Method for producing diol compound having cyclohexane skeleton

Abstract

To provide a process capable of obtaining a diol compound having a cyclohexane skeleton with a high ratio of total trans compounds / cis-containing compounds under a mild reaction condition.SOLUTION: A method of producing a diol compound having a cyclohexane skeleton includes: reacting at least one compound selected from a dione compound having a cyclohexane skeleton, a ketol compound having a cyclohexane skeleton or a dihydroxy aryl compound, and a diol compound having a cyclohexane skeleton as (a) raw material(s) in the presence of a metal catalyst without adding a solvent in a solid phase state under hydrogen environment, where the ratio of total trans compounds / cis-containing compounds is higher than 1.5 and 10,000 or lower.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing a diol compound having a cyclohexane skeleton with a high ratio of all-trans isomer / cis content. [Background technology]

[0002] Diol compounds are used to produce various polymer materials, and for example, polyesters derived from dicarboxylic acids and diol compounds have excellent mechanical properties, heat resistance, and chemical resistance, and polycarbonates made from diol compounds have excellent properties such as impact resistance and light weight, making them useful as medical materials, engineering plastics, and the like. Among diol compounds, various polymers made from alicyclic diols having an alicyclic structure in their main chain structure are useful polymer materials because they exhibit higher glass transition points than polymers made from other aliphatic diols. Stereoisomers of the hydroxyl group of an alicyclic diol include trans and cis isomers. For example, a technique is known for catalytically hydrogenating the raw material hydroquinone or 1,4-cyclohexanedione under heating and pressure in the presence of a solvent and a metal catalyst, and the trans / cis ratio of the 1,4-cyclohexanediol obtained at this time is usually in the range of about 0 to 1.5 (Patent Document 1). It is known that the trans / cis ratio affects important properties of polymers obtained from 1,4-cyclohexanediol as a raw material, and stable control of the trans / cis ratio is important because it leads to stable quality of the polymer. In particular, 1,4-cyclohexanediol compounds with a high trans / cis ratio are important for obtaining polymers with high stability and stable quality in terms of glass transition temperature, impact strength, weather resistance, and hydrolysis stability.

[0003] Known methods for obtaining 1,4-cyclohexanediol with a high trans / cis ratio include a method of recrystallizing cyclohexanediol using a specific solvent (Patent Document 2) and a method of recrystallization using protection / deprotection (Non-Patent Document 1). However, the yield of these methods is greatly affected by the isomer ratio of the original 1,4-cyclohexanediol.

[0004] Furthermore, as a method for synthetically obtaining 1,4-cyclohexanediol with a high trans / cis ratio, a method has been reported in which a labeling functional group is bonded to cyclohexanol, then a hydroxyl group is stereoselectively introduced using an enzyme, and the labeling functional group is then removed to selectively synthesize 1,4-cyclohexanediol (Non-Patent Document 2). This method produces trans-1,4-cyclohexanediol with high selectivity. profit However, this process requires protection and deprotection steps, and the eliminated labeled functional group becomes waste, so it cannot be considered an environmentally friendly process from the perspective of green chemistry.

[0005] On the other hand, from the viewpoint of green and sustainable chemistry, there have been reports of hydrogenation and Suzuki coupling in a solid phase state in which the raw materials, intermediates, products, and catalysts are solid, without using solvents. Hydrogenation has been confirmed to proceed smoothly with unsaturated hydrocarbons, azide derivatives, benzyl ethers, etc., in the presence of a palladium catalyst and under atmospheric hydrogen partial pressure conditions (Non-Patent Document 3). However, no studies have been conducted so far on methods for catalytic hydrogenation and isomerization of diol compounds having a cyclohexane skeleton, such as 1,4-cyclohexanediol, in a solid phase state without using solvents.

[0006] From the perspective of green chemistry, it was necessary to develop an environmentally friendly manufacturing process for diol compounds having a cyclohexane skeleton, and there was a demand for the development of a process that could obtain diol compounds having a cyclohexane skeleton with a high ratio of trans / cis isomers under mild reaction conditions. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Special Publication No. 45-6009 [Patent Document 2] Japanese Patent Application Publication No. 5-155797 [Non-patent literature]

[0008] [Non-Patent Document 1] J.Am.Chem.Soc. 66 (1944) 1096-1099 [Non-Patent Document 2] Org. Biomol. Chem. 12 (2014) 2479-2488 [Non-Patent Document 3] Tetrahedron 67 (2011) 8628-8634 Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention aims to develop a process for producing a diol compound having a cyclohexane skeleton that is environmentally friendly from the perspective of green chemistry, and that can stably produce a diol compound having a cyclohexane skeleton with a high ratio of all-trans isomers / cis isomers. [Means for solving the problem]

[0010] Means for Solving the Problems The present inventors have conducted intensive research to achieve the above object and have found that a diol compound having a cyclohexane skeleton with a high ratio of all-trans isomers to cis isomers can be obtained under mild reaction conditions by carrying out a catalytic hydrogenation reaction or a trans-cis isomerization reaction in the presence of a metal catalyst in a solid phase without using a solvent. Based on the above findings, the present invention has been completed. That is, the present invention is as follows.

[0011] [1] A method for producing a compound represented by general formula (1), in which the ratio of all trans isomers to cis isomers is greater than 1.5 and is not greater than 10,000, by reacting at least one compound selected from dione compounds having a cyclohexane skeleton, ketol compounds having a cyclohexane skeleton, dihydroxyaryl compounds, and diol compounds having a cyclohexane skeleton in a solid phase in the presence of a metal catalyst without the addition of a solvent under a hydrogen atmosphere. TIFF0007669841000001.tif2496Here, in formula (1), each hydrogen atom directly bonded to a carbon atom not substituted with a hydroxy group may be independently substituted with a halogen, an alkyl having 1 to 20 carbon atoms, a halogenated alkyl having 1 to 20 carbon atoms, a cycloalkyl having 3 to 20 carbon atoms, or an aryl having 4 to 30 carbon atoms, and each substituent may be bonded to each other to form a cyclic structure.In addition, in formula (1), n ​​is an integer of 0 to 2, and the bonding position of the hydroxy group is 2nd place , 3rd place or 4th place When n is 1 or 2, the bonding position of each cyclohexane skeleton is 1st and 2nd place , 1st and 3rd place or 1,4th place Shows.

[0012] [2] The method according to [1], wherein the raw material is a diol compound having a cyclohexane skeleton, and the reaction is an isomerization reaction that increases the ratio of all-trans isomers / cis-containing isomers of the diol compound having a cyclohexane skeleton.

[0013] [3] The method according to [1], wherein the raw material is at least one compound selected from the group consisting of a dione compound having a cyclohexane skeleton, a ketol compound having a cyclohexane skeleton, and a dihydroxyaryl compound, and the reaction includes a catalytic hydrogenation reaction.

[0014] [4] The method according to any one of [1] to [3], wherein the metal catalyst is a catalyst containing at least one metal selected from groups 8, 9, 10, and 11 of the periodic table.

[0015] [5] The method according to any one of [1] to [4], wherein the metal catalyst is a catalyst containing Ru, Rh, Ni or Pt.

[0016] [6] The metal catalyst is a metal salt, a metal oxide, a metal Single , a metal fine powder, a porous metal catalyst, or a metal-supported catalyst, and the support of the metal-supported catalyst is at least one support selected from an oxide, a hydrate, carbon, and cellulose.

[0017] [7] The method according to any one of [1] to [6], wherein the partial pressure of hydrogen in the reaction is 0.01 to 50 MPa and the reaction temperature is 10 to 180°C. Effect of the Invention

[0018] The method for producing a diol compound having a cyclohexane skeleton according to the present invention can obtain a diol compound having a cyclohexane skeleton having a higher ratio of all-trans isomer / cis-containing isomers than conventional methods under mild reaction conditions, and since no reaction solvent is used, the method can be said to be an environmentally friendly process from the perspective of green chemistry. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described below. However, the present invention is not limited to the following embodiment.

[0020] The method for producing a diol compound having a cyclohexane skeleton of the present invention is characterized in that the reaction is carried out in a solid phase under a hydrogen atmosphere without adding a solvent to the raw materials and metal catalyst, thereby achieving a higher ratio of all-trans isomers / cis-containing isomers in the diol compound having a cyclohexane skeleton than when the reaction is carried out in a solution system as in conventional methods.

[0021] The diol compound having a cyclohexane skeleton obtained by the production method of the present invention is a compound represented by general formula (1), and its ratio of all trans isomers / cis content exceeds 1.5 and is not more than 10,000, preferably 1.8 to 5,000, and more preferably 2.0 to 1,000. By setting the ratio of all trans isomers / cis content within the above range, the compound can be suitably used as a raw material for high-quality polyesters, polycarbonates, and the like. Here, the all-trans form means a compound in which the hydroxy groups bonded to each cyclohexane skeleton or other cyclohexane skeletons are all bonded at the trans position in general formula (1), and the cis-containing form means a compound in which at least one of the hydroxy groups bonded to each cyclohexane skeleton or other cyclohexane skeletons is bonded at the cis position in general formula (1). More specifically, in the case of a diol compound having one cyclohexane skeleton (n=0 in general formula (1)), an all-trans isomer is a compound in which two hydroxy groups are bonded to the cyclohexane skeleton at the trans positions, and a cis-containing isomer is a compound in which two hydroxy groups are bonded to the cyclohexane skeleton at the cis positions. In addition, in the case of a diol compound having two cyclohexane skeletons (n=1 in general formula (1)), a hydroxy group or another cyclohexane skeleton is a compound in which both of the hydroxy groups or the other cyclohexane skeleton are bonded at the trans position to the two cyclohexane skeletons, and a cis-containing compound is a compound in which at least one of the hydroxy groups or the other cyclohexane skeleton is bonded at the cis position to the two cyclohexane skeletons. In addition, in the case of a diol compound having three cyclohexane skeletons (n=2 in general formula (1)), the compound has all of the hydroxyl groups or other cyclohexane skeletons bonded at the trans position to the three cyclohexane skeletons, and a cis-containing compound has at least one of the hydroxyl groups or other cyclohexane skeletons bonded at the cis position to the three cyclohexane skeletons. The ratio of all trans isomers to cis-containing species means the total amount of all trans isomers divided by the total amount of cis-containing species (if there are multiple cis-containing species, the total amount of all cis-containing species). TIFF0007669841000002.tif2496 In the formula (1), each hydrogen atom directly bonded to a carbon atom not substituted with a hydroxy group may be independently substituted with a halogen, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 4 to 30 carbon atoms, and each substituent may be bonded to each other to form a cyclic structure. In the formula (1), n ​​is an integer of 0 to 2, and the bonding position of the hydroxy group is 2nd place , 3rd place or 4th place When n is 1 or 2, the bonding position of each cyclohexane skeleton is 1st and 2nd place , 1st and 3rd place or 1,4th place Shows.

[0022] The raw material used in the present invention is at least one compound selected from a dione compound having a cyclohexane skeleton, a ketol compound having a cyclohexane skeleton, a dihydroxyaryl compound, and a diol compound having a cyclohexane skeleton, without any particular limitation.

[0023] When a dione compound having a cyclohexane skeleton is used as the raw material, as shown in the reaction scheme below, the two carbonyl groups are reduced by catalytic hydrogenation, and a diol compound having a cyclohexane skeleton with a low ratio of all-trans isomers / cis isomers is obtained. In this case, a ketol compound having a cyclohexane skeleton with one carbonyl group reduced is produced as a reaction intermediate. Then, a diol compound having a cyclohexane skeleton with a high ratio of all-trans isomers / cis isomers is obtained by further isomerization. TIFF0007669841000003.tif26170

[0024] When a ketol compound having a cyclohexane skeleton is used as the raw material, as shown in the following reaction scheme, one carbonyl group is reduced by a catalytic hydrogenation reaction to give a diol compound having a cyclohexane skeleton with a low ratio of all-trans isomer / cis content, and then a diol compound having a cyclohexane skeleton with a high ratio of all-trans isomer / cis content is obtained by an isomerization reaction. TIFF0007669841000004.tif25123

[0025] When a dihydroxyaryl compound is used as the raw material, as shown in the reaction scheme below, reduction of the aryl occurs by a catalytic hydrogenation reaction to produce a diol compound having a cyclohexane skeleton with a low ratio of all-trans isomers to cis isomers, and then a diol compound having a cyclohexane skeleton with a high ratio of all-trans isomers to cis isomers is obtained. TIFF0007669841000005.tif26125

[0026] When a diol compound having a cyclohexane skeleton is used as the raw material, a diol compound having a cyclohexane skeleton with a high ratio of all-trans isomers to cis isomers can be obtained by an isomerization reaction.

[0027] The metal of the metal catalyst used in the present invention is not particularly limited, but is preferably at least one metal selected from groups 8, 9, 10, and 11 of the periodic table, more preferably Ru, Rh, Ni, or Pt, and even more preferably Ru. The state of the metal catalyst is not particularly limited, and may be a metal salt, a metal oxide, a metal Single The metal catalyst may be a metal fine powder, and these metal catalysts may be used as they are, or in a porous state (porous metal catalyst), or may be supported on a carrier (metal supported catalyst).

[0028] The carrier may be an oxide, a hydrate, carbon, cellulose, or the like, and at least one of these may be used. Examples of oxides include silica, alumina, titania, ceramics, zirconia, niobia, and zeolite. Examples of hydrates include hydroxyapatite, niobic acid, zirconic acid, tungstic acid, and titanic acid. Examples of carbon include activated carbon, carbon black, graphite, graphene, graphene oxide, and carbon nanotubes.

[0029] The amount of metal supported in the metal-supported catalyst is not particularly limited, but is preferably 0.1 to 15% by weight, more preferably 0.2 to 10% by weight. The metal catalyst may be in a dry state, or may be in a wet state with water or the like in order to facilitate transportation, storage, and weighing of the catalyst. The amount of water in the wet state is preferably 1 to 5000% by weight, more preferably 5 to 1000% by weight.

[0030] The catalyst concentration may be changed within a wide range. The higher the catalyst concentration, the easier the reaction of the present invention will proceed. However, from an economical perspective, the catalyst concentration is preferably adjusted to within a range of 0.001 to 50 mol % (molar amount of catalyst metal relative to the molar amount of raw material), more preferably 0.01 to 20 mol %, and even more preferably 0.1 to 10 mol %.

[0031] In an embodiment of the present invention, the raw material and the metal catalyst are charged into a reaction apparatus, hydrogen is replaced in a solid phase state without adding a solvent, and the reaction is carried out at a predetermined reaction temperature and mixing conditions. The reactor may be any vessel capable of gas replacement, and flasks, autoclaves, etc. may be used. Rotary evaporators, which rotate and mix the inside of the vessel, and the "rocking mixer" manufactured by Aichi Electric Co., Ltd. may also be used, and a method of feeding hydrogen into a column-type fixed bed in which the raw material and catalyst are mixed in advance and packed is also possible. In addition, fluidized bed reactors capable of semi-continuously handling solids, Nauta mixers, ribbon blenders, and Kobelco Eco-Solutions Co., Ltd.'s "SV mixer" and "PV mixer" may also be used.

[0032] The raw materials and the metal catalyst may be charged separately or in a premixed state. In order to prevent a sudden load on the stirring power of the reactor, the raw materials and the metal catalyst may be charged while the stirring of the reactor is in operation.

[0033] The hydrogen replacement method in the reactor includes a method of replacing by introducing a large amount of hydrogen, a method of repeatedly pressurizing with hydrogen or an inert gas and purging, a method of repeatedly introducing hydrogen after depressurizing the reactor, etc. In the embodiment of the present invention, since the reaction is in a solid phase state without adding a solvent, there is no concern about evaporation of the solvent, etc., and therefore the method of repeatedly introducing hydrogen after depressurizing the reactor is preferable.

[0034] The hydrogen in the reactor may be in a mixed state with an inert gas, and the partial pressure of hydrogen is not particularly limited, but is preferably 0.01 to 50 MPa, more preferably 0.05 to 5 MPa, and further preferably 0.08 to 0.98 MPa. The reaction temperature is not particularly limited, but is preferably 10 to 180°C, more preferably 30 to 150°C, and further preferably 50 to 120°C. The mixing conditions are such that the raw material and the metal catalyst are kept in a sufficiently mixed state. If the raw materials are charged in a premixed state, there is no need to mix them in the reactor.

[0035] The metal catalyst can be easily removed from the reaction mixture by dissolving the reaction mixture in a solvent after the reaction to make it homogenous and filtering it. The filtered metal catalyst may be repeatedly used in catalytic hydrogenation reactions or isomerization reactions without further treatment. The catalyst may also be washed with water or the like and repeatedly used in the initial wet state with water or the like.

[0036] The reaction mixture can be dissolved in at least one solvent selected from water, alcohol, ether, hydrocarbon, ketone and ester. For example, water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-ethylhexanol, diethyl ether, diisopropyl ether, tetrahydrofuran, hexane, heptane, cyclohexane, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate, isobutyl isobutyrate, and mixtures thereof. In view of availability and ease of operation, water, methanol, 2-propanol, tetrahydrofuran, acetone, and ethyl acetate are preferred.

[0037] As a method for removing the catalyst from the reaction mixture after the reaction other than the above, a conventional method such as distillation, sublimation, melting, etc. can also be used, although it depends on the physical properties of the compound. EXAMPLES

[0038] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0039] [Example 1] (Example of catalytic hydrogenation reaction under atmospheric pressure) The reaction equipment was the "Personal Organic Synthesis Equipment ChemiStation" manufactured by Tokyo Rikakikai Co., Ltd. TM We used the PPM-5512 model. 8.92mmol of 1,4-cyclohexanedione (1,4-CHK) as raw material and 1.5g of 50wt% water-containing 5wt% Ru / C (A-type / manufactured by N.E. Chemcat) as metal catalyst (Ru content in catalyst Ru / C is 4.2mol% of raw material) were put into a 120mL test tube. After degassing the inside of the test tube, a hydrogen gas balloon was attached and replaced with hydrogen gas atmosphere. The reaction temperature was set to 80℃ and the reaction was carried out with stirring at 300rpm for 6 hours.

[0040] (Post-reaction treatment) Then, 20 mL of methanol was added to the obtained reaction mixture to dissolve the reaction mixture, and the reaction mixture was filtered using a membrane filter (ADVANTEC, DISMIC (registered trademark), 13HP020AN, pore size 0.20 μm) to obtain a reaction filtrate from which the metal catalyst Ru / C had been removed. The metal catalyst Ru / C used in the reaction was washed with 10 mL of ethyl acetate separately, and the washing liquid was collected. The washing liquid was combined with the reaction filtrate obtained earlier, and the ratio of the raw material to the reaction product was calculated by measuring it by gas chromatography (Shimadzu Corporation, GC-2030). The reaction products were the raw material 1,4-cyclohexanedione (1,4-CHK), the monoreductant 4-hydroxycyclohexanone (4-CHO), the direductant cis isomer cis-1,4-cyclohexanediol (cis-CHD), the trans isomer trans-1,4-cyclohexanediol (trans-CHD), and others as by-products, and the GC composition was shown in the table below. The ratio of all-trans to cis 1,4-CHD is also shown in the table.

[0041] [Example 2] (Example of catalytic hydrogenation reaction under pressure) The reaction equipment was the "Personal Organic Synthesis Equipment ChemiStation" manufactured by Tokyo Rikakikai Co., Ltd. TM The PPV-4400 model was used. The raw material 1,4-CHK (8.92 mmol) and 50 wt% water content 5 wt% Ru / C (A-type / NE Chemcat) (0.40 g) were added to a 120 mL reaction tube. After that, a gas line was connected and the atmosphere was replaced with hydrogen gas. The hydrogen partial pressure was set to 0.8 MPaG, the reaction temperature was set to 80°C, and the reaction was carried out with stirring at a stirring speed of 300 rpm for 6 hours. The post-treatment after the reaction was carried out in the same manner as in Example 1.

[0042] [Comparative Example 1] (Example of catalytic hydrogenation reaction under pressure in isopropanol) The reaction equipment was the "Personal Organic Synthesis Equipment ChemiStation" manufactured by Tokyo Rikakikai Co., Ltd. TMThe PPV-4400 model was used. The raw material 1,4-CHK (8.92 mmol), 50 wt% water content 5 wt% Ru / C (A-type / NE Chemcat) (0.40 g) as a metal catalyst, and 20 mL of isopropanol (IPA) as a reaction solvent were placed in a 120 mL reaction tube. After that, a gas line was connected and the atmosphere was replaced with hydrogen gas, and the hydrogen partial pressure was set to 0.8 MPaG, the reaction temperature was set to 80°C, and the reaction was carried out with stirring at a stirring speed of 600 rpm for 6 hours. Thereafter, the obtained reaction solution was filtered with a membrane filter (manufactured by ADVANTEC, DISMIC (registered trademark), 13HP020AN, pore size 0.20 μm) to obtain a reaction filtrate from which the metal catalyst Ru / C had been removed. The subsequent operations were carried out in the same manner as in Example 1. The results of Examples 1 and 2 and Comparative Example 1 are shown in Table 1 below.

[0043] [Table 1] A comparison between Examples 1 and 2 and Comparative Example 1 shows that 1,4-cyclohexanediol having a high ratio of all-trans isomer / cis isomer can be obtained by carrying out catalytic hydrogenation in a solid phase without adding a solvent.

[0044] [Example 3] (Example of isomerization reaction under atmospheric pressure) The reaction equipment was the "Personal Organic Synthesis Equipment ChemiStation" manufactured by Tokyo Rikakikai Co., Ltd. TM We used the PPM-5512 model. The raw material 1,4-cyclohexanediol (1,4-CHD) (8.61 mmol) and 5 wt% Ru / C (A-type dry / N.E. Chemcat) (0.20 g) were placed in a 120 mL test tube. After degassing the inside of the test tube, a hydrogen gas balloon was attached and replaced with a hydrogen gas atmosphere. The reaction temperature was set to 60°C and the reaction was carried out with stirring at a stirring speed of 300 rpm for 6 hours. The post-reaction treatment was carried out in the same manner as in Example 1. The reaction products were cis-1,4-cyclohexanediol (cis-CHD) for the cis isomer of 1,4-CHD, trans-1,4-cyclohexanediol (trans-CHD) for the trans isomer, and others as by-products, and their GC compositions are shown in the table below. The ratio of all trans isomers of 1,4-CHD to cis-containing isomers is also shown in the table.

[0045] [Example 4] The same procedure as in Example 3 was carried out except that the reaction temperature was changed to 80°C.

[0046] [Example 5] The same procedure was carried out as in Example 4, except that the catalyst was changed to 0.20 g of sponge nickel (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0047] [Example 6] (Example of isomerization reaction under pressure) The reaction equipment was the "Personal Organic Synthesis Equipment ChemiStation" manufactured by Tokyo Rikakikai Co., Ltd. TM The PPV-4400 model was used. The raw material 1,4-cyclohexanediol (1,4-CHD) 8.61 mmol and 5 wt% Ru / C (A-type dry / NE Chemcat) 0.20 g as a metal catalyst were placed in a 120 mL reaction tube. After that, a gas line was connected and the atmosphere was replaced with hydrogen gas. The hydrogen partial pressure was set to 0.8 MPaG, the reaction temperature was set to 80°C, and the reaction was carried out with stirring at a stirring speed of 300 rpm for 6 hours. The post-treatment after the reaction was carried out in the same manner as in Example 1.

[0048] [Comparative Example 2] (Example of isomerization reaction in methanol at atmospheric pressure) The reaction equipment was the "Personal Organic Synthesis Equipment ChemiStation" manufactured by Tokyo Rikakikai Co., Ltd. TM We used the PPM-5512 model. The raw material 1,4-CHD (8.61 mmol), 50 wt% water-containing 5 wt% Ru / C (A-type / NE Chemcat) (0.40 g) as a metal catalyst, and 20 mL of methanol as a reaction solvent were placed in a 120 mL test tube. After degassing the inside of the test tube, a hydrogen gas balloon was attached and replaced with a hydrogen gas atmosphere. The reaction temperature was set to 60°C and the reaction was carried out with stirring at a stirring speed of 600 rpm for 6 hours. The post-treatment after the reaction was carried out in the same manner as in Comparative Example 1.

[0049] [Comparative Examples 3 to 4] The same procedures as in Comparative Example 2 were carried out except that the reaction solvents were changed to isopropyl alcohol (IPA) and tetrahydrofuran (THF), respectively. The results of Examples 3 to 6 and Comparative Examples 2 to 4 are shown in Table 2 below.

[0050] [Table 2] A comparison of Examples 3 to 6 with Comparative Examples 2 to 4 shows that the ratio of all trans-isomers to cis-isomers increases when the isomerization reaction is carried out in a solid phase without adding a solvent.

[0051] [Example 7] The same procedure was carried out as in Example 4, except that the raw material was changed to 1,2-cyclohexanediol (1,2-CHD). The reaction products include the stereoisomers of 1,2-CHD, the cis isomer being cis-1,2-cyclohexanediol (cis-CHD), the trans isomer being trans-1,2-cyclohexanediol (trans-CHD), and by-products such as "others." The GC composition is shown in the table below. The ratio of all trans isomers of 1,2-CHD to cis isomers is also shown in the table.

[0052] [Example 8] The same procedure was carried out as in Example 7, except that the catalyst was changed to 0.20 g of sponge nickel (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0053] [Example 9] (Example of isomerization reaction under pressure) The reaction equipment was the "Personal Organic Synthesis Equipment ChemiStation" manufactured by Tokyo Rikakikai Co., Ltd. TM The PPV-4400 model was used. The raw material 1,2-cyclohexanediol (1,2-CHD) 8.61 mmol and 5 wt% Ru / C (A-type dry / NE Chemcat) 0.20 g as a metal catalyst were placed in a 120 mL reaction tube. After that, a gas line was connected and the atmosphere was replaced with hydrogen gas. The hydrogen partial pressure was set to 0.8 MPaG, the reaction temperature was set to 80°C, and the reaction was carried out with stirring at a stirring speed of 300 rpm for 6 hours. The post-treatment after the reaction was carried out in the same manner as in Example 1.

[0054] [Comparative Example 5] (Example of isomerization reaction in methanol at atmospheric pressure) The reaction equipment was the "Personal Organic Synthesis Equipment ChemiStation" manufactured by Tokyo Rikakikai Co., Ltd. TM We used the PPM-5512 model. The raw material 1,2-CHD (8.61 mmol), 50 wt% water-containing 5 wt% Ru / C (A-type / NE Chemcat) (0.40 g) as a metal catalyst, and 20 mL of methanol as a reaction solvent were placed in a 120 mL reaction tube. After degassing the inside of the test tube, a hydrogen gas balloon was attached and replaced with a hydrogen gas atmosphere. The reaction temperature was set to 60°C and the reaction was carried out with stirring at a stirring speed of 600 rpm for 6 hours. The post-treatment after the reaction was carried out in the same manner as in Comparative Example 1.

[0055] [Comparative Examples 6 to 8] The same procedures as in Comparative Example 5 were carried out except that the reaction solvents were changed to isopropyl alcohol (IPA), ethyl acetate, and tetrahydrofuran (THF), respectively. The results of Examples 7 to 9 and Comparative Examples 5 to 8 are shown in Table 3 below.

[0056] [Table 3] A comparison of Examples 7 to 9 and Comparative Examples 5 to 8 shows that the ratio of all trans-isomers to cis-isomers increases when the isomerization reaction is carried out in a solid phase without adding a solvent.

[0057] [Example 10] (Example of isomerization reaction under pressure) The reaction equipment was the "Personal Organic Synthesis Equipment ChemiStation" manufactured by Tokyo Rikakikai Co., Ltd. TM The PPV-4400 model was used. 5.04 mmol of 4,4'-bicyclohexanol as the raw material and 0.40 g of 50% by weight water-containing 5% by weight Ru / C (A-type / NE Chemcat) as the metal catalyst were placed in a 120 mL reaction tube. After that, a gas line was connected and the atmosphere was replaced with hydrogen gas. The partial pressure of hydrogen was set to 0.4 MPaG, the reaction temperature was set to 80°C, and the reaction was carried out with stirring at a stirring speed of 300 rpm for 6 hours. The post-treatment after the reaction was carried out in the same manner as in Example 1. The reaction products were stereoisomers of 4,4'-bicyclohexanol, namely (1s,1's,4S,4'S)-[1,1'-bi(cyclohexane)]-4,4'-diol (cc-isomer), (1r,1's,4R,4'S)-[1,1'-bi(cyclohexane)]-4,4'-diol (ct-isomer), (1r,1'r,4R,4'R)-[1,1'-bi(cyclohexane)]-4,4'-diol (tt-isomer), and by-products, others, and their GC compositions are shown in the table below. The ratio of all trans-isomers / cis-containing isomers shown in the table is the ratio of the tt-isomer to the total amount of the cc-isomer and ct-isomer.

[0058] [Example 11] The same procedure as in Example 10 was carried out except that the reaction temperature was changed to 100°C.

[0059] [Example 12] The same procedure as in Example 10 was carried out except that the reaction temperature was changed to 120°C.

[0060] [Example 13] The same procedure as in Example 12 was carried out except that the hydrogen partial pressure was changed to 0.8 MPaG.

[0061] [Example 14] The same procedure was carried out as in Example 13, except that the metal catalyst was changed to 1.00 g of 5 wt % Rh / C (A-type / manufactured by N.E. Chemcat Corporation) containing 50 wt % water.

[0062] [Example 15] (Example of isomerization reaction under atmospheric pressure) The reaction equipment was the "Personal Organic Synthesis Equipment ChemiStation" manufactured by Tokyo Rikakikai Co., Ltd. TM We used the PPM-5512 model. 2.52 mmol of 4,4'-bicyclohexanol as the raw material and 1.50 g of 50% by weight water-containing 5% by weight Ru / C (A-type / NE Chemcat) as the catalyst were placed in a 120 mL test tube. After degassing the inside of the test tube, a hydrogen gas balloon was attached and replaced with a hydrogen gas atmosphere. The reaction temperature was set to 120°C and the reaction was carried out with stirring at a stirring speed of 300 rpm for 6 hours. The post-treatment after the reaction was carried out in the same manner as in Example 1.

[0063] [Example 16] The same procedure was carried out as in Example 15, except that the catalyst was changed to 0.75 g of 5 wt % Ru / Al2O3 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0064] [Example 17] The same procedure was carried out as in Example 15, except that the catalyst was changed to 0.10 g of 3 wt % Pt / C containing 50 wt % water (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.).

[0065] [Comparative Example 9] (Example of isomerization reaction under pressure in methanol) The reaction equipment was the "Personal Organic Synthesis Equipment ChemiStation" manufactured by Tokyo Rikakikai Co., Ltd. TM The PPV-4400 model was used. 5.04 mmol of 4,4'-bicyclohexanol as raw material, 0.40 g of 50 wt% water-containing 5 wt% Ru / C (A-type / NE Chemcat) as metal catalyst, and 20 mL of methanol as reaction solvent were charged into a 120 mL reaction tube. After that, a gas line was connected and the atmosphere was replaced with hydrogen gas. The partial pressure of hydrogen was set to 0.8 MPaG, the reaction temperature was set to 80°C, and the reaction was carried out with stirring at a stirring speed of 600 rpm for 6 hours. The post-treatment after the reaction was carried out in the same manner as in Comparative Example 1. The results of Examples 10 to 17 and Comparative Example 9 are shown in Table 4 below.

[0066] [Table 4] A comparison of Examples 10 to 17 with Comparative Example 9 shows that the ratio of all trans-isomers to cis-isomers increases when the isomerization reaction is carried out in a solid phase without adding a solvent.

[0067] [Example 18] (Example of catalytic hydrogenation reaction under pressure) The reaction equipment was the "Personal Organic Synthesis Equipment ChemiStation" manufactured by Tokyo Rikakikai Co., Ltd. TM The PPV-4400 model was used. 5.04 mmol of 4,4'-dihydroxybiphenyl as the raw material and 0.40 g of 50% by weight water-containing 5% by weight Ru / C (A-type / NE Chemcat) as the metal catalyst were placed in a 120 mL reaction tube. After that, a gas line was connected and the atmosphere was replaced with hydrogen gas. The hydrogen partial pressure was set to 0.8 MPaG, the reaction temperature was set to 120°C, and the reaction was carried out with stirring at a stirring speed of 300 rpm for 6 hours. The post-treatment after the reaction was carried out in the same manner as in Example 1. The reaction products were stereoisomers of 4,4'-bicyclohexanol, namely (1s,1's,4S,4'S)-[1,1'-bi(cyclohexane)]-4,4'-diol (cc-isomer), (1r,1's,4R,4'S)-[1,1'-bi(cyclohexane)]-4,4'-diol (ct-isomer), (1r,1'r,4R,4'R)-[1,1'-bi(cyclohexane)]-4,4'-diol (tt-isomer), and by-products, others, and their GC compositions are shown in the table below. The ratio of all trans-isomers / cis-containing isomers shown in the table is the ratio of the tt-isomer to the total amount of the cc-isomer and ct-isomer.

[0068] [Example 19] The same procedure was carried out as in Example 18, except that the catalyst was changed to 0.75 g of 5 wt % Ru / Al2O3 (S-type / manufactured by N.E. Chemcat Corporation).

[0069] [Comparative Example 10] (Example of catalytic hydrogenation reaction under pressure in isopropanol) The reaction equipment was the "Personal Organic Synthesis Equipment ChemiStation" manufactured by Tokyo Rikakikai Co., Ltd. TM The PPV-4400 model was used. 5.04 mmol of 4,4'-dihydroxybiphenyl as the raw material, 0.40 g of 50 wt% water-containing 5 wt% Ru / C (A-type / NE Chemcat) as the metal catalyst, and 20 mL of isopropanol as the reaction solvent were placed in a 120 mL reaction tube. After that, a gas line was connected and the atmosphere was replaced with hydrogen gas, and the hydrogen partial pressure was set to 0.8 MPaG, the reaction temperature was set to 120°C, and the reaction was carried out with stirring at a stirring speed of 900 rpm for 6 hours. The post-treatment after the reaction was carried out in the same manner as in Comparative Example 1. The results of Examples 18 to 19 and Comparative Example 10 are shown in Table 5 below.

[0070] [Table 5] A comparison of Examples 18 to 19 and Comparative Example 10 shows that 4,4'-bicyclohexanol with a high ratio of all-trans isomer / cis isomer can be obtained by carrying out the isomerization reaction in a solid phase without adding a solvent. [Industrial Applicability]

[0071] The diol compound having a cyclohexane skeleton with a high ratio of all-trans isomers / cis isomers obtained by the production method of the present invention can be suitably used as a raw material for polyesters, polycarbonates, and the like, which have high stability and consistent quality in terms of glass transition temperature, impact strength, weather resistance, and hydrolysis stability.

Claims

1. The present invention relates to a method for producing a compound represented by general formula (1), the compound having an all-trans / cis ratio of which is 1.6 to 5,000, by using as a raw material at least one compound selected from a dione compound having a cyclohexane skeleton, a ketol compound having a cyclohexane skeleton, a dihydroxyaryl compound, and a diol compound having a cyclohexane skeleton, and carrying out a reaction in a solid phase in a hydrogen atmosphere without adding a solvent in the presence of a metal catalyst containing Ru, Rh, Ni, or Pt. Here, in formula (1), each hydrogen atom directly bonded to a carbon atom not substituted with a hydroxy group may be independently substituted with a halogen, an alkyl having 1 to 20 carbon atoms, a halogenated alkyl having 1 to 20 carbon atoms, a cycloalkyl having 3 to 20 carbon atoms, or an aryl having 4 to 30 carbon atoms, and each substituent may be bonded to each other to form a cyclic structure. In addition, in formula (1), n ​​is an integer of 0 to 2, the bonding position of the hydroxy group may be any of the ortho, meta, or para positions, and when n is 1 or 2, the bonding position of each cyclohexane skeleton is the ortho, meta, or para position.

2. 2. The method according to claim 1, wherein the raw material is a diol compound having a cyclohexane skeleton, and the reaction is an isomerization reaction for increasing the ratio of all-trans isomers to cis isomers of the diol compound having a cyclohexane skeleton.

3. 2. The method according to claim 1, wherein the raw material is at least one compound selected from the group consisting of a dione compound having a cyclohexane skeleton, a ketol compound having a cyclohexane skeleton, and a dihydroxyaryl compound, and the reaction comprises a catalytic hydrogenation reaction.

4. The production method according to any one of claims 1 to 3, wherein the metal catalyst is a metal salt, a metal oxide, a metal element, a metal fine powder, a porous metal catalyst, or a metal-supported catalyst, and a support of the metal-supported catalyst is at least one support selected from an oxide, a hydrate, carbon, and cellulose.

5. The method according to any one of claims 1 to 4, wherein the partial pressure of hydrogen in the reaction is 0.01 to 50 MPa and the reaction temperature is 10 to 180°C.

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