Method for producing fluorene compound

Abstract

The purpose of the present invention is to provide a method for producing a fluorene compound (fluorenediol compound having a cyclohexane structure), the method being excellent in terms of yield and purity. The method for producing a fluorene compound includes a hydrogenation step in which a fluorene compound represented by formula (1) is hydrogenated in the presence of a catalyst and a solvent to obtain a fluorene compound represented by formula (2), wherein the catalyst is at least one metal catalyst selected from the group consisting of ruthenium, palladium, rhodium, osmium, iridium, platinum, and nickel and the solvent is at least one solvent selected from the group consisting of ether-based solvents and ester-based solvents. [In formulae (1) and (2), each m independently indicates an integer of 0 or 1 and each n independently indicates an integer of 0-6.]

Description

Method for producing fluorene compounds

[0001] The present invention relates to a method for producing a fluorene compound.

[0002] Fluorene compounds having two hydroxyl groups (also called fluorenediol compounds) are known to be useful as raw material monomers for resins such as polyester resins, polyester polycarbonate resins, polycarbonate resins, epoxy resins, polyurethane resins, polyacrylic ester resins, and polymethacrylic ester resins. Furthermore, fluorenediol compounds can be used as resin modifiers to broadly adjust the physical properties of the resin, such as the glass transition temperature, refractive index, birefringence, and Abbe number. Therefore, they are used in optical materials such as optical lenses and optical films.

[0003] Among these, fluorenediol compounds having a cyclohexane structure have attracted attention as highly heat-resistant compounds whose refractive index can be adjusted.

[0004] For example, Patent Document 1 discloses a fluorenediol compound having a cyclohexane structure as a compound having heat resistance, solubility, flexibility, and impact resistance as an optical material in addition to a high refractive index, and also discloses a method for producing the compound by reacting fluorenone with a cyclohexylphenol compound in the presence of an acid catalyst.

[0005] Japanese Patent Application Laid-Open No. 2000-026349

[0006] In the method for synthesizing a fluorenediol compound having a cyclohexane structure described in Patent Document 1, a cyclohexylphenol compound is used as a raw material.

[0007] Although cyclohexylphenol compounds can be obtained by hydrogenating phenylphenol compounds, this reaction has not provided a sufficient yield (approximately 35%).Therefore, a synthetic route in which a phenylphenol compound is hydrogenated to obtain a cyclohexylphenol compound, and then the cyclohexylphenol compound is reacted with fluorenone to synthesize a fluorenediol compound having a cyclohexane structure has a problem of low yield (total yield of approximately 25%).

[0008] Because the conventional methods have the above problems, a method (synthetic route) capable of obtaining a fluorenediol compound having a cyclohexane structure in high yield has been sought.

[0009] Therefore, the present invention provides a method for producing a fluorene compound (a fluorenediol compound having a cyclohexane structure) with excellent yield and purity.

[0010] The present inventors have discovered that a method for synthesizing a fluorene compound represented by formula (1) described below by reacting a phenylphenol compound with fluorenone has a sufficiently high yield (approximately 85%). The present inventors have conducted extensive research into a method for hydrogenating a fluorene compound represented by formula (1) as a method for synthesizing a fluorene compound represented by formula (2) described below (a fluorenediol compound having a cyclohexane structure). As a result, they have found that the fluorene compound represented by formula (2) can be obtained in high yield and purity by hydrogenating the fluorene compound represented by formula (1) in the presence of a specific catalyst and solvent. It has been found that by using such a method, the fluorene compound represented by formula (2) can be obtained in high yield and purity, even when a phenylphenol compound and fluorenone are used as starting materials, similar to the method described in Patent Document 1.

[0011] That is, the present invention is a method for producing a fluorene compound, which includes a hydrogenation step of hydrogenating a fluorene compound represented by the following formula (1) in the presence of a catalyst and a solvent to obtain a fluorene compound represented by the following formula (2), wherein the catalyst is at least one metal catalyst selected from the group consisting of ruthenium, palladium, rhodium, osmium, iridium, platinum, and nickel, and the solvent is at least one selected from the group consisting of ether-based solvents and ester-based solvents. [In formulas (1) and (2), each m independently represents an integer of 0 or 1, and each n independently represents an integer of 0 to 6.]

[0012] In the method for producing a fluorene compound of the present invention, the catalyst is preferably at least one metal catalyst selected from the group consisting of ruthenium, palladium, rhodium, and nickel. The catalyst is preferably supported on at least one support selected from the group consisting of carbon, alumina, silica gel, diatomaceous earth, titanium oxide, zirconium, and calcium carbonate. When the catalyst is at least one metal catalyst selected from the group consisting of ruthenium, palladium, rhodium, osmium, iridium, and platinum, the supported amount is preferably 0.1 to 10 mass%. When the catalyst is a nickel catalyst, the supported amount is preferably 40 to 50 mass%. The solvent is preferably at least one solvent selected from the group consisting of diethylene glycol dimethyl ether and triethylene glycol dimethyl ether. The reaction temperature in the hydrogenation step is preferably 80°C to 150°C. The hydrogen pressure in the hydrogenation step is preferably 1 MPa to 10 MPa (gauge pressure). The reaction time in the hydrogenation step is preferably 4 hours to 10 hours.

[0013] The present invention provides a method for producing a fluorene compound (a fluorenediol compound having a cyclohexane structure) with excellent yield and purity.

[0014] The present invention provides a method for producing a fluorene compound, which comprises a hydrogenation step of hydrogenating a fluorene compound represented by the following formula (1) in the presence of a catalyst and a solvent to obtain a fluorene compound represented by the following formula (2), wherein the catalyst is at least one metal catalyst selected from the group consisting of ruthenium, palladium, rhodium, osmium, iridium, platinum, and nickel, and the solvent is at least one selected from the group consisting of ether-based solvents and ester-based solvents. [In formulas (1) and (2), m each independently represents an integer of 0 or 1, and n each independently represents an integer of 0 to 6.] Hereinafter, the method for producing the fluorene compound of the present invention will be described in detail.

[0015] <Hydrogenation Step> The method for producing a fluorene compound of the present invention includes a hydrogenation step of hydrogenating the fluorene compound represented by the above formula (1) in the presence of a catalyst and a solvent.

[0016] [Fluorene Compound Represented by Formula (1)] In the above formula (1), m each independently represents an integer of 0 or 1, and n each independently represents an integer of 0 to 6. Note that m and n in the above formula (1) are the same as m and n in the above formula (2) obtained by the hydrogenation step.

[0017] In the above formula (1), m is preferably 0 from the viewpoint of suitably increasing the purity of the fluorene compound represented by the above formula (2).

[0018] In the above formula (1), n ​​is preferably 0 from the viewpoint of suitably increasing the purity of the fluorene compound represented by the above formula (2).

[0019] The method for obtaining the fluorene compound represented by the above formula (1) is not particularly limited, and any known method can be used.

[0020] For example, as described in Japanese Patent Application Laid-Open No. 2001-206863, the fluorene compound represented by the formula (1) may be synthesized by reacting a phenylphenol compound with fluorenone. This method is preferred because the yield of the fluorene compound represented by the formula (1) is as high as about 85%.

[0021] (Catalyst) The catalyst is at least one metal catalyst selected from the group consisting of ruthenium, palladium, rhodium, osmium, iridium, platinum, and nickel.

[0022] From the viewpoint of reactivity, the catalyst is preferably at least one metal catalyst selected from the group consisting of ruthenium, palladium, rhodium, and nickel.

[0023] In addition, from the viewpoint of suitably increasing the purity of the fluorene compound represented by the formula (2), the catalyst is preferably supported on at least one carrier selected from the group consisting of carbon, alumina, silica gel, diatomaceous earth, titanium oxide, zirconium, and calcium carbonate.

[0024] When the catalyst is at least one metal catalyst selected from the group consisting of ruthenium, palladium, rhodium, osmium, iridium, and platinum, the supported amount is preferably 0.1 to 10 mass %, and when the catalyst is a nickel catalyst, the supported amount is preferably 40 to 50 mass %.

[0025] Specific examples of the catalyst supported on the carrier include palladium-carbon (Pd / C), palladium-alumina (Pd / Al ２ O ３ ), ruthenium-carbon (Ru / C), ruthenium-alumina (Ru / Al ２ O ３ ), rhodium-carbon (Rh / C), rhodium-alumina (Rh / Al ２ O ３ ), nickel-carbon (Ni / C), nickel-silica (Ni / SiO ２ ), nickel-diatomaceous earth (Ni / diatomaceous earth), Raney nickel (Ni / Al), etc.

[0026] Among these, ruthenium is more preferred from the viewpoint of suitably increasing the purity of the fluorene compound represented by the above formula (2).

[0027] The amount of the catalyst used is preferably 0.01 to 50 parts by mass relative to 100 parts by mass of the fluorene compound represented by the formula (1).

[0028] (Solvent) The solvent is at least one selected from the group consisting of ether-based solvents and ester-based solvents.

[0029] The ether solvent may be at least one selected from the group consisting of diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, ethylene glycol dimethyl ether, diethyl ether, tetrahydrofuran, dioxane, dibutyl ether, diethylene glycol diethyl ether, and ethylene glycol dibutyl ether.

[0030] The ester solvent may be at least one selected from the group consisting of ethyl acetate, butyl acetate, methyl isobutyrate, isobutyl acetate, normal propyl acetate, isopropyl acetate, diethylene glycol monoethyl ether acetate, butyl propionate, and cellosolve acetate.

[0031] From the viewpoint of the solubility of the fluorene compound represented by the formula (1), the solvent is preferably at least one selected from the group consisting of diethylene glycol dimethyl ether and triethylene glycol dimethyl ether.

[0032] The amount of the solvent used is preferably 100 to 10,000 parts by mass relative to 100 parts by mass of the fluorene compound represented by the formula (1).

[0033] (Reaction Temperature) The reaction temperature in the hydrogenation step is preferably 80° C. to 150° C. By using a reaction temperature in the above range, the yield and purity of the fluorene compound represented by the formula (2) can be suitably increased.

[0034] (Hydrogen Pressure) In the hydrogenation step, the hydrogen pressure is preferably 1 MPa to 10 MPa in gauge pressure. By setting the hydrogen pressure within this range, the yield and purity of the fluorene compound represented by formula (2) can be suitably increased. The hydrogen pressure is more preferably 1 MPa to 5 MPa in gauge pressure. Note that the gauge pressure means a pressure that does not include atmospheric pressure (atmospheric pressure is set to 0 MPa).

[0035] (Reaction Time) The reaction time of the hydrogenation step is preferably 4 to 10 hours. By keeping the reaction time within this range, the yield and purity of the fluorene compound represented by formula (2) can be suitably increased. The reaction time is more preferably 5 to 8 hours. The reaction time means the time from when the reaction temperature is reached to when the reaction is completed.

[0036] (Others) The hydrogen used in the hydrogenation step may be any hydrogen used in conventional hydrogenation reactions, and specifically, pure hydrogen or a mixed gas of hydrogen and an inert gas such as nitrogen may be used.

[0037] The hydrogenation step can be carried out as a batch or continuous suspension reaction using a powder catalyst, or as a fixed bed reaction using a tablet catalyst or the like.

[0038] The equipment used in the hydrogenation step is not particularly limited, and any known equipment may be appropriately selected.

[0039] (Purification) After the hydrogenation step, purification may be carried out. Examples of the purification include filtering the catalyst used in the hydrogenation step and recrystallization. The purification method is not particularly limited, and any known method may be used. For example, the recrystallization may be carried out by adding ion-exchanged water to the filtrate obtained by filtering the catalyst used in the hydrogenation step to obtain crude crystals, adding ethyl acetate and normal hexane to the crude crystals, heating the mixture to dissolve the crude crystals, and then cooling the mixture to crystallize them.

[0040] (Analysis Method) The fact that the fluorene compound represented by the above formula (2) has been obtained can be confirmed by gas chromatography (GC). As a specific method, the method described in the Examples of this specification may be used.

[0041] The present specification discloses the following: The present disclosure (1) is a method for producing a fluorene compound, comprising a hydrogenation step of hydrogenating a fluorene compound represented by the following formula (1) in the presence of a catalyst and a solvent to obtain a fluorene compound represented by the following formula (2), wherein the catalyst is at least one metal catalyst selected from the group consisting of ruthenium, palladium, rhodium, osmium, iridium, platinum, and nickel, and the solvent is at least one selected from the group consisting of an ether-based solvent and an ester-based solvent. [In formulas (1) and (2), each m independently represents an integer of 0 or 1, and each n independently represents an integer of 0 to 6.]

[0042] The present disclosure (2) is the method for producing a fluorene compound according to the present disclosure (1), wherein the catalyst is at least one metal catalyst selected from the group consisting of ruthenium, palladium, rhodium, and nickel. The present disclosure (3) is the method for producing a fluorene compound according to the present disclosure (1) or (2), wherein the catalyst is supported on at least one support selected from the group consisting of carbon, alumina, silica gel, diatomaceous earth, titanium oxide, zirconium, and calcium carbonate. The present disclosure (4) is the method for producing a fluorene compound according to any one of the present disclosures (1) to (3), wherein when the catalyst is at least one metal catalyst selected from the group consisting of ruthenium, palladium, rhodium, osmium, iridium, and platinum, the supported amount is 0.1 to 10 mass%, and when the catalyst is a nickel catalyst, the supported amount is 40 to 50 mass%. The present disclosure (5) is the method for producing a fluorene compound according to any one of the present disclosures (1) to (4), wherein the solvent is at least one selected from the group consisting of diethylene glycol dimethyl ether and triethylene glycol dimethyl ether. The present disclosure (6) is the method for producing a fluorene compound according to any one of the present disclosures (1) to (5), wherein the reaction temperature of the hydrogenation step is 80°C to 150°C. The present disclosure (7) is the method for producing a fluorene compound according to any one of the present disclosures (1) to (6), wherein the hydrogen pressure in the hydrogenation step is 1 MPa to 10 MPa in gauge pressure. The present disclosure (8) is the method for producing a fluorene compound according to any one of the present disclosures (1) to (7), wherein the reaction time of the hydrogenation step is 4 hours to 10 hours.

[0043] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Reagents were used for compounds not specifically mentioned.

[0044] In the examples and comparative examples, the following catalysts and solvents were used: (Catalysts) Ru / C (ruthenium-carbon, manufactured by N.E. Chemcat Corporation) Pd / C (palladium-carbon, manufactured by N.E. Chemcat Corporation) Ni / diatomaceous earth (nickel-diatomaceous earth, manufactured by Sakai Chemical Industry Co., Ltd.) Rh / C (rhodium-carbon, manufactured by N.E. Chemcat Corporation) Note that the above Ru / C, Pd / C, and Rh / C all have a metal loading of 5% and are dried products, and Ni / diatomaceous earth has a metal loading of 40 to 50% and is a dried product. (Solvents) Diethylene glycol dimethyl ether (manufactured by Nacalai Tesque, Inc.) Triethylene glycol dimethyl ether (manufactured by Nacalai Tesque, Inc.) Ethyl acetate (manufactured by Nacalai Tesque, Inc.) Butyl acetate (manufactured by Nacalai Tesque, Inc.) Cyclohexanone (manufactured by Kishida Chemical Co., Ltd.) N-methyl-2-pyrrolidone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0045] [Synthesis of Fluorene Compound Represented by Formula (1)] 45 g of fluorenone with a purity of 99.5% by mass and 170 g of 2-phenylphenol were charged into a 1000 mL vessel equipped with a stirrer, a condenser, and a burette. 0.2 mL of thiol, specifically β-mercaptopropionic acid, was added and the mixture was heated to 65°C and melted. 40 mL of 95% sulfuric acid was added dropwise over 10 minutes. The reaction solution was then heated to 65°C and stirred for 1 hour to complete the reaction. After completion of the reaction, 200 g of methanol was added to the reaction solution, which was then heated to 60°C. After stirring for 1 hour, the mixture was cooled to 30°C, 900 g of pure water was added, and the resulting solid was filtered and dried. Using the above method, 9-9-bis-(3'-phenyl-4'-hydroxyphenyl)-fluorene [a fluorene compound represented by Formula (1) where m = 0 and n = 0] was obtained in a yield of 85.6%.

[0046] A 1000 mL vessel equipped with a stirrer, condenser, and buret was charged with 100 g of fluorenone with a purity of 99.5% by mass and 480 g of o-phenylphenol (2-hydroxyethyl) ether. 0.5 mL of β-mercaptopropionic acid was added and the mixture was heated to 65°C and melted. 40 mL of 36% hydrochloric acid was added dropwise over 10 minutes. The reaction solution was then heated to 65°C and stirred for 1 hour to complete the reaction. After completion of the reaction, 600 g of methanol was added to the reaction solution, which was then heated to 60°C and stirred for 1 hour. Next, 300 g of pure water was added to precipitate the reaction product, which was cooled to room temperature and then separated by filtration. The resulting solid was filtered and dried. Using the above method, 9-9-bis-[4-(2-hydroxyethoxy)-3-phenyl]-fluorene (a fluorene compound represented by the above formula (1), where m = 1 and n = 2) was obtained in an 83.6% yield.

[0047] Example 1: A 1500 mL stainless steel autoclave equipped with a magnetic stirrer was charged with 80 g of 9-9-bis-(3'-phenyl-4'-hydroxyphenyl)-fluorene [a fluorene compound represented by the formula (1) above, where m = 0 and n = 0], 12 g of 5% Ru / C, and 452 g of diethylene glycol dimethyl ether. The system was then purged with hydrogen, and hydrogenation was carried out for 7.5 hours at 100 ° C and 5 MPa (gauge pressure) while stirring. After completion of the reaction, an additional 600 g of diethylene glycol dimethyl ether was added to the reaction product, heated to 60 ° C, and the catalyst was filtered off. The resulting filtrate was transferred to a 2 L eggplant flask, and 211 g of the reaction solvent was distilled off in an evaporator at an oil temperature of 80 ° C and a vacuum of 20 mmHg. The concentrated reaction product was added to a 2000 mL four-neck flask equipped with a stirrer and thermometer, and then cooled to 20 ° C with stirring. The resulting crystals were filtered and rinsed with 320 g of ion-exchanged water. The wet crystals were dried under reduced pressure at 100°C for 31 hours to obtain 52 g (0.1 mol) of 9-9-bis(4-hydroxy-3-cyclohexylphenyl)fluorene [a fluorene compound represented by formula (2) above, where m = 0 and n = 0] with a purity of 98.9% (GC area percentage). The melting point of the crystals was 210°C. The yield of 9-9-bis(4-hydroxy-3-cyclohexylphenyl)fluorene [a fluorene compound represented by formula (2) above, where m = 0 and n = 0] was 64.0%.

[0048] (Examples 2 to 11, Comparative Examples 1 and 2) Fluorene compounds were produced in the same manner as in Example 1, except that the catalyst, solvent, hydrogen pressure, reaction temperature, and reaction time were changed as shown in Table 1. Note that the term "target product" in Table 1 refers to 9-9-bis(4-hydroxy-3-cyclohexylphenyl)fluorene [a fluorene compound in the above formula (2) where m = 0 and n = 0]. The hydrogen pressure refers to a gauge pressure value.

[0049] Example 12 A 1500 mL stainless steel autoclave equipped with a magnetic stirrer was charged with 80 g of 9-9-bis-(3'-phenyl-4'-hydroxyphenyl)-fluorene [a fluorene compound represented by the formula (1) above, where m = 0 and n = 0], 40 g of 5% Ru / C, and 452 g of diethylene glycol dimethyl ether. The system was then purged with hydrogen, and hydrogenation was carried out for 8 hours under conditions of 150°C and 1 MPa (gauge pressure) with stirring. A fluorene compound was produced in the same manner as in Example 1, except as described above.

[0050] (Example 13) In a 1500 mL stainless steel autoclave equipped with a magnetic stirrer, 90 g of 9-9-bis-[4-(2-hydroxyethoxy)-3-phenyl]-fluorene [a fluorene compound in the above formula (1), where m = 1, n = 2], 18 g of 5% Ru / C, and 510 g of diethylene glycol dimethyl ether were charged, and the system was purged with hydrogen. After that, hydrogenation was carried out for 8 hours under conditions of 100 ° C. and 5 MPa (gauge pressure) while stirring. After completion of the reaction, the mixture was cooled to 30 ° C. and the catalyst was filtered off. 530 g of the obtained filtrate was placed in a 1 L four-neck flask equipped with a stirrer, thermometer, and condenser, and 100 g of ion-exchanged water was added at 28 ° C. to precipitate crystals. The resulting crystals were filtered off, and the obtained crystals were rinsed with 260 g of ion-exchanged water. 9-9-bis-[4-(2-hydroxyethoxy)-3-cyclohexyl]-fluorene (a fluorene compound represented by the formula (2) above, where m = 1 and n = 2) was obtained as wet crystals with a purity of 93.6 GC% (GC area percentage). 98 g of the obtained wet crystals, 2500 g of ethyl acetate, and 320 g of normal hexane were added to a 5 L four-neck flask equipped with a stirrer, a thermometer, and a condenser, and the mixture was heated to 65°C for dissolution and stirred for 30 minutes. The mixture was then cooled to 15°C, and the precipitated crystals were separated by filtration and rinsed with 50 g of ion-exchanged water. The wet crystals were dried under reduced pressure at 100°C for 30 hours to obtain 70 g (0.12 mol) of 9-9-bis-[4-(2-hydroxyethoxy)-3-cyclohexyl]-fluorene (a fluorene compound in the above formula (2), where m = 1 and n = 2) with a purity of 99.5% (GC area percentage). The yield of 9-9-bis-[4-(2-hydroxyethoxy)-3-cyclohexyl]-fluorene (a fluorene compound in the above formula (2), where m = 1 and n = 2) was 80.0%.

[0051] Examples 14 and 15 Fluorene compounds were produced in the same manner as in Example 13, except that the catalyst, solvent, and reaction time were changed as shown in Table 2. Note that the term "target product" in Table 2 refers to 9-9-bis-[4-(2-hydroxyethoxy)-3-cyclohexyl]-fluorene (a fluorene compound represented by the above formula (2), where m = 1 and n = 2). The hydrogen pressure refers to a gauge pressure value.

[0052] Example 16 A 1500 mL stainless steel autoclave equipped with a magnetic stirrer was charged with 90 g of 9-9-bis-[4-(2-hydroxyethoxy)-3-phenyl]-fluorene (a fluorene compound represented by the formula (1) above, where m = 1 and n = 2), 36 g of 5% Ru / C, and 510 g of diethylene glycol dimethyl ether. The system was then purged with hydrogen, and hydrogenation was carried out for 8 hours under conditions of 150 ° C. and 1 MPa (gauge pressure) with stirring. A fluorene compound was produced in the same manner as in Example 13, except as described above.

[0053] (GC Analysis) The products obtained in each of the Examples and Comparative Examples were subjected to GC analysis under the following measurement conditions to confirm that the target compounds were obtained. <Measurement Conditions> Model: Gas chromatograph GC-2025 (Shimadzu Corporation) Detector: FID, 325°C Column: DB-1 (30 m x 0.25 mmφ x 0.25 μm) manufactured by Agilent Technologies, Inc. Column temperature: 275°C, heating rate 10°C / min, 320°C (retention time 60 min) Injection temperature: 300°C Carrier gas: Helium (linear velocity: 30 cm / sec) Injection volume: 1.0 μl (split ratio: 46.6)

[0054] <Purity> The purity of the obtained product was calculated by the following method. The purity of the obtained product was determined by preparing a trimethylsilylated sample by the following method, then performing GC analysis. The percentage area of ​​the trimethylsilylated sample relative to the total was determined by the area percentage method, and this value was taken as the purity of the product. (Sample Preparation) 5.0 g of pyridine (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 0.5 g of the obtained product (fluorene compound), and the mixture was dissolved by shaking at room temperature. Then, 1.5 g of BSTFA-TMCS (99:1) [Derivatizing Reagent for GC] (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and the mixture was shaken at room temperature to prepare a sample. The obtained purity was evaluated according to the following criteria. The results are shown in Tables 1 and 2. (Evaluation Criteria) ⊚: 80% or more. ◯: 60% or more, but less than 80%. ×: Less than 60%.

[0055]

[0056]

[0057] It has been confirmed that the method for producing a fluorene compound described in the examples can obtain the target fluorene compound represented by the above formula (2) with high purity.Furthermore, it has been confirmed that the method for producing a fluorene compound described in Examples 1 and 13 can obtain the fluorene compound represented by the above formula (2) from a phenylphenol compound and fluorenone with a yield of 50% or more.Compared to the conventional method (a method in which a phenylphenol compound is hydrogenated to obtain a cyclohexylphenol compound, and then the cyclohexylphenol compound is reacted with fluorenone) with a yield of about 25%, this method has also been shown to be excellent in yield.

[0058] The fluorene compound obtained by the method for producing a fluorene compound of the present invention is useful as a raw material monomer for resins such as polyester resins, polyester polycarbonate resins, polycarbonate resins, epoxy resins, polyurethane resins, polyacrylic acid ester resins, and polymethacrylic acid ester resins, or as a resin modifier.

Claims

1. A method for producing a fluorene compound, comprising a hydrogenation step of hydrogenating a fluorene compound represented by the following formula (1) in the presence of a catalyst and a solvent to obtain a fluorene compound represented by the following formula (2), wherein the catalyst is at least one metal catalyst selected from the group consisting of ruthenium, palladium, rhodium, osmium, iridium, platinum, and nickel, and the solvent is at least one selected from the group consisting of an ether solvent and an ester solvent. [In formulas (1) and (2), m each independently represents an integer of 0 or 1, and n each independently represents an integer of 0 to 6. ] 2. The method for producing a fluorene compound according to claim 1, wherein the catalyst is at least one metal catalyst selected from the group consisting of ruthenium, palladium, rhodium, and nickel.

3. The method for producing a fluorene compound according to claim 1, wherein the catalyst is supported on at least one carrier selected from the group consisting of carbon, alumina, silica gel, diatomaceous earth, titanium oxide, zirconium, and calcium carbonate.

4. The method for producing a fluorene compound according to claim 3, wherein when the catalyst is at least one metal catalyst selected from the group consisting of ruthenium, palladium, rhodium, osmium, iridium, and platinum, the supported amount is 0.1 to 10% by mass, and when the catalyst is a nickel catalyst, the supported amount is 40 to 50% by mass.

5. The method for producing a fluorene compound according to any one of claims 1 to 4, wherein the solvent is at least one selected from the group consisting of diethylene glycol dimethyl ether and triethylene glycol dimethyl ether.

6. The method for producing a fluorene compound according to any one of claims 1 to 4, wherein the hydrogenation step is carried out at a reaction temperature of 80°C to 150°C.

7. The method for producing a fluorene compound according to any one of claims 1 to 4, wherein the hydrogenation step is carried out at a hydrogen pressure of 1 MPa to 10 MPa in gauge pressure.

8. The method for producing a fluorene compound according to any one of claims 1 to 4, wherein the hydrogenation step is carried out for a reaction time of 4 hours to 10 hours.

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