Method for producing 9,9-bis(4-amino-3-halogenophenyl)fluorene compound

Abstract

To provide a production method allowing high-yield and high-purity production of a 9,9-bis(4-amino-3-halogenophenyl)fluorene compound.SOLUTION: The production method of 9,9-bis(4-amino-3-halogenophenyl)fluorene compound comprises reacting 9-fluorenone with a 2-halogenoaniline represented by the general formula (1) in the figure, where X represents chlorine or fluorine, in the presence of a dissolved heteropolyacid.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing a 9,9-bis(4-amino-3-halogenophenyl)fluorene compound, and more particularly to a method for producing an industrially useful 9,9-bis(4-amino-3-halogenophenyl)fluorene compound. [Background technology]

[0002] 9,9-bis(4-amino-3-halogenophenyl)fluorene compounds are used in the field of polymer chemistry, and are particularly useful as raw materials for polyimides, polyamides, and epoxy resins. Polyimides, polyamides, and epoxy resins containing this compound can be used in a wide variety of industrial fields, such as electronic information materials, optical materials, and composite materials.

[0003] In Patent Document 1, in the reaction of 9-fluorenone with 2-fluoroaniline, a condensation reaction is carried out in the presence of a large excess of 2-fluoroaniline, using 0.9 moles of hydrochloric acid or 2-fluoroaniline hydrochloride relative to 9-fluorenone.

[0004] In Patent Document 2, in the reaction of 9-fluorenone with 2-chloroaniline, ortho-dichlorobenzene is used as a solvent, and a condensation reaction is carried out using 0.5 moles of methanesulfonic acid relative to 9-fluorenone.

[0005] In Patent Document 3, in the reaction of 9-fluorenone with 2-chloroaniline, a condensation reaction is carried out in a glycol solvent using 0.5 molar times concentrated sulfuric acid relative to 9-fluorenone.

[0006] On the other hand, in Patent Document 4, although not involving a 9,9-bis(4-amino-3-halogenophenyl)fluorene compound, a condensation reaction is carried out in the reaction of 9-fluorenone with an aniline compound using a heteropolyacid heterogeneous catalyst supported on a silica-based solid oxide such as white clay or diatomaceous earth.

[0007] In Patent Documents 1, 2, and 3, when the acid catalyst is added, the acid catalyst forms a salt with the raw material halogenoaniline, which becomes lumpy and difficult to stir. In addition, the 9,9-bis(4-amino-3-halogenophenyl)fluorene compound produced by the condensation reaction also forms a salt with the acid catalyst, so that at the end of the reaction, the mixture becomes a viscous slurry, which is difficult to stir. Furthermore, in order to isolate the target 9,9-bis(4-amino-3-halogenophenyl)fluorene compound, a process of desalination of the salt using an alkali equivalent to or greater than the acid catalyst used is required. In other words, a large amount of alkali is required, and as a result, a large amount of wastewater containing these neutralized salts is produced.

[0008] On the other hand, in Patent Document 4, a heteropolyacid supported on a silica-based solid oxide such as white clay or diatomaceous earth is used as a solid catalyst. However, as described in "Catalysts, Vol. 47, No. 1, 2005, 32-37, Effect of Support on Acid Catalysis of Heteropolyacid, p. 36, 5. Insolubilization of Heteropolyacid Catalyst Using a Support," there is an issue that the supported heteropolyacid dissolves in a polar solvent.

[0009] In the condensation reaction of Patent Document 4, the heteropolyacid is very easily eluted from the supported heteropolyacid catalyst because the reaction temperature is 140°C or higher in the presence of highly polar 2-halogenoanilines. Therefore, if the catalyst filtered after the reaction is reused as it is, the reaction activity is greatly reduced. In other words, there is a limit to the repeated use of the recovered supported heteropolyacid catalyst. If a new supported heteropolyacid catalyst is used for each reaction, a large amount of waste of the supported heteropolyacid catalyst, which is difficult to dispose of by burning, is generated. In addition, in order to remove the supported heteropolyacid catalyst from the reaction solution containing 2-halogenoanilines after the reaction, filtration is required at a high temperature at which the 9,9-bis(4-amino-3-halogenophenyl)fluorene compound does not crystallize, that is, hot filtration. Since 2-halogenoanilines are substances that are of concern for their high toxicity to the human body, hot filtration at a high temperature where the vapor pressure of 2-halogenoanilines is high is not preferable from the viewpoint of safety. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] JP 2011-084502 A [Patent Document 2] International Publication No. 2020 / 132406 [Patent Document 3] Chinese Patent No. 110437078 [Patent Document 4] Chinese Patent No. 108863807 [Non-patent literature]

[0011] [Non-Patent Document 1] Yuichi Kamiya and Toshio Okuhara, Effect of Support on Acid Catalysis of Heteropolyacids, Catalysts, 2005, Vol. 47, No. 1, pp. 32-37 DISCLOSURE OF THEINVENTION [Problem to be solved by the invention]

[0012] An object of the present invention is to provide a process for producing a 9,9-bis(4-amino-3-halogenophenyl)fluorene compound in high yield and with high purity. [Means for solving the problem]

[0013] The method for producing the 9,9-bis(4-amino-3-halogenophenyl)fluorene compound of the present invention comprises the steps of: [ka] (In the formula, X represents chlorine or fluorine.) A 2-halogenoaniline represented by the following formula: No solvent or at least one azeotropic solvent selected from cyclohexane, methylcyclohexane, benzene, toluene, and xylene; In the presence of a dissolved heteropolyacid, a reaction is carried out according to the following general formula (2): [ka] (In the formula, X represents chlorine or fluorine.) The present invention is characterized in that a 9,9-bis(4-amino-3-halogenophenyl)fluorene compound represented by the following formula is produced. Effect of the Invention

[0014] According to the method for producing a 9,9-bis(4-amino-3-halogenophenyl)fluorene compound of the present invention, a 9,9-bis(4-amino-3-halogenophenyl)fluorene compound represented by general formula (2) can be produced in high yield and high purity by reacting 9-fluorenone with a 2-halogenoaniline represented by general formula (1) in the presence of a heteropolyacid in which the 2-halogenoaniline is dissolved, and this is an industrially excellent production method. The 9,9-bis(4-amino-3-halogenophenyl)fluorene compound obtained by the production method of the present invention can be used in electronic information materials, optical materials, composite materials, etc. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The details of the present invention are described below. The 9,9-bis(4-amino-3-halogenophenyl)fluorene compound produced in the present invention is represented by general formula (2) and is produced by a condensation reaction of 9-fluorenone with a 2-halogenoaniline represented by the following general formula (1). [ka] [ka] (In the formulas (1) and (2), X represents chlorine or fluorine.)

[0016] Specific examples of the 2-halogenoanilines represented by the general formula (1) include 2-chloroaniline and 2-fluoroaniline. The 9,9-bis(4-amino-3-halogenophenyl)fluorene compounds represented by the general formula (2) include 9,9-bis(4-amino-3-chlorophenyl)fluorene and 9,9-bis(4-amino-3-fluorophenyl)fluorene.

[0017] The 2-halogenoanilines used in the condensation reaction of the present invention are preferably 2.0 to 20 times by mole, more preferably 2.0 to 15 times by mole, relative to the number of moles of 9-fluorenone. By using 2.0 times or more by mole of 2-halogenoanilines, the desired 9,9-bis(4-amino-3-halogenophenyl)fluorene compound can be produced. In addition, by using 20 times or less by mole of anilines, the effort of removing unreacted anilines from the reaction solution can be reduced.

[0018] The condensation reaction of 9-fluorenone and 2-halogenoanilines is carried out in the presence of a dissolved heteropolyacid. Examples of heteropolyacids include phosphotungstic acid, silicotungstic acid, and phosphomolybdic acid. More preferred are phosphotungstic acid and silicotungstic acid.

[0019] The dissolved heteropolyacid can be prepared by dissolving the heteropolyacid in water or a polar solvent, etc. The heteropolyacid can also be dissolved in 2-halogenoanilines.

[0020] The amount of heteropolyacid is preferably 0.001 to 0.2 molar times, more preferably 0.005 to 0.1 molar times, relative to the number of moles of 9-fluorenone. By using 0.001 molar times or more of heteropolyacid, the condensation reaction can be efficiently carried out. In addition, by using 0.2 molar times or less of heteropolyacid, an expensive heteropolyacid catalyst can be efficiently used. In addition, since heteropolyacid does not form a salt with 9,9-bis(4-amino-3-halogenophenyl)fluorene compound, a salt dissolving operation is not required during purification, and the production process can be simplified.

[0021] In the condensation reaction of 9-fluorenone and 2-halogenoanilines, water is generated, and it is preferable to carry out the reaction while removing the water. For this purpose, a method is used in which an inert gas is passed through the reaction system while the generated water is entrained therewith, or an azeotropic solvent is made to coexist and the generated water is continuously removed. As the inert gas, nitrogen is preferably used. As the azeotropic solvent, a solvent inert to the reaction system is used, such as cyclohexane, methylcyclohexane, benzene, toluene, xylene, etc. Preferably, toluene or xylene is used. The amount of the azeotropic solvent used is preferably 0.5 to 10 times the mass of 9-fluorenone.

[0022] The condensation reaction is preferably carried out under an inert atmosphere that does not contain oxygen. Specifically, the condensation reaction can be carried out by passing nitrogen gas that does not substantially contain oxygen through the reaction system. If the condensation reaction is carried out in the presence of oxygen, the 2-halogenoanilines are oxidized and colored, and this color may remain in the 9,9-bis(4-amino-3-halogenophenyl)fluorene compound, causing the 9,9-bis(4-amino-3-halogenophenyl)fluorene compound to be colored.

[0023] The reaction temperature is preferably 80 to 200°C. More preferably, it is 120 to 180°C. If the reaction temperature is lower than 80°C, it takes a long time to complete the reaction, and if the reaction temperature is higher than 200°C, a dimer is generated in which 9-fluorenone is further reacted with the 9,9-bis(4-amino-3-halogenophenyl)fluorene compound, and the yield of the 9,9-bis(4-amino-3-halogenophenyl)fluorene compound decreases. In addition, in mass production of the 9,9-bis(4-amino-3-halogenophenyl)fluorene compound, recovery and reuse of unreacted 2-halogenoanilines is important for reducing production costs, but if the reaction temperature is higher than 200°C, a part of the unreacted 2-halogenoanilines will be altered, resulting in a decrease in the recovery rate. As a result, this leads to a deterioration in the unit consumption of 2-halogenoanilines and an increase in waste.

[0024] The reaction time depends on the reaction temperature, but is preferably 3 to 100 hours, more preferably 5 to 80 hours. The end point of the reaction can be set as the time when 9-fluorenone is completely consumed and the remaining amount of an imine body in which one molecule of 2-halogenoanilines is condensed with 9-fluorenone as an intermediate is preferably 5.0 area % or less, more preferably 2.0 area % or less of the total peak area excluding the peak area of ​​2-halogenoanilines, in liquid chromatography analysis of the reaction solution.

[0025] The isolated 9,9-bis(4-amino-3-halogenophenyl)fluorene compound may contain impurities, so it is purified to obtain a high purity. Purification methods include, for example, rinsing the obtained 9,9-bis(4-amino-3-halogenophenyl)fluorene compound with a solvent, reslurrying the compound with a solvent, or recrystallization, which can be used to obtain a high purity 9,9-bis(4-amino-3-halogenophenyl)fluorene compound.

[0026] As the solvent for the rinse washing, reslurry washing or recrystallization, an alcohol-based solvent, an aromatic hydrocarbon-based solvent, an ether-based solvent, an ester-based solvent or an amide-based solvent may be used, but as the solvent for the rinse washing or reslurry washing, an alcohol-based solvent is preferably used. As the alcohol solvent, methanol, ethanol, isopropyl alcohol, etc. are exemplified. As the solvent for the recrystallization, an ether-based solvent or an ester-based solvent is used. As the ether-based solvent, tetrahydrofuran, etc. are exemplified, and as the ester-based solvent, methyl acetate, ethyl acetate, etc. are exemplified.

[0027] The amount of the solvent used in the rinsing is preferably 0.1 to 10 times the mass of 9-fluorenone.

[0028] The reslurry washing may be carried out at room temperature or at a temperature at which the solvent refluxes. The amount of the solvent used in the reslurry washing is preferably 1.0 to 30 times the mass of 9-fluorenone.

[0029] In the recrystallization, the 9,9-bis(4-amino-3-halogenophenyl)fluorene compound is dissolved in a solvent, and the resulting organic phase is mixed with a solvent containing at least one selected from water, alcohols, and lower aliphatic ketones as a poor solvent to crystallize the 9,9-bis(4-amino-3-halogenophenyl)fluorene compound. This makes it possible to obtain a high-purity 9,9-bis(4-amino-3-halogenophenyl)fluorene compound. Note that, as the poor solvent, a solvent that is a good solvent at high temperatures but becomes a poor solvent when the temperature is lowered can also be used.

[0030] The alcohols used as the poor solvent are alcohols having 1 to 6 carbon atoms and / or glycols having 2 to 3 carbon atoms, for example, primary alcohols such as methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, and 1-hexanol, secondary alcohols such as isopropanol, 2-butanol, 2-pentanol, 3-pentanol, 2-hexanol, and cyclohexanol, tertiary butanol, tertiary pentanol, ethylene glycol, and propylene glycol. Methanol, ethanol, and isopropanol are preferred.

[0031] The lower aliphatic ketones used as the poor solvent are aliphatic ketones having 3 to 9 carbon atoms, such as acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl ketone, diisopropyl ketone, dibutyl ketone, and methyl butyl ketone. Acetone, methyl ethyl ketone, and methyl isopropyl ketone are preferred.

[0032] The amount of the poor solvent used for recrystallization is preferably 0.5 to 30 times, and more preferably 1.0 to 5 times, the mass of 9-fluorenone.

[0033] After crystallization, the resulting slurry is subjected to solid-liquid separation to obtain a 9,9-bis(4-amino-3-halogenophenyl)fluorene compound in high yield and high purity. Since the crystallization mother liquor may adhere to the surface of the resulting 9,9-bis(4-amino-3-halogenophenyl)fluorene compound, a high-purity 9,9-bis(4-amino-3-halogenophenyl)fluorene compound can be obtained by washing the resulting 9,9-bis(4-amino-3-halogenophenyl)fluorene compound with a rinse liquid or by reslurry washing with a solvent. EXAMPLES

[0034] The present invention will be described in detail below with reference to examples, but is not limited to these examples. The analytical values ​​of the 9,9-bis(4-amino-3-halogenophenyl)fluorene compound obtained in this specification were measured by the following methods.

[0035] (chemical purity) The peak area fraction (HPLC area%) of the 9,9-bis(4-amino-3-halogenophenyl)fluorene compound relative to the total peak area minus the peak area of ​​anilines, measured by liquid chromatography (Shimadzu CLASS-VP) under the following conditions, was determined and used as the chemical purity (%). Column: YMC-Pack ODS-AM303 4.6φ×250mm Column temperature: 40℃ Mobile phase: 0.1% (v / v) phosphoric acid aqueous solution (A) and acetonitrile (B) were used, and the composition was changed according to the gradient (A / B) shown below. Gradient Time (min) Composition (A / B) 0 60 / 40 10 45 / 55 15 20 / 80 25 20 / 80 30 60 / 40 40 60 / 40 ·Flow rate: 1ml / min ·Injection volume: 10μl Detection: UV 254nm ·Analysis time: 40 minutes Analytical sample preparation: Weigh out 0.02 g of sample and dilute it in approximately 40 ml of acetonitrile. However, the analysis conditions are not limited to these as long as the same analysis results as those based on the above analysis conditions are obtained.

[0036] Example 1 A 200 mL four-neck flask equipped with a thermometer, a dropping funnel, a cooling tube and a stirrer was charged with 6.31 g (0.035 mol) of 9-fluorenone, 51.24 g (0.402 mol; 11.5 mol times / 9-fluorenone), 12.62 g (2.0 mass times / 9-fluorenone) of toluene and 0.50 g (0.005 mol times / 9-fluorenone) of phosphotungstic acid hydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The liquid temperature was raised to 140°C under nitrogen purging and stirring to start the reaction. During the reaction, the condensation reaction was carried out by aging for 30 hours while distilling off water. After the reaction was completed, the conversion rate of 9-fluorenone was 99.9 (LC area%) and the reaction yield of 9,9-bis(4-amino-3-chlorophenyl)fluorene was 93.7 (%).

[0037] The resulting reaction solution was cooled to 50°C or less, and 18.93g of isopropanol (3.0 times by mass / 9-fluorenone) was added to the reaction system and cooled as it was. The slurry containing the crystallized 9,9-bis(3-chloro-4-aminophenyl)fluorene was filtered, and the resulting cake was rinsed with 6.31g of isopropanol (1.0 times by mass / 9-fluorenone). The cake was vacuum-dried overnight at a temperature of 60°C and a reduced pressure of 0.01kPa or less to obtain 12.02g of 9,9-bis(4-amino-3-chlorophenyl)fluorene (isolation yield 82.3% / based on 9-fluorenone). The chemical purity by liquid chromatography analysis was 99.0 (LC area%).

[0038] Example 2 In Example 1, the amount of phosphotungstic acid hydrate was changed from 0.50 g (0.005 mole times / 9-fluorenone) to 1.01 g (0.01 mole times / 9-fluorenone), and the reaction time was changed from 30 hours to 24 hours, but the reaction was carried out in the same manner as in Example 1. After the reaction was completed, the conversion rate of 9-fluorenone was 100 (LC area%), and the reaction yield of 9,9-bis(4-amino-3-chlorophenyl)fluorene was 97.4 (%).

[0039] As a result of the crystallization operation, 12.34 g of 9,9-bis(4-amino-3-chlorophenyl)fluorene was obtained (isolation yield 84.5% / based on 9-fluorenone). The chemical purity by liquid chromatography analysis was 99.3 (LC area%).

[0040] Example 3 In Example 1, the amount of phosphotungstic acid hydrate was changed from 0.50 g (0.005 mol times / 9-fluorenone) to 2.02 g (0.02 mol times / 9-fluorenone), and the reaction time was changed from 30 hours to 12 hours, but the reaction was carried out in the same manner as in Example 1. After the reaction was completed, the conversion rate of 9-fluorenone was 100 (LC area%), and the reaction yield of 9,9-bis(4-amino-3-chlorophenyl)fluorene was 97.1 (%).

[0041] As a result of the crystallization operation, 12.37 g of 9,9-bis(4-amino-3-chlorophenyl)fluorene was obtained (isolation yield 84.7% / based on 9-fluorenone). The chemical purity by liquid chromatography analysis was 99.3 (LC area%).

[0042] Example 4 The reaction was carried out in the same manner as in Example 2, except that the reaction temperature was changed from 140°C to 160°C and the reaction time was changed from 24 hours to 8 hours. After the reaction was completed, the conversion rate of 9-fluorenone was 100 (LC area%) and the reaction yield of 9,9-bis(4-amino-3-chlorophenyl)fluorene was 95.0(%).

[0043] As a result of the crystallization operation, 13.22 g of 9,9-bis(4-amino-3-chlorophenyl)fluorene was obtained (isolation yield 90.5% / based on 9-fluorenone). The chemical purity by liquid chromatography analysis was 99.0 (LC area%).

[0044] Example 5 The reaction was carried out in the same manner as in Example 2, except that toluene was not added, the reaction temperature was changed from 140°C to 170°C, and the reaction time was changed from 24 hours to 6 hours. After the reaction was completed, the conversion rate of 9-fluorenone was 100 (LC area%), and the reaction yield of 9,9-bis(4-amino-3-chlorophenyl)fluorene was 95.9 (%).

[0045] As a result of the crystallization operation, 12.77 g of 9,9-bis(4-amino-3-chlorophenyl)fluorene was obtained (isolation yield 87.4% / based on 9-fluorenone). The chemical purity by liquid chromatography analysis was 98.6 (LC area%).

[0046] Example 6 In Example 5, 1.01 g (0.01 mole times / 9-fluorenone) of phosphotungstic acid hydrate was added to silicotungstic acid hydrate. 1.16 The reaction was carried out in the same manner as in Example 5, except that the reaction mixture was changed to 160°C instead of 170°C, and the reaction time was changed from 6 hours to 9 hours. After the reaction was completed, the conversion rate of 9-fluorenone was 100 (LC area%), and the reaction yield of 9,9-bis(4-amino-3-chlorophenyl)fluorene was 94.6(%).

[0047] As a result of the crystallization operation, 12.00 g of 9,9-bis(4-amino-3-chlorophenyl)fluorene was obtained (isolation yield 82.2% / based on 9-fluorenone). The chemical purity by liquid chromatography analysis was 98.0 (LC area%).

[0048] Example 7 In Example 5, 1.01 g (0.01 mol times / 9-fluorenone) of phosphotungstic acid hydrate was changed to 0.83 g (0.01 mol times / 9-fluorenone) of phosphomolybdic acid n-hydrate, the reaction temperature was changed from 170°C to 160°C, and the reaction time was changed from 6 hours to 9 hours, but the reaction was carried out in the same manner as in Example 5. After the reaction was completed, the conversion rate of 9-fluorenone was 100 (LC area%), and the reaction yield of 9,9-bis(4-amino-3-chlorophenyl)fluorene was 70.7 (%).

[0049] As a result of the crystallization operation, 7.68 g of 9,9-bis(4-amino-3-chlorophenyl)fluorene was obtained (isolation yield 52.6% / based on 9-fluorenone). The chemical purity by liquid chromatography analysis was 98.0 (LC area%).

[0050] Comparative Example 1 A 200 mL four-neck flask equipped with a thermometer, a dropping funnel, a cooling tube and a stirrer was charged with 6.31 g (0.035 mol) of 9-fluorenone, 51.24 g (0.402 mol; 11.5 mol times / 9-fluorenone), and 12.62 g (2.0 mass times / 9-fluorenone) of toluene. The solution was cooled to 15°C or less under nitrogen purging and stirring, and 10.95 g (3.0 mol times / 9-fluorenone) of 35% hydrochloric acid was added dropwise. After the dropwise addition was completed, the liquid temperature was raised to 140°C, and the reaction was started. During the reaction, the condensation reaction was carried out by aging for 20 hours while distilling off water. After the reaction was completed, the conversion rate of 9-fluorenone was 25.3 (LC area%), and the reaction yield of 9,9-bis(4-amino-3-chlorophenyl)fluorene was 14.8 (%).

[0051] The obtained reaction liquid was cooled to 50°C or less, and 24.71g (3.0 moles / 9-fluorenone) of 20% aqueous caustic soda solution was added dropwise. This was aged for 3 hours while stirring at a reaction temperature of 60°C, and the resulting 9,9-bis(4-amino-3-chlorophenyl)fluorene dihydrochloride was desalted. 18.93g (3.0 mass times / 9-fluorenone) of isopropanol was added to this, and the aqueous phase was removed by liquid separation to obtain an organic phase. 18.93g (3.0 mass times / 9-fluorenone) of isopropanol was added again to this, and the mixture was cooled to 10°C or less, but 9,9-bis(4-amino-3-chlorophenyl)fluorene did not crystallize and could not be obtained.

[0052] Comparative Example 2 In a 200mL four-neck flask equipped with a thermometer, a dropping funnel, a cooling tube and a stirrer, 6.31g (0.035 mol) of 9-fluorenone and 51.24g (0.402 mol; 11.5 mol times / 9-fluorenone) were charged. Under nitrogen purging and stirring, the solution was cooled to below 15°C, and 10.95g (3.0 mol times / 9-fluorenone) of 35% hydrochloric acid was added dropwise. After the dropwise addition was completed, the liquid temperature was raised to 160°C, and the reaction was started. During the reaction, the condensation reaction was carried out by aging for 24 hours while distilling off water. After the reaction was completed, the conversion rate of 9-fluorenone was 99.6 (LC area%), and the reaction yield of 9,9-bis(4-amino-3-chlorophenyl)fluorene was 61.9 (%).

[0053] The obtained reaction liquid was cooled to 50°C or less, and 24.71g (3.0 mole times / 9-fluorenone) of 20% aqueous caustic soda solution was added dropwise. This was aged for 3 hours while stirring at a reaction temperature of 60°C, and the resulting 9,9-bis(4-amino-3-chlorophenyl)fluorene dihydrochloride was desalted. 18.93g (3.0 mass times / 9-fluorenone) of isopropanol was added to this, and the aqueous phase was removed by liquid separation to obtain an organic phase. 18.93g (3.0 mass times / 9-fluorenone) of isopropanol was added again to this, and the mixture was cooled to 10°C or less, and 9,9-bis(4-amino-3-chlorophenyl)fluorene was crystallized. This slurry was filtered, and the resulting cake was rinsed with 6.31g (1.0 mass times / 9-fluorenone) of isopropanol. The cake was vacuum-dried overnight at 60°C and a reduced pressure of 0.01 kPa or less to obtain 7.16 g of 9,9-bis(4-amino-3-chlorophenyl)fluorene (isolated yield 49.0% / based on 9-fluorenone). The chemical purity by liquid chromatography analysis was 93.7 (LC area%).

[0054] Comparative Example 3 The same procedure as in Comparative Example 2 was carried out except that 10.95 g of 35% hydrochloric acid (3.0 mole times / 9-fluorenone) was replaced with 0.05 g of 98% sulfuric acid (0.015 mole times / 9-fluorenone). After the reaction was completed, the conversion rate of 9-fluorenone was 94.2 (LC area%), and the reaction yield of 9,9-bis(4-amino-3-chlorophenyl)fluorene was 32.6 (%).

[0055] Although the same crystallization procedure as in Comparative Example 2 was carried out, 9,9-bis(4-amino-3-chlorophenyl)fluorene did not crystallize and could not be obtained.

[0056] Comparative Example 4 The same procedure as in Comparative Example 2 was carried out except that 10.95 g of 35% hydrochloric acid (3.0 mole times / 9-fluorenone) was replaced with 0.11 g of methanesulfonic acid (0.030 mole times / 9-fluorenone). After the reaction was completed, the conversion rate of 9-fluorenone was 94.2 (LC area%), and the reaction yield of 9,9-bis(4-amino-3-chlorophenyl)fluorene was 48.0(%).

[0057] Although the same crystallization procedure as in Comparative Example 2 was carried out, 9,9-bis(4-amino-3-chlorophenyl)fluorene did not crystallize and could not be obtained.

[0058] (Reference Example) Preparation of Silica-Supported Phosphotungstic Acid 2.0 g of phosphotungstic acid hydrate was dissolved in 10.0 g of ion-exchanged water. 8.0 g of spherical silica gel 60 (particle size 100-210 μm) manufactured by Kanto Chemical was immersed in this aqueous solution in a porcelain evaporating dish and thoroughly stirred at room temperature. The porcelain evaporating dish was then placed on a hot plate and heated while stirring to evaporate the water. This was then calcined in an electric furnace under an air atmosphere at 300° C. for 3 hours to prepare silica-supported phosphotungstic acid (supported amount of phosphotungstic acid: 20% by mass).

[0059] Comparative Example 5 In Example 4, 1.01 g (0.01 mol times / 9-fluorenone) of phosphotungstic acid hydrate was changed to 5.05 g (0.01 mol times / 9-fluorenone) of silica-supported phosphotungstic acid prepared in Reference Example, and the reaction time was changed from 8 hours to 12 hours, except that the reaction was carried out in the same manner as in Example 4. After the reaction was completed, the conversion rate of 9-fluorenone was 100 (LC area%), and the reaction yield of 9,9-bis(4-amino-3-chlorophenyl)fluorene was 94.0 (%).

[0060] The reaction solution obtained was filtered while hot at 70°C, and the catalyst was filtered off. 18.93g of isopropanol (3.0 times by mass / 9-fluorenone) was added to the filtrate, and the filtrate was cooled as it was. The slurry containing the crystallized 9,9-bis(3-chloro-4-aminophenyl)fluorene was filtered, and the resulting cake was rinsed with 6.31g of isopropanol (1.0 times by mass / 9-fluorenone). The cake was vacuum-dried overnight at a temperature of 60°C and a reduced pressure of 0.01kPa or less, and 11.20g of 9,9-bis(4-amino-3-chlorophenyl)fluorene (isolation yield 76.7% / based on 9-fluorenone) was obtained. The chemical purity by liquid chromatography analysis was 99.1 (LC area%).

[0061] Comparative Example 6 Comparative Example 4 was carried out in the same manner as Comparative Example 5, except that the total amount of silica-supported tungstic phosphonate separated in Comparative Example 5 was used as it was, and the reaction time was changed from 12 hours to 42 hours. After the reaction was completed, the conversion rate of 9-fluorenone was 96.2 (LC area%), and the reaction yield of 9,9-bis(4-amino-3-chlorophenyl)fluorene was 42.0(%).

[0062] Although the same crystallization procedure as in Comparative Example 5 was carried out, 9,9-bis(4-amino-3-chlorophenyl)fluorene did not crystallize and could not be obtained.

[0063] Table 1 shows an outline of the above-mentioned Examples 1 to 7, and Table 2 shows an outline of the above-mentioned Comparative Examples 1 to 6.

[0064] [Table 1]

[0065] [Table 2]

Claims

1. 9-Fluorenone and a compound represented by the following general formula (1) 【Chemistry 1】 (In the formula, X represents chlorine or fluorine.) A 2-halogenoaniline represented by the following general formula (2): 【Chemistry 2】 (In the formula, X represents chlorine or fluorine.) The present invention relates to a method for producing a 9,9-bis(4-amino-3-halogenophenyl)fluorene compound represented by the following formula:

2. 2. The method for producing a 9,9-bis(4-amino-3-halogenophenyl)fluorene compound according to claim 1, wherein the amount of the heteropolyacid used is 0.001 to 0.2 moles per mole of 9-fluorenone.

3. 3. The method for producing a 9,9-bis(4-amino-3-halogenophenyl)fluorene compound according to claim 1, wherein the heteropolyacid is phosphotungstic acid or silicotungstic acid.

4. The method for producing a 9,9-bis(4-amino-3-halogenophenyl)fluorene compound according to any one of claims 1 to 3, wherein the reaction temperature is 80 to 200°C.

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