Method for producing fluorine-containing biphenols

Abstract

To provide a more industrially feasible method for producing fluorine-containing biphenols. [Solution] The following general formula (1) JPEG2026168799000048.jpg9170 A method for producing fluorine-containing biphenols, comprising reacting a perfluoroalkyl dihalide represented by formula (1) (wherein Rf may have 1 to 5 ether-bonded oxygen atoms between carbon atoms, or may have 1 to 5 ether-bonded oxygen atoms between carbon atoms, and X is a fluorine atom, a bromine atom, or an iodine atom, and Y is a bromine atom or an iodine atom) with phenols or biphenols in a solvent in the presence of sodium dithionite and a base.

Description

Technical Field

[0001] The present invention relates to a method for producing fluorine-containing biphenols. Polymer compounds having a fluorine-containing biphenol skeleton are materials that have a low refractive index, a low dielectric constant, high transparency, as well as high heat resistance and high solvent resistance, and are important materials in the aerospace field, semiconductor and photonics fields. In addition, biphenols linked by perfluoroalkyl groups are useful as monomer raw materials capable of introducing fluoroalkyl groups into polymer materials.

Background Art

[0002] Conventionally, as a method for producing fluorine-containing biphenols, a method of allowing a iodofluoroalkyl compound to act under light irradiation conditions in the presence of a catalyst has been known. The light irradiation reaction is a clean reaction because it does not use a radical initiator, but light irradiation requires special equipment, and from the viewpoint of equipment introduction cost, a method for producing fluorine-containing biphenols that can be carried out with general-purpose equipment is desired.

[0003] Non-Patent Document 1 reports a method of introducing a perfluorobutyl group into hydroquinone using perfluorobutyl iodide, hydrogen peroxide and dimethyl sulfoxide in the presence of an Fe(II) catalyst using a flow apparatus. Since this reaction utilizes the generation of methyl radicals from dimethyl sulfoxide, the solvent is limited to dimethyl sulfoxide.

[0004] Non-Patent Document 2 reports a method of introducing a perfluorobutyl group into hydroquinone by allowing BrCF2CF2Br, sulfur dioxide and pyridine to act on biphenol. In this method, highly toxic sulfur dioxide that causes respiratory system disorders is used in an equivalent amount relative to the substrate, but in an industrial production method, a method using a reagent with low toxicity is desired.

Prior Art Documents

Non-Patent Documents

[0005] [Non-Patent Document 1] Jffllia L. Monteiro et al., Chem.Eur.J.2017, 23, 176-186. [Non-Patent Document 2] Vyacheslav G. et al., Journal of Fluorine Chemistry, 2010, 131, 208-211. [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] In view of these prior arts, the present invention aims to provide a more industrially feasible method for producing fluorine-containing biphenols and novel fluorine-containing biphenols obtainable by this method. [Means for solving the problem]

[0007] Therefore, the present inventors diligently investigated methods for producing fluorine-containing biphenols and, as a result, discovered that fluorine-containing biphenols can be easily obtained by reacting phenols with perfluoroalkyl iodides in an organic solvent in the presence of sodium dithionite and a base, thus completing the present invention.

[0008] In other words, the present invention relates to the following. [1] The following general formula (1) [ka] (In formula (1), R f This refers to a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, which may have 1 to 5 ether-bonded oxygen atoms between carbon atoms. X is a fluorine atom, a bromine atom, or an iodine atom. Y is either a bromine atom or an iodine atom. A perfluoroalkyl dihalide represented by and the following general formula (2)

Chemical Formula

Chemical Formula

Chemical Formula

Chemical Formula

[0009] According to the present invention, a more industrially feasible method for producing fluorine-containing biphenols can be provided. Furthermore, the method of the present invention yields novel fluorine-containing biphenols. [Modes for carrying out the invention]

[0010] The present invention will be described in detail below.

[0011] A first embodiment of the present invention is the following general formula (1) [ka] (In formula (1), R f This represents a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, which may have 1 to 5 ether-bonded oxygen atoms between carbon atoms. X is a fluorine atom, a bromine atom, or an iodine atom. Y is either a bromine atom or an iodine atom. A perfluoroalkyl dihalide represented by the following general formula (2) [ka] (In formula (2), R 1a and R 1b Each of these independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a methoxy group, or an ethoxy group. The following general formula (5) is characterized by reacting phenols represented by in a solvent in the presence of sodium dithionite and a base. [ka] (In formula (5), R 1a and R 1b Each of these independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a methoxy group, or an ethoxy group.) This relates to a method for producing fluorine-containing biphenols represented by ).

[0012] The perfluoroalkyl dihalides used in this invention are represented by general formula (1), and in formula (1) R f This represents a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms, which may have 1 to 5 ether-bonded oxygen atoms between carbon atoms. Here, a perfluoroalkyl group refers to a branched or linear alkyl group that can be partially, substantially, or completely fluorinated.

[0013] The present invention relates to a perfluoroalkyl dihalide represented by general formula (1), where X is a fluorine atom, a bromine atom, or an iodine atom, preferably an iodine atom, and Y is a bromine atom or an iodine atom, preferably an iodine atom. As explained above, more specific examples of perfluoroalkyl dihalides are given below.

[0014] Examples of perfluoroalkyl dihalides represented by the general formula (1) of the present invention that have two iodine atoms at their termini include octafluoro-1,4-diiodobutane, dodecafluoro-1,6-diiodohexane, hexadecafluoro-1,8-diiodooctane, and eicosafluoro-1,10-diiododecane.

[0015] Examples of perfluoroalkyl halides represented by the general formula (1) of the present invention that have one bromine atom at one end include bromotrifluoromethane, 1-bromopentafluoroethane, 1-bromoheptafluoropropane, 1-bromononafluorobutane, 1-bromoundecafluoropentane, 1-bromotridecafluorohexane, 1-bromopentadecafluoroheptane, 1-bromoheptadecafluorooctane, 1-bromonadecafluorononane, and 1-bromohenicosafluorodecane.

[0016] Examples of perfluoroalkyl halides represented by the general formula (1) of the present invention that have one iodine atom at one end include trifluoroiodomethane, pentafluoroiodoethane, heptafluoro-1-iodopropane, nonafluoro-1-iodobutane, undecafluoro-1-iodopentane, tridecafluoro-1-iodohexane, pentadecafluoro-1-iodoheptane, heptadecafluoro-1-iodooctane, nonadecafluoro-1-iodononane, henicosafluoro-1-iododecane, and the like.

[0017] Examples of perfluoroalkyl halides represented by the general formula (1) of the present invention that have etheric oxygen atoms 1 to 5 between carbon atoms include, specifically, 1,6-dibromoperfluoro2,5-dioxanohexane, 1-bromoperfluoro2,5,8-trioxanonanane, 1-bromoperfluoro2,5-dioxanonanane, and 1,9-dibromoperfluoro2,5,8-trioxanonanane.

[0018] The phenols used in this invention are represented by general formula (2), and in formula (2) R 1a and R 1bEach of these independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a methoxy group, or an ethoxy group. Specifically, examples include phenol, 4-hydroxy-3,5-methylbenzene, 4-hydroxy-3,5-diethylbenzene, 4-hydroxy-3,5-di-n-propylbenzene, 4-hydroxy-3,5-diisopropylbenzene, 4-hydroxy-3,5-dimethoxybenzene, and 4-hydroxy-3,5-diethoxybenzene.

[0019] The present invention relates to the production of fluorine-containing biphenols represented by general formula (5) by reacting the above-mentioned perfluoroalkyl dihalides with phenols in a solvent in the presence of sodium dithionite and a base.

[0020] In the present invention, the amount of phenols used is preferably 2.0 to 10.0 molar times the amount of the perfluoroalkyl halide or perfluoroalkyl dihalide present in the reaction.

[0021] In the present invention, the solvent used is preferably at least one organic solvent selected from the group consisting of dimethyl sulfoxide, dimethylacetamide, and acetonitrile, or a mixed solvent of these organic solvents and water. By carrying out the reaction using these solvents, the target product can be efficiently obtained.

[0022] In the present invention, commercially available industrial-grade, reagent-grade, or equivalently pure sodium dithionite can be used. While not particularly limited, it is preferable to use a dithionite with a purity of 60% or higher, preferably 75% or higher. Furthermore, since metal impurities such as iron, copper, and zinc may inhibit the reaction, a low content of these impurities is preferable. The amount of sodium dithionite used should be 1.0 to 5.0 molar times the amount of the perfluoroalkyl halide or perfluoroalkyl dihalide present in the reaction.

[0023] Examples of bases applicable to the implementation of the present invention include lithium carbonate, lithium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, cesium carbonate, and cesium bicarbonate. The amount of base to be used should be 1.0 to 8.0 molar times the amount of perfluoroalkyl halide or perfluoroalkyl dihalide present in the reaction.

[0024] The solvents applicable to the present invention are not particularly limited as long as they are inert to the reaction, but specifically, examples include dichloromethane, chloroform, 1,2-dichloroethane, acetonitrile, propionitrile, tetrahydrofuran, dioxane, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide, among which acetonitrile, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide are preferred. These solvents may be used individually or in combination, or, if necessary, water may be added to each solvent individually or in combination. When water is added, it is possible to use 0.1 to 2.0 times the weight of the solvent used in the reaction.

[0025] The amount of the organic solvent or mixture of organic solvent and water used in the present invention is 0.5 to 500 times the weight of the perfluoroalkyl halide or perfluoroalkyl dihalide present in the reaction.

[0026] In the present invention, the reaction temperature varies depending on the type of phenols involved in the reaction and the type of solvent used, but it is generally preferable to have a temperature range of 0°C to 120°C.

[0027] In this invention, the reaction time varies depending on the type of phenols involved in the reaction, but is generally preferably in the range of 30 minutes to 24 hours.

[0028] The fluorine-containing biphenols obtained by the present invention are represented by general formula (5), and in formula (5) R 1a and R 1bEach of these independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a methoxy group, or an ethoxy group. As described above, the following are examples of fluorine-containing biphenols represented by general formula (5).

[0029] The present invention relates to fluorine-containing biphenols represented by general formula (5), R 1 Examples of compounds with hydrogen atoms include 1,4-bis(4-hydroxyphenyl)-1,1,2,2,3,3,4,4-octafluorobutane, 1,6-bis(4-hydroxyphenyl)-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexane, 1,8-bis(4-hydroxyphenyl)-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluorooctane, and 1,10-bis(4-H Examples include hydroxyphenyl)-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-icosafluorodecane, 1,6-bis(4-hydroxyphenyl)-1,1,3,3,4,4,6,6-octafluoro-2,5-dioxahexane, and 1,9-bis(4-hydroxyphenyl)-1,1,3,3,4,4,6,6,7,7,9,9-dodecafluoro-2,5,8-trioxanonanane.

[0030] The present invention relates to fluorine-containing biphenols represented by general formula (5), R 1 Examples of compounds containing a methyl group include 1,4-bis(4-hydroxy-3,5-dimethylphenyl)-1,1,2,2,3,3,4,4-octafluorobutane, 1,6-bis(4-hydroxy-3,5-dimethylphenyl)-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexane, 1,8-bis(4-hydroxy-3,5-dimethylphenyl)-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluorooctane, and 110-bis(4-hydroxy-3,5-dimethylphenyl)-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-icosafluorodecane.

[0031] The present invention relates to fluorine-containing biphenols represented by general formula (5), R 1 Examples of compounds containing an ethyl group include 1,4-bis(4-hydroxy-3,5-diethylphenyl)-1,1,2,2,3,3,4,4-octafluorobutane, 1,6-bis(4-hydroxy-3,5-diethylphenyl)-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexane, 1,8-bis(4-hydroxy-3,5-diethylphenyl)-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluorooctane, and 110-bis(4-hydroxy-3,5-diethylphenyl)-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-icosafluorodecane.

[0032] The present invention relates to fluorine-containing biphenols represented by general formula (5), R 1 Examples of compounds containing an n-propyl group include 1,4-bis(4-hydroxy-3,5-di-n-propylphenyl)-1,1,2,2,3,3,4,4-octafluorobutane, 1,6-bis(4-hydroxy-3,5-di-n-propylphenyl)-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexane, 1,8-bis(4-hydroxy-3,5-di-n-propylphenyl)-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluorooctane, and 110-bis(4-hydroxy-3,5-di-n-propylphenyl)-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-icosafluorodecane.

[0033] The present invention relates to fluorine-containing biphenols represented by general formula (5), R 1Examples of compounds containing an isopropyl group include 1,4-bis(4-hydroxy-3,5-diisopropylphenyl)-1,1,2,2,3,3,4,4-octafluorobutane, 1,6-bis(4-hydroxy-3,5-diisopropylphenyl)-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexane, 1,8-bis(4-hydroxy-3,5-diisopropylphenyl)-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluorooctane, and 110-bis(4-hydroxy-3,5-diisopropylphenyl)-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-icosafluorodecane.

[0034] The present invention relates to fluorine-containing biphenols represented by general formula (5), R 1 Examples of compounds containing a methoxy group include 1,4-bis(4-hydroxy-3,5-dimethoxyphenyl)-1,1,2,2,3,3,4,4-octafluorobutane, 1,6-bis(4-hydroxy-3,5-dimethoxyphenyl)-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexane, 1,8-bis(4-hydroxy-3,5-dimethoxyphenyl)-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluorooctane, and 110-bis(4-hydroxy-3,5-dimethoxyphenyl)-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-icosafluorodecane.

[0035] The present invention relates to fluorine-containing biphenols represented by general formula (5), R 1Examples of compounds containing an ethoxy group include 1,4-bis(4-hydroxy-3,5-diethoxyphenyl)-1,1,2,2,3,3,4,4-octafluorobutane, 1,6-bis(4-hydroxy-3,5-diethoxyphenyl)-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexane, 1,8-bis(4-hydroxy-3,5-diethoxyphenyl)-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluorooctane, and 110-bis(4-hydroxy-3,5-diethoxyphenyl)-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-icosafluorodecane.

[0036] A second embodiment of the present invention is the following general formula (1) [ka] (In formula (1), R f This represents a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, which may have 1 to 5 ether-bonded oxygen atoms between carbon atoms. X is a fluorine atom, a bromine atom, or an iodine atom. Y is either a bromine atom or an iodine atom. A perfluoroalkyl dihalide represented by the following general formula (3) [ka] (In formula (3), R 1a and R 1b Each of these independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a methoxy group, or an ethoxy group. The following general formula (6) is characterized by reacting biphenols represented by in a solvent with sodium dithionite and a base. [ka] (In formula (6), R 1a and R 1bEach of these independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a methoxy group, or an ethoxy group. Fluorine-containing biphenols represented by the following general formula (7) [ka] (In formula (7), R f This represents a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, which may have 1 to 5 ether-bonded oxygen atoms between carbon atoms. X is a fluorine atom, a bromine atom, or an iodine atom. R 1a and R 1b Each of these independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a methoxy group, or an ethoxy group. This invention relates to a method for producing fluorine-containing biphenols represented by [the formula shown].

[0037] The perfluoroalkyl dihalides used in this invention are represented by general formula (1), and in formula (1) R f This represents a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 2 to 6 carbon atoms, which may have 1 to 5 ether-bonded oxygen atoms between carbon atoms. Here, a perfluoroalkyl group refers to a branched or linear alkyl group that can be partially, substantially, or completely fluorinated.

[0038] The present invention relates to a perfluoroalkyl dihalide represented by general formula (1), where X is a fluorine atom, a bromine atom, or an iodine atom, preferably an iodine atom, and Y is a bromine atom or an iodine atom, preferably an iodine atom. As described above, specific examples of perfluoroalkyl dihalides are the same as those in the first embodiment described above.

[0039] The phenols used in this invention are represented by general formula (3), and in formula (3) R 1a and R 1bEach of these independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a methoxy group, or an ethoxy group. Specifically, examples include hydroquinone, 2,3-dimethylhydroquinone, 2,3-diethylhydroquinone, 2,3-di-n-propylhydroquinone, 2,3-diisopropylhydroquinone, 2,3-dimethoxyhydroquinone, and 2,3-diethoxyhydroquinone.

[0040] The present invention relates to the production of fluorine-containing biphenols represented by general formula (6) or general formula (7) by reacting the above-mentioned perfluoroalkyl dihalides with phenols in a solvent in the presence of sodium dithionite and a base.

[0041] In the present invention, the amount of phenols used is preferably 2.0 to 10.0 molar times the amount of the perfluoroalkyl halide or perfluoroalkyl dihalide present in the reaction.

[0042] The solvents, bases, etc. used in the present invention are the same as those in the first embodiment described above. Furthermore, the reaction temperature and reaction time in the present invention are also the same as those in the first embodiment described above.

[0043] The fluorine-containing biphenols obtained by the present invention are represented by general formula (6) or general formula (7), and R in formula (6) or (7) 1a and R 1b Each of these independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a methoxy group, or an ethoxy group. As described above, the following are examples of fluorine-containing biphenols represented by general formula (6) or general formula (7).

[0044] Examples of fluorine-containing biphenols represented by general formula (6) of the present invention include 1,1,2,2,3,3,4,4-octafluoro-5,8-dihydroxytetralin, 1,1,2,2,3,3,4,4-octafluoro-5,8-dihydroxy-6,7-dimethyltetralin, 1,1,2,2,3,3,4,4-octafluoro-5,8-dihydroxy-6,7-diethyltetralin, and 1,1,2,2,3,3,4,4-octafluoro Examples include oro-5,8-dihydroxy-6,7-di-n-propyltetralin, 1,1,2,2,3,3,4,4-octafluoro-5,8-dihydroxy-6,7-diisopropyltetralin, 1,1,2,2,3,3,4,4-octafluoro-5,8-dihydroxy-6,7-dimethoxytetralin, and 1,1,2,2,3,3,4,4-octafluoro-5,8-dihydroxy-6,7-diethoxytetralin.

[0045] The fluorine-containing biphenols represented by the general formula (7) of the present invention include 2-(pentafluoroethyl)-1,4-dihydroxybenzene, 2-(nonafluorobutyl)-1,4-dihydroxybenzene, 2-(tridecafluorohexyl)-1,4-dihydroxybenzene, 2-(pentafluoroethyl)-1,4-dihydroxy-2,3-dimethylbenzene, 2-(pentafluoroethyl)-1,4-dihydroxy-2,3-dimethoxybenzene, and 2-(2-bromo-1,1,2,2-tetrafluoroethyl)-1,4 Examples include -dihydroxybenzene, 2-(4-bromo-1,1,2,2,3,3,4,4-octafluorobutyl)-1,4-dihydroxybenzene, 2-(2-iodo-1,1,2,2-tetrafluoroethyl)-1,4-dihydroxybenzene, 2-(4-iodo-1,1,2,2,3,3,4,4-octafluorobutyl)-1,4-dihydroxybenzene, and 2-(1,1,3,3,4,4,6,6,7,7,9,9-dodecafluoro-2,5,8-trioxanonanane)-1,4-dihydroxybenzene.

[0046] A third embodiment of the present invention is the following general formula (1) [ka] (In formula (1), R f This represents a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, which may have 1 to 5 ether-bonded oxygen atoms between carbon atoms. X is a fluorine atom, a bromine atom, or an iodine atom. Y is either a bromine atom or an iodine atom. A perfluoroalkyl dihalide represented by the following general formula (4) [ka] (In formula (4), R 2 This represents a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 1 to 10 carbon atoms, a cyclic alkylene group having 5 to 10 carbon atoms, a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a difluoromethylene chain, or -C(CF3)2-. R 3a and R 3b Each of these independently represents a hydrogen atom, a methyl group, a hydroxymethyl group, an ethyl group, or a tert-butyl group (t-butyl group). The following general formulas (8) and (9) are characterized by reacting biphenols represented by these formulas in a solvent in the presence of sodium dithionite and a base. [ka] [ka] (In equations (8) and (9), R f This represents a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, which may have 1 to 5 ether-bonded oxygen atoms between carbon atoms. X is a fluorine atom, a bromine atom, or an iodine atom. R 2This represents a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 1 to 10 carbon atoms, a cyclic alkylene group having 5 to 10 carbon atoms, a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a difluoromethylene chain, or -C(CF3)2-. Fluorine-containing biphenols represented by the following general formulas (10) and (11) [ka] [ka] (In equations (10) and (11), R f This represents a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, which may have 1 to 5 ether-bonded oxygen atoms between carbon atoms. X is a fluorine atom, a bromine atom, or an iodine atom. R 2 This represents a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 1 to 10 carbon atoms, a cyclic alkylene group having 5 to 10 carbon atoms, a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a difluoromethylene chain, or -C(CF3)2-. R 3a and R 3b Each of these independently represents a hydrogen atom, a methyl group, a hydroxymethyl group, an ethyl group, or a tert-butyl group (t-butyl group). This invention relates to a method for producing fluorine-containing biphenols represented by [the formula shown].

[0047] The perfluoroalkyl dihalides used in this invention are represented by general formula (1), and in formula (1) R f This represents a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms, which may have 1 to 5 ether-bonded oxygen atoms between carbon atoms. Here, a perfluoroalkyl group refers to a branched or linear alkyl group that can be partially, substantially, or completely fluorinated.

[0048] The present invention relates to a perfluoroalkyl dihalide represented by general formula (1), where X is a fluorine atom, a bromine atom, or an iodine atom, preferably an iodine atom, and Y is a bromine atom or an iodine atom, preferably an iodine atom. As described above, specific examples of perfluoroalkyl dihalides are the same as those in the first embodiment described above.

[0049] The phenols used in this invention are represented by general formula (4), and in formula (4) R 2 This represents a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 1 to 10 carbon atoms, a cyclic alkylene group having 5 to 10 carbon atoms, a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a difluoromethylene chain, or -C(CF3)2-. R in equation (4) 3a and R 3b Each of these independently represents a hydrogen atom, a methyl group, a hydroxymethyl group, an ethyl group, or a tert-butyl group (t-butyl group).

[0050] Specifically, examples include bisphenol A, bisphenol B, bisphenol E, bisphenol F, bisphenol Z, 4-[1-(4-hydroxyphenyl)-3-methylcyclohexyl]phenol, 4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol, 3,3',5,5'-tetramethylbiphenyl-4,4'-diol, bisphenol AF, 4,4'-dihydroxybenzophenone, 2,2'-bis(4-hydroxy-3-methylphenyl)propane, 4,4'-methylenebis(2,6-dimethylphenol), 2,2'-bis(4-hydroxy-3,5-dimethylphenyl)propane, and diphenolic acids.

[0051] The present invention relates to the production of fluorine-containing biphenols represented by general formula (8), general formula (9), general formula (10), or general formula (11) by reacting the above-mentioned perfluoroalkyl dihalides with phenols in a solvent in the presence of sodium dithionite and a base.

[0052] In the present invention, the amount of phenols used is preferably 2.0 to 10.0 molar times the amount of the perfluoroalkyl halide or perfluoroalkyl dihalide present in the reaction.

[0053] The solvents, bases, etc. used in the present invention are the same as those in the first embodiment described above. Furthermore, the reaction temperature and reaction time in the present invention are also the same as those in the first embodiment described above.

[0054] The fluorine-containing biphenols obtained by the present invention are represented by general formula (8), general formula (9), general formula (10), or general formula (11).

[0055] R in equation (8) or equation (9) f This represents a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, which may have 1 to 5 ether-bonded oxygen atoms between carbon atoms. X is a fluorine atom, a bromine atom, or an iodine atom. R 2 This represents a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 1 to 10 carbon atoms, a cyclic alkylene group having 5 to 10 carbon atoms, a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a difluoromethylene chain, or -C(CF3)2-.

[0056] R in equation (10) or equation (11) f This represents a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, which may have 1 to 5 ether-bonded oxygen atoms between carbon atoms. X is a fluorine atom, a bromine atom, or an iodine atom. R 2 This represents a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 1 to 10 carbon atoms, a cyclic alkylene group having 5 to 10 carbon atoms, a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a difluoromethylene chain, or -C(CF3)2-. R 3a and R 3bEach of these independently represents a hydrogen atom, a methyl group, a hydroxymethyl group, an ethyl group, or a tert-butyl group (t-butyl group).

[0057] As described above, the following are examples of fluorine-containing biphenols represented by general formula (8), general formula (9), general formula (10), or general formula (11).

[0058] The fluorine-containing biphenols represented by the general formula (8) of the present invention include 2-(pentafluoroethyl)-4-[1-(4-hydroxyphenyl)-1-methylethyl]phenol, 2-(nonafluorobutyl)-4-[1-(4-hydroxyphenyl)-1-methylethyl]phenol, 2-(tridecafluorohexyl)-4-[1-(4-hydroxyphenyl)-1-methylethyl]phenol, 2-(2-bromo-1,1,2,2-tetrafluoroethyl)-4-[1-(4-hydroxyphenyl)-1-methylethyl]phenol, and 2-(4-bromo-1,1,2,2,3,3,4,4-oc Examples include tafluorobutyl)-4-[1-(4-hydroxyphenyl)-1-methylethyl]phenol, 2-(2-iodo-1,1,2,2-tetrafluoroethyl)-4-[1-(4-hydroxyphenyl)-1-methylethyl]phenol, 2-(4-iodo-1,1,2,2,3,3,4,4-octafluorobutyl)-4-[1-(4-hydroxyphenyl)-1-methylethyl]phenol, and 2-(1,1,3,3,4,4,6,6,7,7,9,9-dodecafluoro-2,5,8-trioxanonanane)-4-[1-(4-hydroxyphenyl)-1-methylethyl]phenol.

[0059] The fluorine-containing biphenols represented by the general formula (9) of the present invention include 2,2-bis[2-(pentafluoroethyl)-4-hydroxyphenyl]propane, 2,2-bis[2-(nonafluorobutyl)-4-hydroxyphenyl]propane, 2,2-bis[2-(tridecafluorohexyl)-4-hydroxyphenyl]propane, 2,2-bis[2-(2-bromo-1,1,2,2-tetrafluoroethyl)-4-hydroxyphenyl]propane, and 2,2-bis[2-(4-bromo-1,1,2,2,3,3 Examples include ,4,4-octafluorobutyl)-4-hydroxyphenyl]propane, 2,2-bis[2-(2-iodo-1,1,2,2-tetrafluoroethyl)-4-hydroxyphenyl]propane, 2,2-bis[2-(4-iodo-1,1,2,2,3,3,4,4-octafluorobutyl)-4-hydroxyphenyl]propane, and 2,2-bis[2-(1,1,3,3,4,4,6,6,7,7,9,9-dodecafluoro-2,5,8-trioxanonanane)-4-hydroxyphenyl]propane.

[0060] The fluorine-containing biphenols represented by the general formula (10) of the present invention include: 3-(pentafluoroethyl)-4-[1-(2,6-dimethoxy-4-hydroxyphenyl)-1-methylethyl]-2,6-dimethoxyphenol, 3-(nonafluorobutyl)-4-[1-(2,6-dimethoxy-4-hydroxyphenyl)-1-methylethyl]-2,6-dimethoxyphenol, 3-(tridecafluorohexyl)-4-[1-(2,6-dimethoxy-4-hydroxyphenyl)-1-methylethyl]-2,6-dimethoxyphenol, 3-(2-bromo-1,1,2,2-tetrafluoroethyl)-4-[1-(2,6-dimethoxy-4-hydroxyphenyl)-1-methylethyl]-2,6-dimethoxyphenol, 3-(4-bromo-1,1,2,2,3,3,4,4-octafluorobutyl)-4-[1-( Examples include 2,6-dimethoxy-4-hydroxyphenyl)-1-methylethyl]-2,6-dimethoxyphenol, 3-(2-iodo-1,1,2,2-tetrafluoroethyl)-4-[1-(2,6-dimethoxy-4-hydroxyphenyl)-1-methylethyl]-2,6-dimethoxyphenol, 3-(4-iodo-1,1,2,2,3,3,4,4-octafluorobutyl)-4-[1-(2,6-dimethoxy-4-hydroxyphenyl)-1-methylethyl]-2,6-dimethoxyphenol, and 3-(1,1,3,3,4,4,6,6,7,7,9,9-dodecafluoro-2,5,8-trioxanonanane)-4-[1-(2,6-dimethoxy-4-hydroxyphenyl)-1-methylethyl]-2,6-dimethoxyphenol.

[0061] The fluorine-containing biphenols represented by the general formula (11) of the present invention include 2,2-bis[3-(pentafluoroethyl)-2,6-dimethyl-4-hydroxyphenyl]propane, 2,2-bis[3-(nonafluorobutyl)-2,6-dimethyl-4-hydroxyphenyl]propane, 2,2-bis[3-(tridecafluorohexyl)-2,6-dimethyl-4-hydroxyphenyl]propane, 2,2-bis[3-(2-bromo-1,1,2,2-tetrafluoroethyl)-2,6-dimethyl-4-hydroxyphenyl]propane, and 2,2-bis[3-(4 -bromo-1,1,2,2,3,3,4,4-octafluorobutyl)-2,6-dimethyl-4-hydroxyphenyl]propane, 2,2-bis[3-(2-iodo-1,1,2,2-tetrafluoroethyl)-2,6-dimethyl-4-hydroxyphenyl]propane, 2,2-bis[3-(4-iodo-1,1,2,2,3,3,4,4-octafluorobutyl)-2,6-dimethyl-4-hydroxyphenyl]propane, 2,2-bis[3-(1,1,3,3,4,4,6,6,7,7,9,9-dodecafluoro-2,5,8-trioxanonanane)-2 ,6-dimethyl-4-hydroxyphenyl]propane, 2,2-bis[3-(pentafluoroethyl)-2,6-dimethoxy-4-hydroxyphenyl]propane, 2,2-bis[3-(nonafluorobutyl)-2,6-dimethoxy-4-hydroxyphenyl]propane, 2,2-bis[3-(tridecafluorohexyl)-2,6-dimethoxy-4-hydroxyphenyl]propane, 2,2-bis[3-(2-bromo-1,1,2,2-tetrafluoroethyl)-2,6-dimethoxy-4-hydroxyphenyl]propane, 2,2-bis[3-(4-bromo Mo-1,1,2,2,3,3,4,4-octafluorobutyl)-2,6-dimethoxy-4-hydroxyphenyl]propane, 2,2-bis[3-(2-iodo-1,1,2,2-tetrafluoroethyl)-2,6-dimethoxy-4-hydroxyphenyl]propane, 2,2-bis[3-(4-iodo-1,1,2,2,3,3,4,4-octafluorobutyl)-2,6-dimethoxy-4-hydroxyphenyl]propane, 2,2-bis[3-(1,1,3,3,4,4,6,6,7,7,9,9-dodecafluoro-2,5,8-trioxanonanane)-2,Examples include 6-dimethoxy-4-hydroxyphenyl]propane, etc.

[0062] In the present invention, fluorine-containing biphenols represented by any of the following formulas (12) to (14) can be obtained. Fluorine-containing aromatic polymers are materials with high heat resistance and high solvent resistance, making them important materials in the aerospace and semiconductor / photonics fields. These compounds are fluorine-containing compounds with bifunctional reaction sites and can be used as fluorine-containing aromatic polymers. [ka] [ka] [ka]

[0063] In the present invention, the amount of phenols used is preferably 2.0 to 10.0 molar times the amount of the perfluoroalkyl halide or perfluoroalkyl dihalide present in the reaction.

[0064] In the present invention, commercially available industrial-grade, reagent-grade, or equivalently pure sodium dithionite can be used. While not particularly limited, it is preferable to use a dithionite with a purity of 60% or higher, preferably 75% or higher. Furthermore, since metal impurities such as iron, copper, and zinc may inhibit the reaction, a low content of these impurities is preferable. The amount of sodium dithionite used should be 1.0 to 5.0 molar times the amount of the perfluoroalkyl halide or perfluoroalkyl dihalide present in the reaction.

[0065] Examples of bases applicable to the implementation of the present invention include lithium carbonate, lithium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, cesium carbonate, and cesium bicarbonate. The amount of base to be used should be 1.0 to 8.0 molar times the amount of perfluoroalkyl halide or perfluoroalkyl dihalide present in the reaction.

[0066] The solvents applicable to the present invention are not particularly limited as long as they are inert to the reaction, but specifically, examples include dichloromethane, chloroform, 1,2-dichloroethane, acetonitrile, propionitrile, tetrahydrofuran, dioxane, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide, among which acetonitrile, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide are preferred. These solvents may be used individually or in combination, or, if necessary, water may be added to each solvent individually or in combination. When water is added, it is possible to use 0.1 to 2.0 times the weight of the solvent used in the reaction.

[0067] The amount of the organic solvent or mixture of organic solvent and water used in the present invention is 0.5 to 500 times the weight of the perfluoroalkyl halide or perfluoroalkyl dihalide present in the reaction.

[0068] In the present invention, the reaction temperature varies depending on the type of phenols involved in the reaction and the type of solvent used, but it is generally preferable to have a temperature range of 0°C to 120°C.

[0069] In this invention, the reaction time varies depending on the type of phenols involved in the reaction, but is generally preferably in the range of 30 minutes to 24 hours.

[0070] There are no particular restrictions on the post-reaction treatment of the present invention, and it can be carried out by well-known methods. For example, the product may be extracted with a solvent such as ethyl acetate or dichloromethane, dried on sodium sulfate or magnesium sulfate, filtered, and concentrated to obtain a crude product, which may then be purified by silica gel column chromatography or the like to obtain the purified target product. [Examples]

[0071] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0072] The following equipment was used for the analysis. 1 H-NMR and 19 F-NMR: JEOL GSX-400 spectrometer manufactured by JEOL Ltd.

[0073] Example 1 Preparation of 1,1,2,2,3,3,4,4-octafluoro-5,8-dihydroxytetraline (a) [ka]

[0074] Under an argon atmosphere, hydroquinone (198 mg, 1.8 mmol), sodium dithionite (261 mg, 1.5 mmol), sodium bicarbonate (126 g, 1.5 mmol), dimethyl sulfoxide (2 mL), and octafluoro-1,4-diiodobutane (136 mg, 0.3 mmol) were added to a 100 mL two-necked round-bottom flask equipped with a stirring bar, and the reaction was carried out at 100 °C for 1 hour. After the reaction was complete, the crude product was obtained by extraction with a hexane-ethyl acetate mixture, drying over sodium sulfate, filtration, and concentration under reduced pressure. The target product, 1,1,2,2,3,3,4,4-octafluoro-5,8-dihydroxytetraline (a), was then purified by silica gel column chromatography (17 mg, 0.05 mmol, yield 18%).

[0075] The analysis of the target substance was as follows: 1 H-NMR (400MHz, CDCl3) δ=7.12(2H,s),4.29(2H,br). 19 F-NMR (376MHz, CDCl3)δ=-108.0(4F,s),-135.5(4F,s).

[0076] Example 2 Preparation of 1,6-bis(4-hydroxy-3,5-dimethoxyphenyl)-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexane(b) [ka]

[0077] Under an argon atmosphere, 4-hydroxy-3,5-dimethoxybenzene (228 mg, 1.8 mmol), sodium dithionite (157 mg, 0.9 mmol), sodium bicarbonate (76 mg, 0.9 mmol), water (1 mL), acetonitrile (1 mL), and dodecafluoro-1,6-diiodohexane (166 mg, 0.9 mmol) were added to a 100 mL two-necked round-bottom flask equipped with a stirring bar, and the reaction was carried out at room temperature for 1 hour. After the reaction was complete, the crude product was obtained by extraction with a hexane-ethyl acetate mixture, drying over sodium sulfate, filtration, and concentration under reduced pressure. The product was then purified by silica gel column chromatography to obtain the target product, 1,6-bis(4-hydroxy-3,5-dimethoxyphenyl)-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexane(b) (73 mg, 0.12 mmol, yield 39%).

[0078] The analysis of the target substance was as follows: 1 H-NMR (400MHz, CDCl3) δ = 6.79 (4H, s), 5.80 (2H, s), 3.93 (12H, s). 19F-NMR (376MHz, CDCl3)δ=-109.9(4F,s),-121.8(4F,s),-122.2(4F,s).

[0079] Example 3 Preparation of 2-(tridecafluorohexyl)-4-[1-(4-hydroxyphenyl)-1-methylethyl]phenol (c) [ka]

[0080] Under an argon atmosphere, bisphenol A (411 mg, 1.8 mmol), sodium dithionite (157 mg, 0.9 mmol), sodium bicarbonate (76 mg, 0.9 mmol), dimethylacetamide (1 mL), and tridecafluoro-1-iodohexane (134 mg, 0.3 mmol) were added to a 10 mL glass tube equipped with a stirring bar, and the reaction was carried out at 100°C for 1 hour. After the reaction was complete, the crude product was obtained by extraction with a hexane-ethyl acetate mixture, drying over sodium sulfate, filtration, and concentration under reduced pressure. The target product, 4-[1-(4-hydroxyphenyl)-1-methylethyl]-2-perfluorohexylphenol(c), was then purified by silica gel column chromatography (70 mg, 0.13 mmol, yield 43%).

[0081] The analysis of the target substance was as follows: 1 H-NMR (400MHz, CDCl3)δ=7.28(1H,s),7.24(1H,d,J=8.8Hz),7.05(2H,d,J=9.4Hz),6.86(1H,d,J=8.7Hz),6.74(2H,d,J=9.5Hz),1.63(6H,s). 19 F-NMR (376MHz, CDCl3)δ=-81.3(3F,t,J=10.2Hz),-108.6(2F,t,J=14.0Hz),-122.2(2F,s),-122.5(2F,s),-123.2(2F,s),-126.6(2F,s). [Industrial applicability]

[0082] The present invention provides an industrially feasible method for producing fluorine-containing biphenols. Fluorine-containing biphenols can be used as raw materials for synthesizing functional polymer materials used in the aerospace and semiconductor / photonics fields.

Claims

1. The following general formula (1) 【Transformation 34】 (In formula (1), R ｆ This refers to a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, which may have 1 to 5 ether-bonded oxygen atoms between carbon atoms. X is a fluorine atom, a bromine atom, or an iodine atom. Y is either a bromine atom or an iodine atom. A perfluoroalkyl dihalide represented by the following general formula (2) 【Chemistry 35】 (In formula (2), R １ａ and R １ｂ Each of these independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a methoxy group, or an ethoxy group. Phenols represented by the following general formula (3) 【Transformation 36】 (In formula (3), R １ａ and R １ｂ Each of these independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a methoxy group, or an ethoxy group. Biphenols represented by the following general formula (4) 【Chemistry 37】 (In formula (4), R ２ This includes a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 1 to 10 carbon atoms, a cyclic alkylene group having 5 to 10 carbon atoms, a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a difluoromethylene chain, or -C(CF ３ ) ２ - indicates, R ３ａ and R ３ｂ each independently represent a hydrogen atom, a methyl group, a hydroxymethyl group, an ethyl group, or a tert-butyl group (t-butyl group).) The following general formula (5) is characterized by reacting biphenols represented by in a solvent with sodium dithionite and a base. 【Transformation 38】 (In formula (5), R １ａ and R １ｂ Each of these independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a methoxy group, or an ethoxy group.) Fluorine-containing biphenols represented by the following general formula (6) 【Chemistry 39】 (In formula (6), R １ａ and R １ｂ Each of these independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a methoxy group, or an ethoxy group. Fluorine-containing biphenols represented by the following general formula (7) 【Chemistry 40】 (In formula (7), R ｆ This represents a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, which may have 1 to 5 ether-bonded oxygen atoms between carbon atoms. X is a fluorine atom, a bromine atom, or an iodine atom. R １ａ and R １ｂ Each of these independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a methoxy group, or an ethoxy group. Fluorine-containing biphenols represented by the following general formulas (8) and (9) 【Chemistry 41】 【Chemistry 42】 (In equations (8) and (9), R ｆ This represents a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, which may have 1 to 5 ether-bonded oxygen atoms between carbon atoms. X is a fluorine atom, a bromine atom, or an iodine atom. R ２ This includes a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 1 to 10 carbon atoms, a cyclic alkylene group having 5 to 10 carbon atoms, a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a difluoromethylene chain, or -C(CF ３ ) ２ (This indicates -.) Fluorine-containing biphenols represented by the following general formulas (10) and (11) 【Chemistry 43】 【Chemistry 44】 (In equations (10) and (11), R ｆ This represents a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, which may have 1 to 5 ether-bonded oxygen atoms between carbon atoms. X is a fluorine atom, a bromine atom, or an iodine atom. R ２ This includes a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 1 to 10 carbon atoms, a cyclic alkylene group having 5 to 10 carbon atoms, a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a difluoromethylene chain, or -C(CF ３ ) ２ - indicates, R ３ａ and R ３ｂ Each of these independently represents a hydrogen atom, a methyl group, a hydroxymethyl group, an ethyl group, or a tert-butyl group (t-butyl group). A method for producing fluorine-containing biphenols represented by [the specified formula].

2. The method for producing fluorine-containing biphenols according to claim 1, characterized in that the base reacts in the presence of sodium bicarbonate or cesium carbonate.

3. The method for producing fluorine-containing biphenols according to claim 1 or claim 2, characterized in that the solvent is at least one organic solvent selected from the group consisting of dimethyl sulfoxide, dimethyl acetamide, and acetonitrile, or a mixed solvent of the organic solvent and water.

4. Fluorine-containing biphenols represented by any of the following formulas (12) to (15). 【Chemistry 45】 【Chemistry 46】 【Chemistry 47】

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