized to 0.9 MPa with nitrogen, and then heated to 230°C. While maintaining this temperature and stirring, a mixture of 25 g (0.19 mol, equivalent to 0.38 mol of cyclopentadiene) (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.5 g of methylcyclohexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the system over 1.7 hours. After maintaining this temperature for 30 minutes, the reaction was stopped, and 265.5 g of crude product containing the compound (21) was obtained.

As a result of analysis by gas chromatography, the purity of the obtained compound (21) was 6.2%, and the yield based on cyclopentadiene was 19.0%.
As a result of measurement by gas chromatography mass spectrometry (CI), a peak at 229 [(M+H) ⁺ ] corresponding to compound (21) was confirmed.

[Example 2]
[Step 2: Production of compound (31)]
In a 1000 ml autoclave, 265.5 g of crude product containing compound (21) obtained in the same manner as in Example 1 (content of compound (21) 16.5 g, 0.07 mol), 0.53 g (1.70 mmol) of triphenyl phosphite (manufactured by Kanto Chemical Co., Ltd.), and 0.0044 g (0.0170 mmol) of Rh(acac)(CO) ₂ (manufactured by N.E. Chemcat Co., Ltd.) were placed at room temperature, and the system was replaced with nitrogen. The temperature in the system was raised to 50° C., and the system was stirred for 10 minutes while maintaining this temperature. Thereafter, the system was replaced with synthesis gas (molar ratio of CO/H ₂ = 0.8), and the pressure was raised to 7.0 MPa, and the temperature in the system was adjusted to 90° C. and the internal pressure to 8.0 MPa. The reaction was stopped after 2 hours while maintaining this temperature and pressure, and 268.0 g of crude product containing the compound (31) was obtained.

As a result of analysis by gas chromatography, the purity of the obtained compound (31) was 4.6%, and the yield based on the compound (21) was 66.3%.
Gas chromatography-mass spectrometry (CI) measurement confirmed a peak at 259 [(M+H) ⁺ ] corresponding to compound (31).

[Step 3: Production of compound (4)]
Into a 1000 ml autoclave, 268.0 g of the crude product containing compound (31) obtained in the above step 2 (content of compound (31) 12.3 g, 0.05 mol), 200 g of 2-propanol (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 2.0 g of water, and 6.0 g of reduced nickel-supported catalyst were placed, and the system was replaced with hydrogen, and the pressure in the system was increased to 3.0 MPaG with hydrogen gas, and then the temperature in the system was adjusted to 150° C. and the internal pressure to 5.0 MPa. After maintaining this temperature and pressure for 2 hours, the reaction was stopped, and the reduced nickel-supported catalyst was removed by pressure filtration, and 441.7 g of the crude product containing the compound (4) was obtained. The solvent and low boiling points were removed from the obtained crude product by distillation (internal temperature in the range of 105 to 190° C. and a pressure of 0.1 kPa (absolute pressure)), and then silica gel column chromatography and distillation (internal temperature in the range of 200 to 220° C. and a pressure of 0.03 kPa (absolute pressure)) were performed to obtain 2.4 g of compound (4).

As a result of analysis by gas chromatography, the purity of the obtained compound (4) was 98.5%, and the yield based on the compound (31) was 18.9%.
As a result of measurement by gas chromatography mass spectrometry (EI), a peak of 262 [M ⁺ ] corresponding to compound (4) was confirmed.

The results of ¹ H-NMR measurement are shown below.
¹ H-NMR (CDCl ₃ , δppm); 3.53 (2H), 3.40-3.22 (4H), 2.78-0.76 (20H)
For reference, the ¹ H-NMR spectrum is shown in FIG.

[Example 3]
[Production of compound (12)]
In a 1000 ml autoclave, 200 g (1.51 mol) of dicyclopentadiene (Tokyo Chemical Industry Co., Ltd.), 100 g of 2-propanol (Fujifilm Wako Pure Chemical Industries, Ltd.), 0.47 g (1.51 mmol) of triphenyl phosphite (Kanto Chemical Co., Ltd.), and 0.0039 g (0.0151 mmol) of Rh(acac)(CO) ₂ (N.E. Chemcat Corporation) were placed at room temperature, and the system was replaced with nitrogen. The system was heated to 50° C., and stirred for 10 minutes while maintaining this temperature. Thereafter, the system was replaced with synthesis gas (molar ratio of CO/H ₂ = 0.8), and the pressure was increased to 7.0 MPa, and the temperature in the system was adjusted to 90° C. and the internal pressure to 8.0 MPa. The reaction was stopped after 2 hours while maintaining this temperature and pressure, and 335.1 g of a reaction liquid containing compound (11) was obtained. This was transferred to a 1000 ml glass reactor, 100 g of 2-propanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added thereto, and the inside of the system was replaced with nitrogen. Then, 57.1 g (1.51 mol) of sodium borohydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added while maintaining the temperature in the system at 20 to 75° C., and after 4.5 hours, 400 g of water was added to stop the reaction. The obtained liquid was extracted with ethyl acetate and water, and the solvent was removed from the organic layer containing the compound (12), and 239.2 g of a crude product containing the compound (12) was obtained.

Analysis by gas chromatography showed that the purity of the obtained compound (12) was 82.3% and the yield based on dicyclopentadiene was 79.3%.

[Production of compound (4) using compound (12) as a raw material]
235.0 g of crude product containing compound (12) (content of compound (12) 193.4 g, 1.18 mol) obtained in the same manner as in [Production of compound (12)] was placed in a 1000 ml autoclave at room temperature, and the system was replaced with nitrogen. After the pressure in the system was increased to 0.9 MPa with nitrogen, the system was heated to 200° C., and while maintaining this temperature and stirring, a mixture of 100 g (0.76 mol, equivalent to 1.51 mol of cyclopentadiene) (manufactured by Tokyo Chemical Industry Co., Ltd.) and 50 g of methylcyclohexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the system over 3.5 hours, and the reaction was stopped when the addition was completed. Then, 0.47 g (1.51 mmol) of triphenyl phosphite (Kanto Chemical Co., Ltd.) and 0.0039 g (0.0151 mmol) of Rh(acac)(CO) ₂ (N.E. Chemcat Co., Ltd.) were added to the reaction solution at room temperature, and the system was replaced with nitrogen. The temperature in the system was raised to 50° C., and the system was stirred for 10 minutes while maintaining this temperature. The system was then replaced with synthesis gas (CO/H ₂ molar ratio = 0.8) and the pressure was raised to 7.0 MPa, after which the temperature in the system was adjusted to 90° C. and the internal pressure to 8.0 MPa. The reaction was stopped after 2 hours while maintaining this temperature and pressure. Thereafter, 163 g of 2-propanol (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 2.0 g of water, and 6.0 g of reduced nickel-supported catalyst were added to this reaction solution, the system was replaced with hydrogen, and the pressure in the system was increased to 3.0 MPa with hydrogen gas, and then the temperature in the system was adjusted to 150° C. and the internal pressure to 5.0 MPa. After maintaining this temperature and pressure for 2 hours, the reaction was stopped, the reduced nickel-supported catalyst was removed by pressure filtration, and the solvent was distilled off, to obtain 337.5 g of a crude product containing the compound (4).

Analysis by gas chromatography showed that the purity of the obtained compound (4) was 3.4%, and the yield based on compound (12) was 3.7%.

The present invention provides a selective production method for an alicyclic compound having a norbornane ring, which is useful as a raw material for polymers such as polyester resins, polycarbonate resins, and urethane (meth)acrylate resins, and the alicyclic compound.

Claims (9)

General formula (1)

(In the formula, one of R ¹¹ and R ¹² represents a formyl group or a hydroxymethyl group, and the other represents a hydrogen atom.)
and cyclopentadiene by Diels-Alder reaction.

(In the formula, ^R11 and ^R12 are defined as above.)
A method for producing an alicyclic compound represented by the formula: General formula (1)

(In the formula, one of R ¹¹ and R ¹² represents a formyl group or a hydroxymethyl group, and the other represents a hydrogen atom.)
and cyclopentadiene by Diels-Alder reaction to obtain a compound represented by the general formula (2)

(In the formula, R ¹¹ and R ¹² are defined as above.)
and obtaining an alicyclic compound represented by the formula:
The alicyclic compound represented by the general formula (2) is subjected to a hydroformylation reaction to obtain a compound represented by the general formula (3):

(In the formula, R ¹¹ and R ¹² are defined as above, and one of R ³³ and R ³⁴ represents a formyl group, and the other represents a hydrogen atom.)
and obtaining an alicyclic compound represented by the formula:
and a step of subjecting the alicyclic compound represented by the general formula (3) to a reduction reaction to obtain an alicyclic compound represented by the general formula (4).

(In the formula, one of R ⁴¹ and R ⁴² represents a hydroxymethyl group, and the other represents a hydrogen atom; and one of R ⁴³ and R ⁴⁴ represents a hydroxymethyl group, and the other represents a hydrogen atom.)
A method for producing an alicyclic compound represented by the formula: 3. The process for producing an alicyclic compound according to claim 2 , wherein a rhodium compound and an organophosphorus compound are used as catalysts in subjecting the alicyclic compound represented by the general formula (2) to a hydroformylation reaction. 4. The method for producing an alicyclic compound according to claim 2 or 3 , wherein the reduction reaction is a step of subjecting the alicyclic compound represented by the general formula (3) to a hydrogenation reaction in the presence of a metal catalyst. Equation (5)

The method for producing an alicyclic compound according to any one of claims 1 to 4 , further comprising a step of obtaining a compound represented by general formula (1), the step comprising a step of subjecting a compound represented by the following general formula (1) to a hydroformylation reaction. The method for producing an alicyclic compound according to any one of claims 1 to 5 , wherein one of R ¹¹ and R ¹² in general formula (1) is a formyl group, and the other is a hydrogen atom. The method for producing an alicyclic compound according to any one of claims 1 to 6 , wherein in the step of obtaining the alicyclic compound represented by the general formula (2), the amount of cyclopentadiene used is 0.05 to 2.0 mol per 1 mol of the compound represented by the general formula (1). The method for producing an alicyclic compound according to any one of claims 1 to 7, wherein in the step of obtaining the alicyclic compound represented by the general formula (2), cyclopentadiene is supplied at a temperature of 100 to 250°C to a reactor previously charged with the compound represented by the general formula (1 ) . An alicyclic compound represented by general formula (2):

(In the formula, one of R ¹¹ and R ¹² represents a formyl group or a hydroxymethyl group, and the other represents a hydrogen atom.)