Fluorene compound having halogen atom and allyl group and method for producing same

Abstract

To provide a fluorene compound having a halogen atom and an allyl group which can be a precursor of various fluorene skeleton-containing resins, and a production method of the same.SOLUTION: A fluorene compound having a halogen atom and an allyl group is represented by the following formula (1). In the formula, R is each independently a hydrogen atom or a methyl group. X is each independently a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a fluorene compound having a halogen atom and an allyl group, and a method for producing the same. [Background technology]

[0002] Conventionally, as a fluorene compound having an allyl group, a compound having an allyl group and an epoxy group represented by the following formula (X) described in Patent Document 1 has been known as a functional epoxy resin, and it has been found that the introduction of a fluorene skeleton improves heat resistance and electrical properties compared to conventional epoxy resins. [ka]

[0003] Therefore, the introduction of a fluorene skeleton is effective in improving the heat resistance and electrical properties of a resin, and is therefore important for the development of various functional resins. In particular, fluorene compounds having an allyl group, which allows polymers to be easily synthesized by reactions such as hydrosilylation, are of particular importance.

[0004] As fluorene compounds having an allyl group, there are compounds having an epoxy group and compounds having a phenolic hydroxyl group (Patent Documents 1 to 3), but in order to develop a variety of functional resins, compounds having halogen atoms that can be converted into various substituents have been desired. Furthermore, it is expected that fluorene compounds having halogen atoms and allyl groups can promote hydrosilylation reactions by halogen atoms, thereby shortening the maturation time of polymer synthesis using hydrosilylation reactions. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 4873223 [Patent Document 2] JP 2014-47207 A [Patent Document 3] JP 2014-62055 A Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a fluorene compound having a halogen atom and an allyl group, which can be a precursor of various fluorene skeleton-containing resins, and a method for producing the same. [Means for solving the problem]

[0007] As a result of extensive investigations aimed at achieving the above object, the present inventors discovered that the above problems could be solved by a fluorene compound having a specific halogen atom and an allyl group, and thus completed the present invention.

[0008] That is, the present invention provides the following fluorene compound having a halogen atom and an allyl group and a method for producing the same. 1. A fluorene compound having a halogen atom and an allyl group, represented by the following formula (1): [ka] (In the formula, each R is independently a hydrogen atom or a methyl group, and each X is independently a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.) 2. The fluorene compound 1 in which both R are hydrogen atoms. 3. A method for producing a fluorene compound represented by the following formula (1), which comprises reacting a fluorenone represented by the following formula (2) with a compound represented by the following formula (3). [ka] (In the formula, R is a hydrogen atom or a methyl group, and X is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.) [ka] (In the formula, R and X are the same as above.) 4. A method for producing an organosilicon compound having a fluorene skeleton, comprising subjecting the fluorene compound of 1 or 2 to a hydrosilylation reaction with an organosilicon compound having a Si-H group in the presence of a catalyst. Effect of the Invention

[0009] The fluorene compound having a halogen atom and an allyl group of the present invention can easily introduce substituents different from those of the conventionally known fluorene compounds having an allyl group, and is therefore expected to be a useful precursor for developing new functional resins containing a fluorene skeleton. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The fluorene compound having a halogen atom and an allyl group (hereinafter, also simply referred to as a fluorene compound) of the present invention is represented by the following formula (1). [ka]

[0011] In formula (1), each R is independently a hydrogen atom or a methyl group, with a hydrogen atom being preferred since the raw material is easily available.

[0012] In formula (1), each X is independently a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a chlorine atom or a bromine atom.

[0013] The fluorene compound of the present invention can be synthesized by reacting fluorenone represented by the following formula (2) with a compound represented by the following formula (3). [ka] (In the formula, R and X are the same as above.)

[0014] The reaction of the compound represented by formula (2) and the compound represented by formula (3) can be carried out by applying a method known in the art (for example, the methods described in JP 2017-114947 A, JP 2020-075866 A, Japanese Patent No. 6936544 A, etc.). The reaction temperature in the reaction is arbitrary, but it is usually 0 to 150 ° C., and the reaction time is about 2 to 30 hours.

[0015] The amounts of the compound represented by formula (2) and the compound represented by formula (3) used are arbitrary, but the amount of the compound represented by formula (3) used is usually 2.0 to 30 moles per mole of the compound represented by formula (2). In order to obtain the compound represented by formula (1) in good yield, the amount of the compound represented by formula (3) used is preferably 2.0 to 20 moles, more preferably 2.0 to 10 moles, per mole of the compound represented by formula (2).

[0016] In the reaction, an acid may be added. The acid is not particularly limited, but examples thereof include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, trifluoroacetic acid, and paratoluenesulfonic acid. The amount of the acid used is preferably 0.01 to 10 mol, more preferably 0.05 to 3 mol, relative to 1 mol of the compound represented by formula (2). The acid may be used alone or in combination of two or more kinds.

[0017] In addition, a solvent may be used in the reaction. The solvent is preferably selected from carbon tetrachloride, carbon disulfide, dichloromethane, chloroform, and nitromethane. The amount of the solvent used is usually 30 to 500 parts by mass, and preferably 50 to 300 parts by mass, based on 100 parts by mass of the compound represented by formula (2).

[0018] The reaction product of the reaction is washed with water, and then the solvent used is removed under reduced pressure with heating to obtain the fluorene compound of the present invention. When washing with water, an aqueous solution of a metal hydroxide such as sodium hydroxide or potassium hydroxide, a metal carbonate such as sodium carbonate, sodium hydrogen carbonate or potassium carbonate, or a metal hydrogen carbonate may be used.

[0019] The fluorene compound of the present invention can carry out hydrosilylation reaction with an organosilicon compound containing Si-H group by utilizing an allyl group. In the hydrosilylation reaction, the amount of the fluorene compound of the present invention and the organosilicon compound containing Si-H group used is not particularly limited, but it is preferable that the organosilicon compound containing Si-H group is 0.9 to 0.99 moles per mole of the fluorene compound. This allows a polymer having a high molecular weight to be obtained.

[0020] The Si-H group-containing organosilicon compound is not particularly limited, and examples thereof include hydrosilanes such as trimethoxyhydrosilane, triethoxyhydrosilane, and triethylsilane; dimethylpolysiloxanes having Si-H groups at both ends such as 1,1,3,3-tetramethyldisiloxane, α,ω-dihydrodimethylpolysiloxane, and α,ω-dihydromethylphenylpolysiloxane; dimethylpolysiloxanes having Si-H groups at one end such as 1,1,3,3,3-pentamethyldisiloxane and 1,1,1,3,3,5,5-heptamethyltrisiloxane; Examples of such compounds include dimethylpolysiloxanes containing Si-H groups in the side chain, such as 1,1,1,5,5,5-hexamethyl-3-phenyltrisiloxane; methylphenylpolysiloxanes containing Si-H groups in the side chain, such as 1,1,1,5,5,5-hexamethyl-3-phenyltrisiloxane; cyclic polysiloxanes containing Si-H groups, such as 2,4,6-trimethylcyclotrisiloxane and 2,4,6,8-tetramethylcyclotetrasiloxane; branched polysiloxanes containing Si-H groups; methylsilicone resins containing Si-H groups; methylphenylsilicone resins containing Si-H groups; silphenylene compounds containing Si-H groups; and silalkylene compounds containing Si-H groups.

[0021] In addition, when carrying out the hydrosilylation reaction between the compound of the present invention and an organosilicon compound containing a Si-H group, it is also possible to co-react with another vinyl group-containing compound. Examples of other vinyl group compounds include dimethylpolysiloxanes containing vinyl groups at both ends, such as 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, α,ω-divinyldimethylpolysiloxane, and α,ω-divinylmethylphenylpolysiloxane; dimethylpolysiloxanes containing vinyl groups at the side chain, such as 1,1,1,3,5,5,5-heptamethyl-3-vinyltrisiloxane; methylvinylphenylpolysiloxanes containing vinyl groups at the side chain, such as 1,1,1,5,5,5-hexamethyl-3-vinyl-3-phenyltrisiloxane; cyclic polysiloxanes containing vinyl groups, such as 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane and 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane; branched polysiloxanes containing vinyl groups, methylvinylsilicone resins, and methylvinylphenylsilicone resins.

[0022] The hydrosilylation reaction is carried out in the presence of a catalyst. Examples of the catalyst include platinum group metals such as platinum (including platinum black), rhodium, and palladium; platinum chloride, chloroplatinic acid, and chloroplatinic acid salts such as H2PtCl4·xH2O, H2PtCl6·xH2O, NaHPtCl6·xH2O, KHPtCl6·xH2O, Na2PtCl6·xH2O, K2PtCl4·xH2O, PtCl4·xH2O, PtCl2, and Na2HPtCl4·xH2O (wherein x is preferably an integer of 0 to 6, particularly preferably 0 or 6); and alcohol-modified chloroplatinic acid (for example, as described in U.S. Pat. No. 3,220,972). complexes of chloroplatinic acid and olefins (for example, those described in U.S. Pat. Nos. 3,159,601, 3,159,662, and 3,775,452); platinum group metals such as platinum black and palladium supported on supports such as alumina, silica, and carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium (the so-called Wilkinson's catalyst); and complexes of platinum chloride, chloroplatinic acid, or chloroplatinate with vinyl group-containing siloxanes (particularly vinyl group-containing cyclic siloxanes).

[0023] The amount of the catalyst used is a catalytic amount, and is preferably 0.001 to 0.1 mass% as platinum group metal relative to the total amount of the reaction polymer. In the polymerization reaction, a solvent may be used as necessary. As the solvent, for example, a hydrocarbon solvent such as toluene or xylene is preferable. The amount of the solvent used is not particularly limited, but is preferably 30 to 1000 mass parts, which is 0.3 to 10 times the total of 100 mass parts of the fluorene compound and the Si-H group-containing organosilicon compound. As the polymerization conditions, from the viewpoint of not deactivating the catalyst and being able to complete the polymerization in a short time, the polymerization temperature is, for example, 40 to 150°C, particularly 60 to 120°C. The polymerization time depends on the type and amount of the polymer, but is preferably completed within about 0.5 to 100 hours, particularly 0.5 to 30 hours, in order to prevent moisture from entering the polymerization system. After the polymerization reaction is completed, if a solvent is used, it can be distilled off to obtain a silicon-containing fluorene compound.

[0024] The fluorene compound of the present invention has a halogen atom that can be easily converted into another substituent, and therefore serves as a synthetic precursor for a fluorene compound having an allyl group and a substituent different from that of a conventional fluorene compound having an allyl group, and is therefore useful for the development of a fluorene skeleton-containing resin material.

[0025] Furthermore, since the fluorene compound having a halogen atom and an allyl group exhibits good reactivity in hydrosilylation, the reaction time for polymer synthesis by hydrosilylation can be shortened compared to the case where an allyl group-containing fluorene compound not having a halogen atom is used. EXAMPLES

[0026] The present invention will be further described below with reference to examples, but the present invention is not limited to the following examples. In the following examples, Mw was measured by gel permeation chromatography (GPC) using a TSKGEL Super HZM-H (manufactured by Tosoh Corporation) as a GPC column under analysis conditions of a flow rate of 0.6 mL / min, tetrahydrofuran as an elution solvent, and a column temperature of 40° C., with monodisperse polystyrene as a standard.

[0027] The compounds used in the synthesis are shown below. [ka]

[0028] [Example 1] In a 2L flask equipped with a thermometer, a nitrogen gas inlet tube, a reflux condenser, and a dropping funnel, 180.2 g (1.00 mol) of the compound represented by formula (S-1) and 335.8 g (2.20 mol) of the compound represented by formula (S-2) were added, and then 500 g of chloroform was added and stirred. After the compounds represented by formula (S-1) and formula (S-2) were dissolved, 17.2 g (0.10 mol) of paratoluenesulfonic acid was added, heated to 90°C, and stirred for 12 hours. The reaction solution was washed with an aqueous potassium carbonate solution and pure water, and the solvent was distilled off under reduced pressure to obtain a solid. The obtained solid was analyzed by ultraviolet-visible absorption spectroscopy and 1 H-NMR spectrum analysis (Bruker) confirmed that the compound was the compound represented by the following formula (4). 1 H-NMR (CDCl3): δ = 3.27 (4H, d, J=6.3Hz), 4.76-4.91 (4H, m), 5.78 (2H, ddt, J=17.1, 10.6, 6.3Hz), 6.53 (2H, d, J=1.2Hz), 7.22-7.45 (6H, m), 7.52 (2H, d, J=8.3Hz), 7.64 (2H, dd, J=8.1, 1.4Hz), 7.85 (2H, dd, J=8.5, 1.5Hz). [ka]

[0029] [Example 2] In a 2L flask equipped with a thermometer, a nitrogen gas inlet tube, a reflux condenser, and a dropping funnel, 180.2 g (1.00 mol) of the compound represented by formula (S-1) and 512.4 g (2.60 mol) of the compound represented by formula (S-3) were added, and then 500 g of chloroform was added and stirred. After the compounds represented by formulas (S-1) and (S-3) were dissolved, 12.0 g (0.20 mol) of acetic acid was added, heated to 120°C, and stirred for 10 hours. The reaction solution was washed with an aqueous sodium hydroxide solution and pure water, and the solvent was distilled off under reduced pressure to obtain a solid. The obtained solid was analyzed by ultraviolet-visible absorption spectroscopy and 1 H-NMR spectrum analysis (Bruker) confirmed that the compound was the compound represented by the following formula (5). 1 H-NMR (CDCl3): δ = 3.22 (4H, d, J=6.3Hz), 4.80-4.95 (4H, m), 5.73 (2H, ddt, J=17.1, 10.6, 6.3Hz), 6.51 (2H, d, J=1.3Hz), 7.09 (2H, dd, J=8.4, 1.3Hz), 7.31-7.45 (6H, m), 7.64 (2H, dd, J=8.1, 1.4Hz), 7.85 (2H, dd, J=8.5, 1.5Hz). [ka]

[0030] [Example 3] In a 2L flask equipped with a thermometer, a nitrogen gas inlet tube, a reflux condenser, and a dropping funnel, 180.2g (1.00 mol) of the compound represented by formula (S-1) and 516.2g (2.00 mol) of the compound represented by formula (S-4) were added, and then 500g of chloroform was added and stirred. After the compounds represented by formula (S-1) and formula (S-4) were dissolved, 8.61g (0.05 mol) of paratoluenesulfonic acid was added, heated to 130°C, and stirred for 9 hours. The reaction solution was washed with an aqueous sodium carbonate solution and pure water, and the solvent was distilled off under reduced pressure to obtain a solid. The obtained solid was analyzed by ultraviolet-visible absorption spectroscopy and 1 H-NMR spectrum analysis (Bruker) confirmed that the compound was the compound represented by the following formula (6). 1 H-NMR (CDCl3): δ = 2.35 (6H, s), 3.27 (4H, d, J=6.3Hz), 4.75-4.90 (4H, m), 5.82 (2H, ddt, J=16.5, 10.6, 6.3Hz), 6.79 (2H, d, J=1.2Hz), 6.99 (2H, d, J=1.2Hz), 7.27-7.45 (4H, m), 7.64 (2H, dd, J=8.1, 1.4Hz), 7.85 (2H, dd, J=8.5, 1.5Hz). [ka]

[0031] [Example 4] In a 5L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 280g (0.60 mol) of the compound represented by formula (4) and 74.6g (0.40 mol) of the compound represented by formula (S-7) were added, followed by adding 700g of toluene and heating to 70°C. Then, 1.0g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 mass%) was added, and 192g (0.99 mol) of the compound represented by formula (S-5) was added dropwise over 1 hour (total number of moles of hydrosilyl groups / total number of moles of alkenyl groups = 0.99 / 1). After the dropwise addition, the mixture was heated to 100°C and aged for 4 hours, after which toluene was distilled off from the reaction solution under reduced pressure to obtain resin 1. The Mw of resin 1 was 32,000. Note that resin 1 was obtained by 1 It was confirmed by 1 H-NMR (Bruker) that the polymer was the polymer represented by the following formula (7) (a=0.6, b=0.4). [ka]

[0032] [Example 5] In a 5L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 278 g (0.50 mol) of the compound represented by formula (5) and 93.2 g (0.50 mol) of the compound represented by formula (S-7) were added, followed by adding 700 g of toluene and heating to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 mass%) was added, and 133 g (0.99 mol) of the compound represented by formula (S-6) was added dropwise over 1 hour (total number of moles of hydrosilyl groups / total number of moles of alkenyl groups = 0.99 / 1). After the dropwise addition, the mixture was heated to 100°C and aged for 6 hours, after which toluene was distilled off under reduced pressure from the reaction solution to obtain resin 2. The Mw of resin 2 was 34,000. Note that resin 2 was obtained by 1 It was confirmed by 1 H-NMR (Bruker) that the polymer was a polymer represented by the following formula (8) (a=0.5, b=0.5). [ka]

[0033] [Comparative Example 1] In a 5L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 215g (0.50 mol) of the compound represented by formula (S-8) and 93.2g (0.50 mol) of the compound represented by formula (S-7) were added, followed by adding 700g of toluene and heating to 70°C. Then, 1.0g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 133g (0.99 mol) of the compound represented by formula (S-6) was added dropwise over 1 hour (total number of moles of hydrosilyl groups / total number of moles of alkenyl groups = 0.99 / 1). After the dropwise addition, the mixture was heated to 100°C and aged for 14 hours, after which toluene was distilled off under reduced pressure from the reaction solution to obtain comparative resin 1. The Mw of comparative resin 1 was 30,000. The comparative resin 1 was 1 It was confirmed by 1 H-NMR (Bruker) that the polymer was a polymer represented by the following formula (9) (a=0.5, b=0.5). [ka]

[0034] [Comparative Example 2] In a 5L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 217g (0.40 mol) of the compound represented by formula (S-9) and 112g (0.60 mol) of the compound represented by formula (S-7) were added, followed by adding 700g of toluene and heating to 70°C. Then, 1.0g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 192g (0.99 mol) of the compound represented by formula (S-5) was added dropwise over 1 hour (total number of moles of hydrosilyl groups / total number of moles of alkenyl groups = 0.99 / 1). After the dropwise addition, the mixture was heated to 100°C and aged for 16 hours, after which toluene was distilled off from the reaction solution under reduced pressure to obtain comparative resin 2. The Mw of comparative resin 2 was 31,000. The comparative resin 2 was 1 It was confirmed by 1 H-NMR (Bruker) that the polymer was a polymer represented by the following formula (10) (a=0.4, b=0.6). [ka]

[0035] [Aging time comparison] When Resins 1 and 2 and Comparative Resins 1 and 2 were synthesized, Mw was measured during aging every 2 hours until Mw reached 30,000 or more. The results are shown in Table 1.

[0036] [Table 1]

[0037] From the above results, according to the present invention, it is possible to synthesize and provide a fluorene compound having a halogen atom and an allyl group. Since the halogen atom is easily converted to other substituents, the fluorene compound is useful as a precursor of various fluorene-containing functional materials. Furthermore, the fluorene compound having a halogen atom and an allyl group shows good reactivity in hydrosilylation, and can shorten the reaction time of polymer synthesis.

Claims

1. A fluorene compound having a halogen atom and an allyl group, represented by the following formula (1): 【Chemistry 1】 (In the formula, each R is independently a hydrogen atom or a methyl group. Each X is independently a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.)

2. 2. The fluorene compound according to claim 1, wherein both R's are hydrogen atoms.

3. A method for producing a fluorene compound represented by the following formula (1), comprising reacting a fluorenone represented by the following formula (2) with a compound represented by the following formula (3). 【Chemistry 2】 (In the formula, R is a hydrogen atom or a methyl group, and X is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.) 【Chemistry 3】 (In the formula, R and X are the same as above.)

4. 3. A method for producing an organosilicon compound having a fluorene skeleton, comprising subjecting the fluorene compound according to claim 1 or 2 to a hydrosilylation reaction with an organosilicon compound having a Si--H group in the presence of a catalyst.

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