Method for producing fluorine-containing compound

Abstract

This method for producing a fluorine-containing compound comprises fluorinating an organic compound having at least one fluorinated atom or bond in an organic solvent into which fluorine gas is introduced, the organic solvent containing a compound having a halogen atom and having a C-H bond or a double bond. The amount of the compound having a halogen atom and having a C-H bond or a double bond is at least 0.1 times the equivalent of the organic compound having at least one fluorinated atom or bond.

Description

Technical Field

[0001] The present application relates to a method for producing a fluorine-containing compound. Background Art

[0002] There are various industrially useful compounds among fluorine-containing compounds, and various production methods have been developed. As one of the fluorination methods for compounds having a structure capable of fluorination, a method of performing a fluorination reaction in a liquid phase using fluorine gas is known (for example, refer to Patent Document 1). Patent Document 1 describes a method of adding an auxiliary agent to a reaction system to improve the fluorination conversion rate.

[0003] Prior Art Documents

[0004] Patent Documents

[0005] Patent Document 1: WO 2000 / 056694 Summary of the Invention

[0006] Problems to be Solved by the Invention

[0007] According to the present inventors, in the case of fluorinating a fluorine-containing compound by the method of Patent Document 1, there is a need for a step of separately adding an auxiliary agent from the raw material and the organic solvent, or a step of removing the auxiliary agent from the product, or it is difficult to separate the auxiliary agent, or impurities remain in the system without removing the auxiliary agent, etc., and there is still room for improvement. In view of this situation, the present application provides a method for producing a fluorine-containing compound that can perform fluorination with good conversion rate and can simplify the process.

[0008] Solutions to the Problems

[0009] The present application includes the following aspects.

[0010] <1> A method for producing a fluorine-containing compound, comprising: fluorinating an organic compound having at least one atom or bond capable of fluorination in an organic solvent into which fluorine gas is introduced,

[0011] The organic solvent contains a compound having a halogen atom and having a C-H bond or a double bond,

[0012] The amount of the compound having a halogen atom and having a C-H bond or a double bond is 0.1 equivalent or more relative to the organic compound having at least one atom or bond capable of fluorination.

[0013] <2> The method for producing a fluorine-containing compound according to <1>, wherein when the amount of hydrogen atoms in each 1 mL of the organic solvent is set to Ch (mmol) and the amount of double bonds is set to Cd (mmol), Ct represented by Ct = Ch + 2Cd is 0.01 to 100 mmol.

[0014] <3>The method for producing a fluorine-containing compound according to <1> or <2>, wherein the organic solvent includes the compound having a halogen atom and having a C-H bond or a double bond and a perhalogenated compound.

[0015] <4>The method for producing a fluorine-containing compound according to <3>, wherein the content ratio of the compound having a halogen atom and having a C-H bond or a double bond in the organic solvent is 1% by mass or more relative to the total amount of the compound having a halogen atom and having a C-H bond or a double bond and the perhalogenated compound.

[0016] <5>The method for producing a fluorine-containing compound according to any one of <1> to <4>, which does not include the addition of an auxiliary agent.

[0017] <6>The method for producing a fluorine-containing compound according to any one of <1> to <5>, wherein the compound having a halogen atom and having a C-H bond or a double bond includes at least one selected from the group consisting of hydrocarbons, ether compounds, ester compounds, and ketone compounds.

[0018] <7>The method for producing a fluorine-containing compound according to any one of <1> to <6>, wherein the compound having a halogen atom and having a C-H bond or a double bond includes at least one selected from the group consisting of chloroolefins, hydrochloroolefins, hydrochlorofluoroollefins, hydrofluoroethers, hydrofluorocarbons, hydrochlorofluorocarbons, and hydrobromocarbons.

[0019] <8>The method for producing a fluorine-containing compound according to any one of <1> to <7>, wherein, in the organic compound having at least one atom or bond capable of fluorination, the atom capable of fluorination is a hydrogen atom bonded to a carbon atom, a chlorine atom bonded to a carbon atom, a bromine atom bonded to a carbon atom, or an iodine atom bonded to a carbon atom, and the bond capable of fluorination is a carbon-carbon unsaturated double bond or a carbon-carbon unsaturated triple bond.

[0020] Effect of the Invention

[0021] According to the present application, a method for producing a fluorine-containing compound capable of performing fluorination with a good conversion rate and simplifying the process can be provided. Detailed Description of the Embodiment

[0022] Hereinafter, the modes for implementing the embodiments of the present application will be described in detail. However, the embodiments of the present application are not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values and their ranges, which do not limit the embodiments of the present application.

[0023] In the present application, the term "process" includes a process independent of other processes. Even in the case where it cannot be clearly distinguished from other processes, as long as the purpose of the process is achieved, the process is also included.

[0024] In the present application, the numerical ranges represented by using "~" respectively include the numerical values described before and after "~" as the minimum value and the maximum value.

[0025] In the present application, each component may include a plurality of conforming substances. When there are a plurality of substances conforming to each component in the composition, unless otherwise specified, the content rate or content of each component means the total content rate or total content of the plurality of substances present in the composition.

[0026] In the present application, an "organic group" means a group having a carbon atom as a necessity.

[0027] In the present application, a "hydrocarbyl group" can be any of linear, branched, and cyclic, and can also be any of saturated aliphatic hydrocarbyl groups, unsaturated aliphatic hydrocarbyl groups, and aromatic hydrocarbyl groups.

[0028] In the present application, "partially halogenated" means that only a part of the halogenatable sites of a compound is halogenated.

[0029] In the present application, when a compound is represented by a specific formula (X), the compound represented by the formula (X) is sometimes denoted as compound (X).

[0030] [Method for manufacturing a fluorine-containing compound]

[0031] The method for manufacturing a fluorine-containing compound of the present application (hereinafter also denoted as "the present manufacturing method") includes: fluorinating an organic compound having at least one atom or bond capable of being fluorinated (hereinafter also denoted as "raw material compound") in an organic solvent into which fluorine gas is introduced, the organic solvent containing a compound having a halogen atom and having a C-H bond or a double bond (hereinafter also denoted as "specific solvent compound"), and the amount of the specific solvent compound being 0.1 equivalent or more relative to the raw material compound. Hereinafter, the fluorine-containing compound manufactured by the present manufacturing method (that is, the product obtained by fluorination of the raw material compound) is also denoted as "target compound". It should be noted that the raw material compound and the specific solvent compound are different compounds.

[0032] This manufacturing method includes a fluorination step in a liquid phase (hereinafter also referred to as "liquid-phase fluorination"). Generally, in liquid-phase fluorination, as the solvent, an organic solvent that is non-reactive to fluorine gas such as CF2ClCFCl2 (also known as "R-113"), perfluorotributylamine, etc. is used. This is because side reactions or a decrease in fluorination efficiency due to the fluorination of the solvent are suppressed. However, in the case of using only an organic solvent that is non-reactive to fluorine gas, the conversion rate of fluorination is low. Therefore, by adding an auxiliary agent such as benzene or toluene to the reaction system, the conversion rate is increased. On the other hand, the present inventors found that if a specific solvent compound is used as the solvent for liquid-phase fluorination, a good fluorination conversion rate can be obtained even without using an auxiliary agent. The reason is not necessarily clear, but it can be speculated as follows. The specific solvent compound has a C-H bond or a double bond in its structure. Therefore, in the liquid-phase fluorination step, the solvent itself is fluorinated. It is considered that fluorine radicals are generated in this process, promoting the fluorination of the raw material compound and increasing the conversion rate. Therefore, it can be speculated that the target compound can be obtained at a high conversion rate even without adding an auxiliary agent. According to this manufacturing method, for example, the addition step and removal step of the auxiliary agent, etc. can be omitted, or the impurities associated with the mixing of the auxiliary agent can be reduced. And if a compound to be converted into a desired fluorinated compound is used as the specific solvent compound, the desired fluorinated compound can also be obtained together.

[0033] (Raw material compound)

[0034] As the raw material compound for liquid-phase fluorination, an organic compound having at least one atom or bond capable of being fluorinated is used. The raw material compound can be a commercially available substance that can be obtained, or a synthetic product.

[0035] As the atom capable of being fluorinated, a hydrogen atom bonded to a carbon atom, a chlorine atom bonded to a carbon atom, a bromine atom bonded to a carbon atom, and an iodine atom bonded to a carbon atom can be cited.

[0036] As the bond capable of being fluorinated, a carbon-carbon unsaturated double bond and a carbon-carbon unsaturated triple bond can be cited.

[0037] The number of atoms or bonds capable of being fluorinated in the raw material compound only needs to be 1 or more. From the viewpoint of excellent solubility, the number of atoms capable of being fluorinated is preferably 1 to 1,000, more preferably 1 to 500. From the viewpoint of being able to improve the purity of the fluoride, the number of bonds capable of being fluorinated is preferably 1 to 30, more preferably 1 to 20.

[0038] The number of carbon atoms of the raw material compound only needs to be selected according to the target compound, preferably 4 or more, and in one embodiment, more preferably 4 to 1,000, further preferably 4 to 500, particularly preferably 4 to 100, extremely preferably 4 to 50, and even more preferably 4 to 20.

[0039] In one embodiment, from the viewpoint of increasing the yield of the target compound, the starting compound preferably has a halogen atom, more preferably has at least one selected from the group consisting of a fluorine atom and a chlorine atom, and still more preferably has a fluorine atom. From the viewpoints of improving solubility in the solvent and the yield of the target compound, the fluorine content in the starting compound (i.e., the ratio of fluorine atoms in the molecule) is preferably 30% by mass or more, more preferably 30 to 84% by mass, and still more preferably 30 to 76% by mass.

[0040] Examples of the starting compound include aliphatic hydrocarbons, aromatic hydrocarbons, ether compounds, ester compounds, amide compounds, thioether compounds, thioester compounds, etc. These compounds may be partially halogenated or may not be halogenated. The starting compound may be a compound in which the carbon skeleton contains a heteroatom or a heteroatomic group that does not change due to the fluorination reaction. Hereinafter, for convenience, a compound having both an ester bond and an ether bond is classified as an ester compound among the starting compounds.

[0041] The number of carbon atoms of the aliphatic hydrocarbon as the starting compound is preferably 4 or more, and in one embodiment, more preferably 4 to 1,000, still more preferably 4 to 500, particularly preferably 4 to 100, extremely preferably 4 to 50, and even more preferably 4 to 20. The aliphatic hydrocarbon may be saturated or unsaturated and may be linear, branched, or cyclic. The aliphatic hydrocarbon may or may not have a substituent other than a halogen atom, and preferably does not have one.

[0042] The number of carbon atoms of the aromatic hydrocarbon as the starting compound is preferably 4 or more, and in one embodiment, more preferably 4 to 1,000, still more preferably 4 to 500, particularly preferably 4 to 100, extremely preferably 4 to 50, and even more preferably 4 to 20. The aromatic hydrocarbon may or may not have a substituent other than a halogen atom. Examples of the substituent include an aliphatic hydrocarbon group having 1 to 100 carbon atoms.

[0043] The number of carbon atoms of the amide compound as the starting compound is preferably 4 or more, and in one embodiment, more preferably 4 to 1,000, still more preferably 4 to 500, particularly preferably 4 to 100, extremely preferably 4 to 50, and even more preferably 4 to 20. The amide compound is a compound having one or more amide groups. The amide compound may be a polyamide compound.

[0044] The number of carbon atoms of the thioether compound as the starting material compound is preferably 4 or more, and in one embodiment, more preferably 4 to 1,000, further preferably 4 to 500, particularly preferably 4 to 100, extremely preferably 4 to 50, and even more preferably 4 to 20. The thioether compound is a compound having one or more thioether bonds. The thioether compound may be a polysulfide compound.

[0045] The number of carbon atoms of the thioester compound as the starting material compound is preferably 4 or more, and in one embodiment, more preferably 4 to 1,000, further preferably 4 to 500, particularly preferably 4 to 100, extremely preferably 4 to 50, and even more preferably 4 to 20. The thioester compound is a compound having one or more thioester bonds. The thioester compound may be a polythioester compound.

[0046] The number of carbon atoms of the ester compound as the starting material compound is preferably 4 or more, and in one embodiment, more preferably 4 to 1,000, further preferably 4 to 500, particularly preferably 4 to 100, extremely preferably 4 to 50, and even more preferably 4 to 20. The ester compound is a compound having one or more ester bonds. The ester compound may be a polyester compound. The ester compound is preferably a monoester compound or a diester compound.

[0047] Examples of the ester compound include compounds represented by the following formula (1), compounds represented by the following formula (2), and the like.

[0048] R A1 -O-(C=O)-R B1 …(1)

[0049] R B2 -(C=O)-O-R A2 -O-(C=O)-R B3 …(2)

[0050] In formulas (1) and (2),

[0051] R A1 、R B1 、R B2 and R B3 are each independently a monovalent saturated hydrocarbon group, a halogenated monovalent saturated hydrocarbon group, a monovalent saturated hydrocarbon group containing a heteroatom, or a halogenated (monovalent saturated hydrocarbon containing a heteroatom) group,

[0052] R A2 is a divalent saturated hydrocarbon group, a halogenated divalent saturated hydrocarbon group, a divalent saturated hydrocarbon group containing a heteroatom, or a halogenated (divalent saturated hydrocarbon containing a heteroatom) group.

[0053] In the present application, the "monovalent saturated hydrocarbon group" can be any of a linear alkyl group, a branched alkyl group, and a cycloalkyl group. The "divalent saturated hydrocarbon group" can be any of a linear alkylene group, a branched alkylene group, and a cycloalkylene group. The linear alkyl group, the branched alkyl group, the linear alkylene group, and the branched alkylene group may contain an alicyclic structure.

[0054] In the present application, "halogenated" means that one or more hydrogen atoms present in the group are substituted by at least one halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Hydrogen atoms may or may not be present in the group.

[0055] In the present application, the "halogenated monovalent saturated hydrocarbon group" means a group in which one or more hydrogen atoms present in the monovalent saturated hydrocarbon group are substituted by halogen atoms. The "halogenated divalent saturated hydrocarbon group" means a group in which one or more hydrogen atoms present in the divalent saturated hydrocarbon group are substituted by halogen atoms.

[0056] In the present application, a "heteroatom" means an atom other than a carbon atom and a hydrogen atom, and examples thereof include a nitrogen atom, an oxygen atom, and a sulfur atom.

[0057] In the present application, the "monovalent saturated hydrocarbon group containing a heteroatom" means a group that contains a divalent heteroatom or a divalent group containing a heteroatom in the monovalent saturated hydrocarbon group. The "divalent saturated hydrocarbon group containing a heteroatom" means a group that contains a divalent heteroatom or a divalent group containing a heteroatom in the divalent saturated hydrocarbon group. Examples of the divalent heteroatom include -O- and -S-. In addition, examples of the divalent group containing a heteroatom include -NH-, -C(=O)-, and -SO2-.

[0058] In the present application, the "halogenated (monovalent saturated hydrocarbon group containing a heteroatom)" means a group in which one or more hydrogen atoms in the above-mentioned monovalent saturated hydrocarbon group containing a heteroatom are substituted by halogen atoms. The "halogenated (divalent saturated hydrocarbon group containing a heteroatom)" means a group in which one or more hydrogen atoms in the above-mentioned divalent saturated hydrocarbon group containing a heteroatom are substituted by halogen atoms.

[0059] In formula (1), preferably at least one of R A1 and R B1 contains a hydrogen atom. In addition, in formula (2), preferably at least one selected from the group consisting of R A2 , R B2 and R B3 contains a hydrogen atom.

[0060] 〔R A1 〕

[0061] In formula (1), R A1is a monovalent saturated hydrocarbon group, a halogenated monovalent saturated hydrocarbon group, a monovalent saturated hydrocarbon group containing a heteroatom, or a halogenated (monovalent saturated hydrocarbon containing a heteroatom) group.

[0062] As R A1 Examples of the monovalent saturated hydrocarbon group shown in A1 include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, and a cyclohexyl group.

[0063] As R A1 The halogenated monovalent saturated hydrocarbon group shown in A1 is preferably a halogenated alkyl group. The halogen atom contained in the halogenated monovalent saturated hydrocarbon group is preferably a fluorine atom, a chlorine atom, or a bromine atom, and more preferably a fluorine atom.

[0064] R A1 The monovalent saturated hydrocarbon group containing a heteroatom shown in A1 is preferably a monovalent saturated hydrocarbon group containing an etheric oxygen atom (i.e., -O-), and more preferably an alkyl group containing an etheric oxygen atom.

[0065] As R A1 The halogenated (monovalent saturated hydrocarbon containing a heteroatom) group shown in A1 is preferably a halogenated (alkyl group containing a heteroatom). The halogen atom contained in the halogenated (monovalent saturated hydrocarbon containing a heteroatom) group is preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogenated (monovalent saturated hydrocarbon containing a heteroatom) group is preferably a halogenated monovalent saturated hydrocarbon group containing an etheric oxygen atom, and more preferably a halogenated alkyl group containing an etheric oxygen atom.

[0066] From the viewpoint of excellent solubility in a solvent, the number of carbon atoms of R A1 is preferably 1 to 200, and more preferably 3 to 100.

[0067] Among them, from the viewpoint of excellent solubility in a solvent, R A1 is preferably represented by the following formula (A1). In other words, R A1 preferably further has an ether bond, and more preferably contains at least one selected from the group consisting of a polyether chain and a fluoropolyether chain.

[0068] R 11 O-(R 12 O) m1 -R 13 -…(A1)

[0069] In formula (A1), R 11 is an alkyl group optionally having a fluorine atom, R 12 are each independently an alkylene group having 1 to 6 carbon atoms optionally having a fluorine atom, R 13 is an alkylene group having 1 to 6 carbon atoms optionally having a fluorine atom, and m1 is an integer of 0 to 500.

[0070] In formula (A1), as R11 , examples thereof include an alkyl group and a fluoroalkyl group.

[0071] From the viewpoint of excellent solubility in a solvent, the number of carbon atoms of R 11 is preferably 1 to 100, more preferably 1 to 50, still more preferably 1 to 10, and particularly preferably 1 to 6.

[0072] R 11 The alkyl group represented may be a linear alkyl group, a branched alkyl group, or an alkyl group having a ring structure.

[0073] R 11 The fluoroalkyl group represented may be a linear fluoroalkyl group, a branched fluoroalkyl group, or a fluoroalkyl group having a ring structure.

[0074] Among them, R 11 is preferably an alkyl group, more preferably a linear alkyl group, and still more preferably a linear alkyl group having 1 to 6 carbon atoms.

[0075] In formula (A1), -(R 12 O) m1 - is preferably represented by the following formula (A2).

[0076] -[(R f1 O) k1 (R f2 O) k2 (R f3 O) k3 (R f4 O) k4 (R f5 O) k5 (R f6 O) k6 -…(A2)

[0077] Among them,

[0078] R f1 is a fluoroalkylene group having 1 carbon atom,

[0079] R f2 is a fluoroalkylene group having 2 carbon atoms,

[0080] R f3 is a fluoroalkylene group having 3 carbon atoms,

[0081] R f4 is a fluoroalkylene group having 4 carbon atoms,

[0082] R f5 is a fluoroalkylene group having 5 carbon atoms,

[0083] R f6 is a fluoroalkylene group having 6 carbon atoms.

[0084] k1, k2, k3, k4, k5, and k6 each independently represent an integer of 0 or more, and k1 + k2 + k3 + k4 + k5 + k6 is an integer from 0 to 500.

[0085] From the viewpoint of excellent solubility in a solvent, k1 + k2 + k3 + k4 + k5 + k6 is preferably an integer from 1 to 500, more preferably an integer from 1 to 300, still more preferably an integer from 5 to 200, and particularly preferably an integer from 10 to 150.

[0086] It should be noted that the bonding order of (R f1 O) to (R f6 O) in formula (A2) is arbitrary. k1 to k6 in formula (A2) respectively represent the number of (R f1 O) to (R f6 O), and do not represent the configuration. For example, (R f5 O) k5 indicates that the number of (R f5 O) is k5, and does not represent the block configuration structure of (R f5 O) k5 . Similarly, the description order of (R f1 O) to (R f6 O) does not represent the bonding order of each unit.

[0087] Among R f3 to R f6 , the fluoroalkylene group can be a linear fluoroalkylene group, a branched fluoroalkylene group, or a fluoroalkylene group having a ring structure.

[0088] Specific examples of R f1 include -CF2- and -CHF-.

[0089] Specific examples of R f2 include -CF2CF2-, -CF2CHF-, -CHFCF2-, -CHFCHF-, -CH2CF2-, and -CH2CHF-.

[0090] Specific examples of R f3Specific examples include -CF2CF2CF2-, -CF2CHFCF2-, -CF2CH2CF2-, -CHFCF2CF2-, -CHFCHFCF2-, -CHFCHFCHF-, -CHFCH2CF2-, -CH2CF2CF2-, -CH2CHFCF2-, -CH2CH2CF2-, -CH2CF2CHF-, -CH2CHFCHF-, -CH2CH2CHF-, -CF(CF3)-CF2-, -CF(CHF2)-CF2-, -CF(CH2F)-CF2-, -CF(CH3)-CF2-, -CF(CF3)-CHF-, -CF(CHF2)-CHF-, -CF(CH2F)-CHF-, -CF(CH3)-CHF-, -CF(CF3)-CH2-, -CF(CHF2)-CH2-, -CF(CH2F)-CH2-, -CF(CH3)-CH2-, -CH(CF3)-CF2-, -CH(CHF2)-CF2-, -CH(CH2F)-CF2-, -CH(CH3)-CF2-, -CH(CF3)-CHF-, -CH(CHF2)-CHF-, -CH(CH2F)-CHF-, -CH(CH3)-CHF-, -CH(CF3)-CH2-, -CH(CHF2)-CH2-, and -CH(CH2F)-CH2-.

[0091] As R f4 Specific examples include -CF2CF2CF2CF2-, -CF2CF2CF2CHF-, -CF2CF2CF2CH2-, -CF2CHFCF2CF2-, -CHFCHFCF2CF2-, -CH2CHFCF2CF2-, -CF2CH2CF2CF2-, -CHFCH2CF2CF2-, -CH2CH2CF2CF2-, -CHFCF2CHFCF2-, -CH2CF2CHFCF2-, -CF2CHFCHFCF2-, -CHFCHFCHFCF2-, -CH2CHFCHFCF2-, -CF2CH2CHFCF2-, -CHFCH2CHFCF2-, -CH2CH2CHFCF2-, -CF2CH2CH2CF2-, -CHFCH2CH2CF2-, -CH2CH2CH2CF2-, -CHFCH2CH2CHF-, -CH2CH2CH2CHF-, and -cycloC4F6-.

[0092] As R f5Specific examples thereof include -CF2CF2CF2CF2CF2-, -CHFCF2CF2CF2CF2-, -CH2CHFCF2CF2CF2-, -CF2CHFCF2CF2CF2-, -CHFCHFCF2CF2CF2-, -CF2CH2CF2CF2CF2-, -CHFCH2CF2CF2CF2-, -CH2CH2CF2CF2CF2-, -CF2CF2CHFCF2CF2-, -CHFCF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CH2CF2CF2CF2CH2-, and -cycloC5F8-.

[0093] As R f6 Specific examples thereof include -CF2CF2CF2CF2CF2CF2-, -CF2CF2CHFCHF CF2CF2-, -CHFCF2CF2CF2CF2CF2-, -CHFCHFCHFCHFCHFCHF-, -CHFCF2CF2CF2CF2CH2-, -CH2CF2CF2CF2CF2CH2-, and -cycloC6F 10 -.

[0094] Here, -cycloC4F6- refers to a perfluorocyclobutane diyl, and specific examples thereof include perfluorocyclobutane-1,2-diyl. -cycloC5F8- refers to a perfluorocyclopentane diyl, and specific examples thereof include perfluorocyclopentane-1,3-diyl. -cycloC6F 10 - refers to a perfluorocyclohexane diyl, and specific examples thereof include perfluorocyclohexane-1,4-diyl.

[0095] Among them, -(R 12 O) m1 - preferably contains at least one selected from the group consisting of the structures represented by the following formulas (F1) to (F3), and more preferably contains the structure represented by formula (F2).

[0096] -(R f1 O) k1 -(R f2 O) k2 -…(F1)

[0097] -(R f2 O) k2 -(R f4 O) k4 -…(F2)

[0098] -(R f3 O) k3 -…(F3)

[0099] Among them, each symbol in formulas (F1) to (F3) is the same as that in the above formula (A2).

[0100] In formulas (F1) and (F2), (R f1 O) and (R f2 O), (R f2 O) and (R f4 O) can be bonded in any order. For example, (R f1 O) and (R f2 O) can be alternately arranged, (R f1 O) and (R f2 O) can be arranged in block respectively, and in addition, it can also be random. The same is true for formula (F2).

[0101] In formula (F1), k1 is preferably 1 to 30, more preferably 1 to 20. In addition, k2 is preferably 1 to 30, more preferably 1 to 20.

[0102] In formula (F2), k2 is preferably 1 to 30, more preferably 1 to 20. In addition, k4 is preferably 1 to 30, more preferably 1 to 20.

[0103] In formula (F3), k3 is preferably 1 to 30, more preferably 1 to 20.

[0104] In formula (A1), as R 13 , groups the same as the above R f1 to R f6 can be listed.

[0105] Among them, R 13 is preferably a fluoroalkylene group having 1 to 4 carbon atoms.

[0106] As a specific example of R A1 , for example, the following structures can be listed. * represents the bonding site with -O-, n1 represents an integer from 0 to 60, and n2 represents an integer from 0 to 500. As n1, for example, 13 can be listed, and as n2, for example, 7 can be listed.

[0107]

[0108] 〔R B1 〕

[0109] In formula (1), R B1 is a monovalent saturated hydrocarbon group, a halogenated monovalent saturated hydrocarbon group, a monovalent saturated hydrocarbon group containing a heteroatom, or a halogenated (monovalent saturated hydrocarbon containing a heteroatom) group.

[0110] As R B1Examples of the monovalent saturated hydrocarbon group shown include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, and a cyclohexyl group.

[0111] As R B1 The halogenated monovalent saturated hydrocarbon group shown is preferably a halogenated alkyl group. The halogen atom contained in the halogenated monovalent saturated hydrocarbon group is preferably a fluorine atom, a chlorine atom, or a bromine atom.

[0112] R B1 The monovalent saturated hydrocarbon group containing a heteroatom shown is preferably a monovalent saturated hydrocarbon group containing an etheric oxygen atom (i.e., -O-), more preferably an alkyl group containing an etheric oxygen atom. In other words, R B1 Preferably further has an ether bond.

[0113] As R B1 The halogenated (monovalent saturated hydrocarbon group containing a heteroatom) group shown is preferably a halogenated (alkyl group containing a heteroatom). The halogen atom contained in the halogenated (monovalent saturated hydrocarbon group containing a heteroatom) group is preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogenated (monovalent saturated hydrocarbon group containing a heteroatom) group is preferably a halogenated monovalent saturated hydrocarbon group containing an etheric oxygen atom, more preferably a halogenated alkyl group containing an etheric oxygen atom.

[0114] From the viewpoint of excellent solubility in a solvent, the number of carbon atoms of R B1 is preferably 1 to 100, more preferably 2 to 50, and further preferably 3 to 20.

[0115] From the viewpoint of excellent solubility in a solvent, R B1 preferably contains at least one fluorine atom and preferably does not contain a hydrogen atom.

[0116] Among them, from the viewpoint of excellent solubility in a solvent, R B1 is preferably represented by the following formula (B1).

[0117] R 21 O-(R 22 O) m2 -R 23 -…(B1)

[0118] In formula (B1), R 21 is an alkyl group optionally having a fluorine atom, R 22 are each independently an alkylene group having 1 to 6 carbon atoms optionally having a fluorine atom, R 23 is an alkylene group having 1 to 6 carbon atoms optionally having a fluorine atom, and m2 is an integer of 0 to 20.

[0119] In formula (B1), as R 21 , examples include an alkyl group and a fluoroalkyl group.

[0120] From the viewpoint of excellent solubility in a solvent, R 21 preferably has 1 to 50 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 6 carbon atoms.

[0121] R 21 The alkyl group represented by R may be a linear alkyl group, a branched alkyl group, or an alkyl group having a ring structure.

[0122] R 21 The fluoroalkyl group represented by R may be a linear fluoroalkyl group, a branched fluoroalkyl group, or a fluoroalkyl group having a ring structure.

[0123] Among them, R 21 is preferably a fluoroalkyl group, more preferably a linear fluoroalkyl group, still more preferably a linear fluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably a linear perfluoroalkyl group having 1 to 6 carbon atoms.

[0124] In formula (B1), -(R 22 O) m2 - is preferably represented by the above formula (A2).

[0125] In formula (B1), m2 is preferably 0 to 15, more preferably 0 to 10, still more preferably 0 to 4, and particularly preferably 0 to 2.

[0126] In formula (B1), as R 23 , the same groups as those of the above R f1 to R f6 can be mentioned.

[0127] Among them, R 23 is preferably a fluoroalkylene group having 1 to 3 carbon atoms, more preferably a perfluoroalkylene group having 1 to 3 carbon atoms.

[0128] As a specific example of R B1 , for example, the following structures can be mentioned. * indicates the bonding site to the -O-(C=O)- bond.

[0129]

[0130] 〔R A2 〕

[0131] In formula (2), R A2 is a divalent saturated hydrocarbon group, a halogenated divalent saturated hydrocarbon group, a divalent saturated hydrocarbon group containing a heteroatom, or a halogenated (divalent saturated hydrocarbon containing a heteroatom) group.

[0132] As R A2Examples of the divalent saturated hydrocarbon group, halogenated divalent saturated hydrocarbon group, divalent saturated hydrocarbon group containing a hetero atom, or halogenated (divalent saturated hydrocarbon containing a hetero atom) group include those obtained by removing one hydrogen atom or halogen atom from the monovalent saturated hydrocarbon group, halogenated monovalent saturated hydrocarbon group, monovalent saturated hydrocarbon group containing a hetero atom, or halogenated (monovalent saturated hydrocarbon containing a hetero atom) group represented by R in Formula (1). A1 From the viewpoint of excellent solubility in a solvent, the number of carbon atoms of R is preferably 1 to 200, more preferably 3 to 100.

[0133] From the viewpoint of excellent solubility in a solvent, R A2 is preferably represented by the following formula (A5). In other words, R

[0134] preferably further has an ether bond, and more preferably contains at least one selected from the group consisting of a polyether chain and a fluoropolyether chain. A2 -R A2 O-(R

[0135] -R 31 O)-(R 32 O) m5 -R 33 -…(A5)

[0136] In formula (A5), each of R 31 and R 33 is independently an alkylene group having 1 to 6 carbon atoms which may optionally have a fluorine atom, each of R 32 is independently an alkylene group having 1 to 6 carbon atoms which may optionally have a fluorine atom, and m5 is an integer of 0 to 500.

[0137] In formula (A5), as R 31 and R 33 , the same groups as R 13 in formula (A1) can be independently listed.

[0138] In formula (A5), as -(R 32 O) m5 -, the same groups as -(R 12 O) m1 - in formula (A1) can be listed.

[0139] Specific examples of R A2 include, for example, the following structures. * represents the bonding site to -O-, and n2 represents an integer of 0 to 500.

[0140]

[0141] 〔R B2 and R B3 〕

[0142] In formula (2), R B2 and R B3 are each independently a monovalent saturated hydrocarbon group, a halogenated monovalent saturated hydrocarbon group, a monovalent saturated hydrocarbon group containing a heteroatom, or a halogenated (monovalent saturated hydrocarbon containing a heteroatom) group.

[0143] As the monovalent saturated hydrocarbon group, halogenated monovalent saturated hydrocarbon group, monovalent saturated hydrocarbon group containing a heteroatom, or halogenated (monovalent saturated hydrocarbon containing a heteroatom) group represented by R B2 or R B3 the same groups as those of the monovalent saturated hydrocarbon group, halogenated monovalent saturated hydrocarbon group, monovalent saturated hydrocarbon group containing a heteroatom, or halogenated (monovalent saturated hydrocarbon containing a heteroatom) group represented by R B1 shown in formula (1) can be cited.

[0144] As an example of the ester compound, the following compound (T1) etc. can also be cited.

[0145]

[0146] The number of carbon atoms of the ether compound as the starting compound is preferably 4 or more, and in one embodiment, more preferably 4 to 1,000, still more preferably 4 to 500, particularly preferably 4 to 100, extremely preferably 4 to 50, and even more preferably 4 to 20. The ether compound is a compound having one or more ether bonds. The ether compound may be a polyether compound.

[0147] In one embodiment, the ether compound has the following structure.

[0148] R x -O-R Y

[0149] In the formula,

[0150] R x and R Y are each independently a monovalent saturated hydrocarbon group, a halogenated monovalent saturated hydrocarbon group, a monovalent saturated hydrocarbon group containing a heteroatom, or a halogenated (monovalent saturated hydrocarbon containing a heteroatom) group. Among them, at least one of R x and R Y has at least one atom or bond capable of being fluorinated.

[0151] The details of the monovalent saturated hydrocarbon group, halogenated monovalent saturated hydrocarbon group, monovalent saturated hydrocarbon group containing a heteroatom, or halogenated (monovalent saturated hydrocarbon containing a heteroatom) group are the same as the details described respectively in the item of the ester compound as the starting compound, that is, the compound represented by formula (1).

[0152] As R x and R YThe monovalent saturated hydrocarbon groups shown may each independently be exemplified by, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, and cyclohexyl.

[0153] As R x and R Y The halogenated monovalent saturated hydrocarbon groups shown are each independently preferably a halogenated alkyl group. The halogen atom contained in the halogenated monovalent saturated hydrocarbon group is preferably a fluorine atom, a chlorine atom, or a bromine atom, more preferably a fluorine atom.

[0154] As R x and R Y The heteroatom-containing monovalent saturated hydrocarbon groups shown are each independently preferably a monovalent saturated hydrocarbon group containing an etheric oxygen atom (i.e., -O-), more preferably an alkyl group containing an etheric oxygen atom.

[0155] As R x and R Y The halogenated (heteroatom-containing monovalent saturated hydrocarbon) groups shown are each independently preferably a halogenated (heteroatom-containing alkyl) group. The halogen atom contained in the halogenated (heteroatom-containing monovalent saturated hydrocarbon) group is preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogenated (heteroatom-containing monovalent saturated hydrocarbon) group is preferably a halogenated monovalent saturated hydrocarbon group containing an etheric oxygen atom, more preferably a halogenated alkyl group containing an etheric oxygen atom.

[0156] From the viewpoint of excellent solubility in a solvent, the number of carbon atoms of R x and R Y are each independently preferably 1 to 1,000, more preferably 1 to 500, and further preferably 1 to 300.

[0157] Specific examples of the starting compound may also include, for example, the following compounds listed in International Publication No. 2000 / 056694 and International Publication No. 2002 / 004397. In the formula, Cy represents cyclohexyl, Ph represents phenyl, and n, m, p, k, and r represent integers of 1 or more.

[0158] CF3CF2COOCH2CH2CH3,

[0159] CF3CF2COOCH2CH(OCH2CH2CH3)CH3,

[0160] CF3CF2COOCH2CH(OCH2CH2CHClCH2Cl)CH3,

[0161] CF3CF2COO(CH2)4OCHClCH2Cl

[0162] CF3CF2COO(CH2)5OCHClCH2Cl,

[0163] CF3(CF3CF2CF2O)CFCOO(CH2)4OCHClCH2Cl,

[0164] CF3(CF3CF2CF2O)CFCOO(CH2)5OCHClCH2Cl,

[0165] CF3(CF2ClCFClCF2CF2O)CFCOOCH2CH(OCH2CH2CHClCH2Cl)CH3, CF2ClCFClOCF2CF2CF2COO(CH2)4OCHClCH2Cl,

[0166] CClF2COOCH2CH2Cl,

[0167] CBrF2COOCH2CH2Br,

[0168] CF2BrCF2OCF(CF3)COOCH2CH(OCH2CH2Br)CH3,

[0169] CF2ClCFClCF2CF(CF3)OCF(CF3)COOCH2CH[OCH(CH3)CHClCH2Cl]CH3,

[0170] CH2ClCHClCH2COOCH2CF2CFClCF2Cl,

[0171] CF3(CH3CH2CH2O)CFCOOCH2CF(OCF2CF2CF3)CF3,

[0172] CF3(CH3CH2CH2O)CFCOOCH2CF(OCH2CH2CH3)CF3.

[0173] CF3(CF3CF2CF2O)CFCOOCH2CH(OCH2CH2CH3)CH3,

[0174] CF3(CF3CF2CF2O)CFCOOCH2CH(OCH2CH2CHClCH2Cl)CH3,

[0175] CF3(CF3CF2CF2O)CFCOOCH2CH(OCH2Cy)CH3,

[0176] CF3(CF3CF2CF2O)CFCOOCH2CH(OCH2Ph)CH3,

[0177] CF3(CF3CF2CF2O)CFCOOCH2CH(O(CH2)9CH3)CH3,

[0178] CF3(CF3CF2CF2O)CFCOO(CH2)3OCH2Ph,

[0179] CF3(CF3CF2CF2O)CFCOO(CH2)3OCH2CH=CH2,

[0180] CF3CF2COOCH2CH2CHClCH2Cl,

[0181] CF2ClCFClCF2COOCH2CH2CHClCH2Cl,

[0182] CF2ClCF2CFClCOOCH2CH2CHClCH2Cl,

[0183]

[0184] CF3CF2COO(CH2) n OCOCF2CF3,

[0185] CF3CF2COO[CH2CH(CH3)O] m (CH2) p OCOCF2CF3,

[0186] CF3CF2COO(CH2CH2O) k (CH2) r OCOCF2CF3,

[0187] CF3CF2COO(CH2)2O(CH2)2OCOCF2CF3,

[0188] CF3CF2CF2OCF(CF3)COOCH2CH(CH3)O(CH2)5OCOCF(CF3)OCF2CF2CF3,

[0189] CF3CF2COO(CH2)2O(CH2)2OCH(CH3)CH2OCOCF2CF3。

[0190] CH3CH2OCH2CH2OCH2CH2OCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3。

[0191] From the viewpoint of increasing the yield of the target compound, the boiling point of the starting compound is preferably 30 °C or higher, more preferably 50 °C or higher, still more preferably 100 °C or higher. From the same viewpoint, the boiling point of the starting compound is preferably 500 °C or lower, more preferably 400 °C or lower, still more preferably 300 °C or lower. From the foregoing viewpoint, the boiling point of the starting compound is preferably 30 to 500 °C, more preferably 50 to 400 °C, still more preferably 100 to 300 °C. In the present application, "boiling point" is the boiling point under normal pressure (760 mmHg).

[0192] The number average molecular weight (Mn) of the starting compound is preferably 100 to 100,000, more preferably 100 to 20,000, still more preferably 300 to 10,000, and particularly preferably 400 to 6,000. If Mn is at least the foregoing lower limit value, decomposition reactions in the gas phase are easily suppressed in liquid-phase fluorination. If Mn is at most the foregoing upper limit value, purification of the target compound is facilitated. Mn is the number average value of the molecular weights of the respective molecules calculated from the molecular structure determined by 1 1H-NMR and 19 19F-NMR.

[0193] (Target compound)

[0194] The fluorinated compound as the target compound is a compound in which the atoms or bonds capable of being fluorinated in the starting compound are fluorinated. In liquid-phase fluorination, a fluorinated compound having a structure corresponding to the carbon skeleton of the starting compound is produced. Among them, in the case where the starting compound has a carbon-carbon unsaturated bond, one or more fluorine atoms can be added to the unsaturated bond to become a bonded state.

[0195] As the target compound, fluorides of the compounds exemplified in the item of the starting compound can be cited. Therefore, as the target compound, fluorinated aliphatic hydrocarbons, aromatic hydrocarbons, ether compounds, ester compounds, amide compounds, thioether compounds, thioester compounds, etc. can be cited. The target compound may be a compound in which the carbon skeleton of these compounds contains a heteroatom or a heteroatomic group that does not change due to the fluorination reaction.

[0196] Among them, specific examples of useful target compounds include perfluoroalkanes, perfluoroether compounds, chlorofluorocarbons, chlorofluoroether compounds, etc.

[0197] The "target compound" does not necessarily refer to the final target. The fluorinated compound as the target compound can be directly and effectively utilized or can be effectively utilized by chemically converting it into other compounds.

[0198] When the starting compound is an ester compound represented by the aforementioned formula (1), the target compound is preferably a compound represented by the following formula (6). Additionally, when the starting compound is a compound represented by the aforementioned formula (2), the target compound is preferably a compound represented by the following formula (7).

[0199] R AF1 -O-(C=O)-R BF1 …(6)

[0200] R BF2 -(C=O)-O-R AF2 -O-(C=O)-R BF3 …(7)

[0201] In formulas (6) and (7),

[0202] R AF1 、R BF1 、R AF2 、R BF2 and R BF3 are respectively groups corresponding to R A1 、R B1 、R A2 、R B2 and R B3 ;

[0203] R A1 、R B1 、R A2 、R B2 and R B3 are each independently a group that does not contain a hydrogen atom, R AF1 、R BF1 、R AF2 、R BF2 and R BF3 is the same group as R A1 、R B1 、R A2 、R B2 and R B3 ;

[0204] R A1 、R B1 、R A2 、R B2 and R B3 are each independently a group that contains a hydrogen atom, R AF1 、R BF1 、R AF2 、R BF2 and R BF3 is R A1 、R B1 、R A2 、R B2 and R B3A group in which all hydrogen atoms present in [group name] are replaced by fluorine atoms.

[0205] [R AF1

[0206] In formula (6), R AF1 is the group corresponding to R A1 .

[0207] When R A1 contains hydrogen atoms, R AF1 is a group in which all hydrogen atoms present in R A1 are replaced by fluorine atoms. When R A1 does not contain hydrogen atoms, R AF1 is the same group as R A1 .

[0208] From the viewpoint of excellent solubility in a solvent, R AF1 is preferably represented by the following formula (A3).

[0209] R 14 O-(R 15 O) m3 -R 16 -…(A3)

[0210] In formula (A3), R 14 is a perfluoroalkyl group, R 15 are each independently a perfluoroalkylene group having 1 to 6 carbon atoms, R 16 is a perfluoroalkylene group having 1 to 6 carbon atoms, and m3 is an integer of 0 to 500.

[0211] In formula (A3), R 14 corresponds to R 11 in formula (A1). When R 11 contains hydrogen atoms, R 14 is a group in which all hydrogen atoms contained in R 11 are replaced by fluorine atoms. When R 11 does not contain hydrogen atoms, R 14 is the same as R 11 .

[0212] In formula (A3), -(R 15 O) m3 - corresponds to -(R 12 O) m1 - in formula (A1). When R 12 contains hydrogen atoms, R 15 is a group in which all hydrogen atoms contained in R 12 are replaced by fluorine atoms. When R 12 does not contain hydrogen atoms, R 15 is the same as R 12 ​Same.

[0213] In formula (A3), -(R 15 O) m3 - is preferably represented by the following formula (A4).

[0214] -[(R ff1 O) k7 (R ff2 O) k8 (R ff3 O) k9 (R ff4 O) k10 (R ff5 O) k11 (R ff6 O) k12 -…(A4)

[0215] Wherein,

[0216] R ff1 is a perfluoroalkylene group having 1 carbon atom,

[0217] R ff2 is a perfluoroalkylene group having 2 carbon atoms,

[0218] R ff3 is a perfluoroalkylene group having 3 carbon atoms,

[0219] R ff4 is a perfluoroalkylene group having 4 carbon atoms,

[0220] R ff5 is a perfluoroalkylene group having 5 carbon atoms,

[0221] R ff6 is a perfluoroalkylene group having 6 carbon atoms.

[0222] k7, k8, k9, k10, k11 and k12 each independently represent an integer of 0 or more, and k7 + k8 + k9 + k10 + k11 + k12 is an integer of 0 to 500.

[0223] In formula (A4), R ff1 ~R ff6 corresponds to R f1 ~R f6 in formula (A2). For example, when R f1 contains a hydrogen atom, R ff1 is a group in which all hydrogen atoms contained in R f1 are replaced by fluorine atoms. When R f1 does not contain a hydrogen atom, R ff1 is the same as R f1 . Regarding R ff2 ~R ff6 , it is also the same as Rff1 Same

[0224] From the viewpoint of excellent solubility in a solvent, k7 + k8 + k9 + k10 + k11 + k12 is preferably an integer of 1 to 500, more preferably an integer of 1 to 300, still more preferably an integer of 5 to 200, and particularly preferably an integer of 10 to 150.

[0225] Among them, -(R 15 O) m3 - preferably contains at least one selected from the group consisting of the structures represented by the following formulas (G1) to (G3), and more preferably contains the structure represented by formula (G2).

[0226] -(R ff1 O) k7 -(R ff2 O) k8 -…(G1)

[0227] -(R ff2 O) k8 -(R ff4 O) k10 -…(G2)

[0228] -(R ff3 O) k9 -…(G3)

[0229] Among them, each symbol in formulas (G1) to (G3) is the same as that in the above formula (A4).

[0230] In formulas (G1) and (G2), the bonding order of (R ff1 O) and (R ff2 O), (R ff2 O) and (R ff4 O) is arbitrary respectively. For example, (R ff1 O) and (R ff2 O) can be alternately arranged, (R ff1 O) and (R ff2 O) can be block-arranged respectively, and in addition, it can also be random. The same applies to formula (G2).

[0231] In formula (G1), k7 is preferably 1 to 30, more preferably 1 to 20. In addition, k8 is preferably 1 to 30, more preferably 1 to 20.

[0232] In formula (G2), k8 is preferably 1 to 30, more preferably 1 to 20. In addition, k10 is preferably 1 to 30, more preferably 1 to 20.

[0233] In formula (G3), k9 is preferably 1 to 30, more preferably 1 to 20.

[0234] In formula (A3), R 16 corresponds to R in formula (A1). 13 . When R 13 contains a hydrogen atom, R 16 is a group in which all hydrogen atoms contained in R 13 are replaced by fluorine atoms. When R 13 does not contain a hydrogen atom, R 16 is the same as R 13 .

[0235] As R 16 , groups the same as the above R ff1 to R ff6 can be exemplified.

[0236] Among them, R 16 is preferably a perfluoroalkylene group having 1 to 3 carbon atoms.

[0237] In formula (A3), m3 corresponds to m1 in formula (A1). m3 is the same as m1.

[0238] As a specific example of R AF1 , for example, the following structures can be exemplified. * represents the bonding site to -O-, n1 represents an integer of 0 to 60, and n2 represents an integer of 0 to 500. As n1, for example, 13 can be exemplified, and as n2, for example, 7 can be exemplified.

[0239]

[0240] 〔R BF1 〕

[0241] In formula (6), R BF1 is a group corresponding to R B1 .

[0242] When R B1 contains a hydrogen atom, R BF1 is a group in which all hydrogen atoms present in R B1 are replaced by fluorine atoms. When R B1 does not contain a hydrogen atom, R BF1 is the same as R B1 .

[0243] From the viewpoint of excellent solubility in a solvent, R BF1 is preferably represented by the following formula (B2).

[0244] R 24 O-(R 25 O) m4 -R 26 -…(B2)

[0245] In formula (B2), R 24 is a perfluoroalkyl group, and each R 25 is independently a perfluoroalkylene group having 1 to 6 carbon atoms. R 26 is a perfluoroalkylene group having 1 to 6 carbon atoms, and m4 is an integer from 0 to 20.

[0246] In formula (B2), R 24 corresponds to R 21 in formula (B1). When R 21 contains a hydrogen atom, R 24 is a group in which all hydrogen atoms contained in R 21 are replaced by fluorine atoms. When R 21 does not contain a hydrogen atom, R 24 is the same as R 21 .

[0247] In formula (B2), -(R 25 O) m4 - corresponds to -(R 22 O) m2 - in formula (B1). When R 22 contains a hydrogen atom, R 25 is a group in which all hydrogen atoms contained in R 22 are replaced by fluorine atoms. When R 22 does not contain a hydrogen atom, R 25 is the same as R 22 .

[0248] In formula (B2), -(R 25 O) m4 - is preferably represented by the above formula (A4).

[0249] In formula (B2), R 26 corresponds to R 23 in formula (B1). When R 23 contains a hydrogen atom, R 26 is a group in which all hydrogen atoms contained in R 23 are replaced by fluorine atoms. When R 23 does not contain a hydrogen atom, R 26 is the same as R 23 .

[0250] In formula (B2), m4 corresponds to m2 in formula (B1). m4 is the same as m2.

[0251] As specific examples of R BF1 , the following structures can be listed, for example. * indicates the bonding site to the -O-(C=O)- bond.

[0252]

[0253] 〔R AF2 〕

[0254] In formula (7), R AF2 is a group corresponding to R A2 .

[0255] When R A2 contains a hydrogen atom, R AF2 is a group formed by substituting all hydrogen atoms present in R A2 with fluorine atoms. When R A2 does not contain a hydrogen atom, R AF2 is the same group as R A2 .

[0256] From the viewpoint of excellent solubility in a solvent, R AF2 is preferably represented by the following formula (A6). In other words, R AF2 preferably also has an ether bond.

[0257] -R 34 O-(R 35 O) m6 -R 36 -…(A6)

[0258] In formula (A6), R 34 and R 36 are each independently a perfluoroalkylene group having 1 to 6 carbon atoms, R 35 are each independently a perfluoroalkylene group having 1 to 6 carbon atoms, and m6 is an integer of 0 to 500.

[0259] In formula (A6), R 34 and R 36 correspond to R 31 and R 33 in formula (A5), respectively. When R 31 contains a hydrogen atom, R 34 is a group formed by substituting all hydrogen atoms contained in R 31 with fluorine atoms. When R 31 does not contain a hydrogen atom, R 34 is the same as R 31 . When R 33 contains a hydrogen atom, R 36 is a group formed by substituting all hydrogen atoms contained in R 33 with fluorine atoms. When R 33 does not contain a hydrogen atom, R 36 is the same as R 33 .

[0260] In formula (A6), -(R 35 O) m6 - corresponds to -(R 32 O)m5 - R 32 When it contains a hydrogen atom, R 35 is a group in which all hydrogen atoms contained in R 32 are replaced by fluorine atoms. When R 32 does not contain a hydrogen atom, R 35 is the same as R 32 .

[0261] In formula (A6), as R 34 and R 36 , groups the same as R 31 and R 33 in formula (A5) can be independently listed respectively.

[0262] In formula (A6), as -(R 35 O) m6 -, a group the same as -(R 32 O) m5 - in formula (A5) can be listed.

[0263] As a specific example of R AF2 , for example, the following structures can be listed. * indicates the bonding site to -O-, and n2 represents an integer from 0 to 500.

[0264]

[0265] 〔R BF2 and R BF3 〕

[0266] In formula (7), R BF2 and R BF3 are groups corresponding to R B2 and R B3 respectively.

[0267] When R B2 contains a hydrogen atom, R BF2 is a group in which all hydrogen atoms present in R B2 are replaced by fluorine atoms. When R B2 does not contain a hydrogen atom, R BF2 is the same as R B2 .

[0268] When R B3 contains a hydrogen atom, R BF3 is a group in which all hydrogen atoms present in R B3 are replaced by fluorine atoms. When R B3 does not contain a hydrogen atom, R BF3 is the same as R B3 .

[0269] R BF2or R BF3 Examples of the group shown may include the same groups as the R BF1 shown in formula (6).

[0270] When the starting compound is the aforementioned R x -O-R Y ether compound shown, the target compound is preferably a compound represented by the following formula.

[0271] R XF -O-R YF

[0272] In the formula, R XF and R YF are respectively groups corresponding to R X and R Y ;

[0273] R X and R Y are each independently a group without a hydrogen atom, R XF and R YF are the same groups as R X and R Y ;

[0274] R X and R Y are each independently a group containing a hydrogen atom, R XF and R YF are groups in which all hydrogen atoms present in R X and R Y are replaced by fluorine atoms.

[0275] The number average molecular weight of the target compound is not particularly limited, preferably 100 to 100,000, more preferably 100 to 20,000, still more preferably 300 to 10,000, and particularly preferably 400 to 6,000.

[0276] (organic solvent)

[0277] In liquid-phase fluorination, an organic solvent is used as a solvent in the liquid phase. The organic solvent contains a specific solvent compound. The organic solvent may contain or may not contain compounds other than the specific solvent compound on the basis of containing the specific solvent compound. From the viewpoint of excellent conversion rate in liquid-phase fluorination, the content rate of the specific solvent compound relative to the total amount of the organic solvent is preferably 1% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and may be 50% by mass or more. From the viewpoint of suppressing heat release, the aforementioned content rate may be 90% by mass or less, may be 80% by mass or less, and may be 70% by mass or less. From the aforementioned viewpoints, the aforementioned content rate may be 1 to 90% by mass, may be 10 to 80% by mass, may be 20 to 70% by mass, and may be 50 to 70% by mass.

[0278] In one mode, the organic solvent may contain a specific solvent compound and a perhalogenated compound. By using this mixed solvent, heat release can be suppressed. From the viewpoint of excellent conversion rate in liquid-phase fluorination, the content rate of the specific solvent compound relative to the total amount of the specific solvent compound and the perhalogenated compound is preferably 1% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more. From the viewpoint of being able to suppress heat release, the aforementioned content rate may be 90% by mass or less, may be 80% by mass or less, and may be 70% by mass or less. From the aforementioned viewpoints, the aforementioned content rate may be 1 to 90% by mass, may be 10 to 80% by mass, may be 20 to 70% by mass, and may be 50 to 70% by mass.

[0279] Examples of the perhalogenated compound include perfluoroalkane, perfluoroether compound, chlorofluorocarbon, chlorofluoroether compound, perfluoroamine, etc. More specifically, examples include the perhalogenated compounds exemplified as fluorine-containing compounds other than the specific solvent compound described later.

[0280] The organic solvent preferably has a high solubility of the raw material compound as a whole, and preferably can dissolve 1% by mass or more of the raw material compound at 25°C, and more preferably can dissolve 5% by mass or more.

[0281] When the amount of substance of hydrogen atoms in each 1 mL of the organic solvent is Ch (mmol) and the amount of substance of double bonds is Cd (mmol), Ct represented by Ct = Ch + 2Cd is preferably 0.01 to 100 mmol, and more preferably 0.01 to 50 mmol. If Ct is above the aforementioned lower limit value, the conversion rate of fluorination is excellent. If Ct is below the aforementioned upper limit value, the reaction heat can be suppressed and the decomposition reaction of the raw material compound can be suppressed.

[0282] When the organic solvent contains only a specific solvent compound, the aforementioned Ct represents the Ct for that specific solvent compound. When the organic solvent contains a specific solvent compound and other compounds, the aforementioned Ct represents the average value calculated by multiplying the Ct of each compound contained in the organic solvent by the volume ratio.

[0283] From the viewpoint of improving the yield, the boiling point of the organic solvent (in the case of a single specific solvent compound, it is the boiling point of that specific solvent compound; in the case of a mixed solvent, it is the boiling point of each compound) is preferably 10 to 500 °C, more preferably 30 to 250 °C, and still more preferably 50 to 150 °C.

[0284] From the viewpoint of improving the yield, the viscosity of the organic solvent at 25 °C is preferably 2,000 mPa·s or less as a whole, more preferably 1,000 mPa·s or less, and still more preferably 500 mPa·s or less. The lower the viscosity, the more preferred. The lower limit value can be 0.5 mPa·s or 1 mPa·s. The viscosity of the organic solvent can be measured in accordance with JIS Z8803:2011 using a rheometer (for example, device name: RE-215L, Toki Sangyo Co., Ltd.).

[0285] The total amount of the organic solvent is preferably 1 mass times or more, more preferably 5 mass times or more, and still more preferably 10 mass times or more relative to the raw material compound. The total amount of the organic solvent can be 100 mass times or less, 50 mass times or less, or 20 mass times or less relative to the raw material compound. The total amount of the organic solvent can be 1 to 100 mass times, 5 to 50 mass times, or 10 to 20 mass times relative to the raw material compound.

[0286] From the viewpoint of improving the yield, the vapor pressure of the organic solvent in the container is preferably 0.009 MPa or less, more preferably 0.007 MPa or less, still more preferably 0.006 MPa or less (49 mmHg), particularly preferably 0.005 MPa or less (38 mmHg), and extremely preferably 0.003 MPa or less (23 mmHg).

[0287] - Specific solvent compound -

[0288] The specific solvent compound is not particularly limited as long as it is a compound having a halogen atom and a C-H bond or a double bond. The specific solvent compound may have only either a C-H bond or a double bond, or may have both.

[0289] The specific solvent compound preferably has one or more halogen atoms, and has at least one selected from the group consisting of a fluorine atom, a chlorine atom, and a bromine atom, more preferably has at least one selected from the group consisting of a fluorine atom and a chlorine atom, and further preferably has a fluorine atom. The fluorine content of the specific solvent compound is preferably 5 to 99% by mass, more preferably 5 to 90% by mass, further preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass.

[0290] When the specific solvent compound has a C-H bond, the number of hydrogen atoms in the molecule is preferably 1 to 10, more preferably 1 to 8, and may be 1 to 6. If the number of hydrogen atoms is not less than the aforementioned lower limit value, the conversion rate is excellent, and if it is not more than the aforementioned upper limit value, the reaction heat can be suppressed and the decomposition reaction of the raw material compound can be suppressed.

[0291] When the specific solvent compound has a double bond, the number of double bonds in the molecule is preferably 1 to 10, more preferably 1 or 2, and further preferably 1.

[0292] From the viewpoint of improving the conversion rate, the number of carbon atoms of the specific solvent compound is preferably 2 or more, more preferably 2 to 100, further preferably 2 to 50, particularly preferably 2 to 20, and extremely preferably 2 to 10.

[0293] From the viewpoint of improving the conversion rate, the molecular weight of the specific solvent compound is preferably 100 or more, more preferably 100 to 50,000, further preferably 100 to 10,000, and particularly preferably 100 to 5,000. When there is a molecular weight distribution, the aforementioned molecular weight represents the weight average molecular weight (Mw).

[0294] The specific solvent compound is preferably a compound having a high solubility of the raw material compound in terms of a single compound, preferably a compound capable of dissolving 1% by mass of the raw material compound, and more preferably a compound capable of dissolving 5% by mass or more.

[0295] Examples of the specific solvent compound include hydrocarbons, ether compounds, ester compounds, ketone compounds, etc., and hydrocarbons and ether compounds are preferred.

[0296] Examples of the hydrocarbon include hydrocarbons having 2 to 100 carbon atoms, preferably 2 to 50 carbon atoms, more preferably 2 to 20 carbon atoms, and further preferably 2 to 10 carbon atoms. The hydrocarbon may be saturated or unsaturated, and may be any of linear, branched, and cyclic.

[0297] Examples of the ether compound include ether compounds having 2 to 100 carbon atoms, preferably 2 to 50 carbon atoms, more preferably 2 to 20 carbon atoms, and further preferably 2 to 10 carbon atoms. The number of ether bonds in the ether compound may be 1 or more.

[0298] Examples of the ester compound include ester compounds having 2 to 100 carbon atoms, preferably 2 to 50 carbon atoms, more preferably 2 to 20 carbon atoms, and even more preferably 2 to 10 carbon atoms. The number of ester bonds in the ester compound may be 1 or more.

[0299] Examples of the ketone compound include ketone compounds having 2 to 100 carbon atoms, preferably 2 to 50 carbon atoms, more preferably 2 to 20 carbon atoms, and even more preferably 2 to 10 carbon atoms. The number of carbonyl groups in the ketone compound may be 1 or more.

[0300] The specific solvent compound may be used alone or in combination of two or more.

[0301] Specific examples of the specific solvent compound include chloroolefins, hydrochloroolefins, hydrochlorofluoroolfins, hydrofluoroethers, hydrochlorofluoroethers, hydrofluorocarbons, hydrochlorofluorocarbons, and hydrobromocarbons.

[0302] The following table shows the specific solvent compounds or their mixtures that can be obtained. Note that (Z) in the table represents the Z-isomer and (E) represents the E-isomer.

[0303] [Table 1]

[0304]

[0305] Examples of the specific solvent compound also include the following compounds.

[0306] CH2ClCHClCH2OCF2CHFCl (also known as "HCFE-473".)

[0307] CF2ClCFClCHFOCF2CF2Cl (also known as "HCFE-428a,b".)

[0308] CHFClCFClCF2OCF2CF2Cl (also known as "HCFE-428c,d".)

[0309] CF2ClCHClCF2OCF2CF2Cl (also known as "HCFE-428e".)

[0310] CHFClCFClCHFOCF2CF2Cl (also known as "HCFE-437a,b".)

[0311] CF2ClCHClCHFOCF2CF2Cl (also known as "HCFE-437c".)

[0312] CHFClCFClCH2OCF2CF2Cl (also known as "HCFE-446a".)

[0313] CF2ClCCl2CF2OCF2CHFCl (also known as “HCFE-427a,b”.

[0314] CF2CFClCF2OCF2CF2Cl (also known as “HCFE-429”.

[0315] In liquid-phase fluorination, the amount of the specific solvent compound is 0.1 equivalent or more, preferably 1 equivalent or more, more preferably 5 equivalents or more, and may be 10 equivalents or more, based on the raw material compound. The amount of the specific solvent compound is preferably 200 equivalents or less, more preferably 100 equivalents or less, and may be 50 equivalents or less, based on the raw material compound. When the amount of the specific solvent compound is at least the aforementioned lower limit value, the conversion rate of fluorination is excellent. When the amount of the specific solvent compound is at most the aforementioned upper limit value, it is advantageous when the usage amount of the specific solvent compound is desired to be suppressed. From the foregoing viewpoints, the amount of the specific solvent compound is preferably 0.1 to 200 equivalents, more preferably 1 to 100 equivalents, may be 5 to 50 equivalents, and may be 10 to 50 equivalents, based on the raw material compound.

[0316] -Organic solvents other than the specific solvent compound-

[0317] As the organic solvent other than the specific solvent compound, a fluorine-containing compound other than the specific solvent compound is preferred. Examples thereof include perfluoroalkanes and organic compounds obtained by perfluorinating an organic compound having at least one atom selected from the group consisting of a chlorine atom, a nitrogen atom, and an oxygen atom.

[0318] The fluorine-containing compound other than the specific solvent compound is preferably a compound having a high solubility of the raw material compound as a single compound, preferably a compound capable of dissolving 1% by mass or more of the raw material compound at 25°C, and more preferably a compound capable of dissolving 5% by mass or more.

[0319] As the fluorine-containing compound other than the specific solvent compound, at least one selected from the group consisting of a chlorine-containing solvent and a fluorine-containing solvent other than the chlorine-containing solvent can be cited.

[0320] Examples of the chlorine-containing solvent include CClF2CClFCF2OCF2CClF2 (also known as “CFE-419”), 1,2,3,4-tetrachloroperfluorobutane (also known as “R-113”), CF2ClCFClCFClOCF2CF2Cl (also known as “CFE-418”), and the like.

[0321] Examples of fluorinated solvents other than chlorinated solvents include perfluoroalkanes (such as FC-72), perfluoroethers (such as FC-75 and FC-77), perfluoropolyethers (trade names: Krytox, Fomblin, GALDEN, DEMNUM, etc.), inert fluids (trade name: Fluorinert), perfluorocarboxylic acid fluorides, and the like.

[0322] Examples of fluorinated compounds other than specific solvent compounds also include the following acid fluorides.

[0323] CF3CF2CF2OCF(CF3)COF

[0324] CF3CF2CF2OCF(CF3)CF2OCF(CF3)COF

[0325] CF3CF2CF2OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)COF

[0326] The organic solvents other than specific solvent compounds can be used alone or in combination of two or more.

[0327] 〔Liquid-phase fluorination process〕

[0328] The reaction forms of the fluorination reaction include a batch method and a continuous method, and the continuous method is preferred. As the fluorination method, fluorination methods 1 and 2 described below can be cited. From the viewpoint of excellent conversion rate, it is preferred to carry out the fluorination method 2 described below in a continuous manner.

[0329] Fluorination method 1: A raw material compound and a solvent are charged into a reactor, and stirring is started. While continuously supplying fluorine gas, the reaction is carried out at a specified reaction temperature and reaction pressure.

[0330] Fluorination method 2: A solvent is charged into a reactor, and stirring is started. At a specified reaction temperature and reaction pressure, a raw material compound and fluorine gas are continuously supplied simultaneously at a specified molar ratio.

[0331] In fluorination method 2, when supplying the raw material compound, the raw material compound can be directly supplied without dilution with a solvent. When diluting the raw material compound with a solvent, it is preferred that the amount of the solvent relative to the raw material compound is 1 mass times or more, and more preferably 2 mass times or more.

[0332] In liquid-phase fluorination, fluorine gas can be directly used, or a mixed gas obtained by diluting fluorine gas with an inert gas can be used. Examples of the inert gas include nitrogen, helium, neon, argon, etc. Nitrogen or helium is preferred, and nitrogen is more preferred. From the viewpoint of excellent conversion rate, the fluorine gas concentration in the mixed gas is preferably 10% by volume or more, more preferably 15% by volume or more, and further preferably 20% by volume or more. From the viewpoint of suppressing the reactivity from becoming too high, it is preferably 60% by volume or less, more preferably 50% by volume or less, and further preferably 40% by volume or less. From the foregoing viewpoints, the fluorine gas concentration in the mixed gas is preferably 10-60% by volume, more preferably 15-50% by volume, and further preferably 20-40% by volume.

[0333] From the viewpoint of excellent conversion rate, the amount of fluorine used in liquid-phase fluorination is preferably an excessive equivalent amount relative to the hydrogen atoms in the raw material compound, and more preferably an amount reaching 1.5 times equivalent (i.e., 1.5 times mole) or more. The amount of fluorine is preferably maintained at an excessive equivalent from the beginning to the end of the liquid-phase fluorination.

[0334] The reaction temperature of the liquid-phase fluorination is preferably -60°C or higher and below the boiling point of the raw material compound. From the viewpoints of reaction yield, selectivity, and ease of industrial implementation, it is more preferably -50°C to 100°C, and further preferably -20°C to 50°C.

[0335] The reaction pressure of the liquid-phase fluorination is not particularly limited. From the viewpoints of excellent conversion rate and ease of industrial implementation, it is preferably 0-2 MPa.

[0336] The reaction time in the liquid-phase fluorination (i.e., the residence time of the reaction field of the raw material compound) is preferably 200 hours or less, more preferably 190 hours or less, further preferably 170 hours or less, particularly preferably 150 hours or less, and extremely preferably 100 hours or less. The aforementioned reaction time is preferably 0.3 hours or more, more preferably 0.6 hours or more, and further preferably 1 hour or more. If the reaction time is above the aforementioned lower limit value, the reaction is likely to be sufficient. If it is below the aforementioned upper limit value, it is easy to reduce the manufacturing time and cost. From the foregoing viewpoints, the reaction time is preferably 0.3-200 hours, more preferably 0.6-190 hours, further preferably 1-170 hours, particularly preferably 1-150 hours, and extremely preferably 1-100 hours.

[0337] In the fluorination process, the content rate of the raw material compound in the liquid phase is preferably 10-70% by mass, and more preferably 20-50% by mass.

[0338] From the viewpoint of effectively performing liquid-phase fluorination and increasing the yield, it is preferable to irradiate the reaction system with ultraviolet rays. In the batchwise reaction, it is preferable to irradiate the reaction system with ultraviolet rays in the latter stage of liquid-phase fluorination. The ultraviolet irradiation time is preferably 0.1 to 3 hours.

[0339] In order to effectively perform liquid-phase fluorination, a compound having a C-H bond (which is a compound different from a specific solvent compound) or a compound having a carbon-carbon double bond can be added as an auxiliary agent. It should be noted that when using a specific compound having a C-H bond or a compound having a carbon-carbon double bond in an amount less than 0.1 times the equivalent amount relative to the raw material compound, this compound is classified as an auxiliary agent.

[0340] Regarding the compound having a C-H bond as an auxiliary agent, an aromatic hydrocarbon is preferable, and benzene, toluene, etc. are more preferable. The addition amount of the compound having a C-H bond is preferably 0.1 mol% or more and less than 10 mol%, more preferably 0.1 to 5 mol%, relative to the hydrogen atoms of the raw material compound.

[0341] Regarding the compound having a carbon-carbon double bond as an auxiliary agent, CF3CF=CF2, CF2=CF-CF=CF2 can be cited.

[0342] The addition amount of the compound having a carbon-carbon double bond is preferably 0.1 mol% or more and less than 10 mol%, more preferably 0.1 to 5 mol%, relative to the hydrogen atoms in the raw material compound.

[0343] For example, in the batchwise reaction, an auxiliary agent can be added to the reaction system in the latter stage of liquid-phase fluorination. The auxiliary agent is preferably added in a state where fluorine exists in the reaction system. When adding the auxiliary agent, it is preferable to pressurize the reaction system. As the pressure during pressurization, 0.01 to 5 MPa is preferable.

[0344] On the other hand, this manufacturing method can be carried out without using an auxiliary agent. According to this manufacturing method, a suitable yield can be obtained even without using an auxiliary agent.

[0345] In the liquid-phase fluorination of the raw material compound, when a reaction occurs in which a hydrogen atom is replaced by a fluorine atom, HF is by-produced. In order to capture HF, it is preferable to coexist a HF capture agent in the reaction system or to bring the HF capture agent into contact with the outlet gas at the gas outlet of the reactor. As the HF capture agent, for example, NaF is preferably used.

[0346] The crude product containing the fluorinated compound obtained by liquid-phase fluorination can be directly used in the subsequent process, or can be purified to obtain a high-purity product. As the purification method, a method of directly distilling the crude product under normal pressure or reduced pressure can be cited.

[0347] Examples

[0348] Next, the implementation modes of the present application will be specifically described by way of examples, but the implementation modes of the present application are not limited to these examples. In the following examples, Examples 1 to 4 are examples, and Example 5 is a comparative example.

[0349] In the examples, the respective compounds used as solvents are as follows.

[0350] (HFPO)3 ··· CF3CF2CF2OCF(CF3)CF2OCF(CF3)C(=O)F, boiling point is 113 °C

[0351] AE-3000 (trade name) ··· CF3CH2OCF2CHF2, boiling point is 56 °C, molecular weight is 200, specific gravity is 1.47 (25 °C, g / mL)

[0352] AS-300 (trade name) ··· CF2HCF=CHCl(Z), boiling point is 54 °C, molecular weight is 130.5, specific gravity is 1.38 (25 °C, g / mL)

[0353] (HFPO)3, AE-3000, and AS-300 are all products manufactured by AGC Inc.

[0354] [Example 1]

[0355] CF3CF2OCF2CF2OCF2CF2OCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3 (target compound) was manufactured by the following method.

[0356] According to Example 1 (Step 1-1) of International Publication No. 2008 / 026707, CH3CH2OCH2CH2OCH2CH2OCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3 (raw material compound, molecular weight is 612) was prepared. 20 g of the raw material compound was dissolved in 200 g of AE-3000 to obtain a raw material solution. 200 g of AE-3000 was added to a 500 mL autoclave made of SUS316 and stirred. After blowing nitrogen for 1 hour, fluorine gas diluted to 30 vol% with nitrogen was introduced. Thereafter, at 25 °C, the flow rate was set to 25.01 L / hour, and while blowing fluorine gas diluted to 30 vol% with nitrogen, the raw material solution was injected over 24 hours. Thereafter, after stirring at 25 °C for 1 hour, nitrogen was blown for 2 hours, and the obtained crude liquid was concentrated using a rotary evaporator. Using 19 F-NMR and 1 H-NMR to quantify the product and calculate the conversion rate. The conversion rate is shown by the following formula.

[0357] Conversion rate (%) = {1 - (number of fluorinated atoms per molecule of product) / (number of atoms capable of fluorination per molecule of starting compound)} × 100

[0358] [Example 2]

[0359] Use AS-300 to replace AE-3000. Otherwise, fluorinate the starting compound in the same manner as in Example 1. Use 19 F-NMR and 1 H-NMR to quantify the product and determine the conversion rate.

[0360] [Example 3]

[0361] Use a solvent prepared by mixing AE-3000 and (HFPO)3 at a ratio of 1:99 (mass ratio) to replace AE-3000. Otherwise, fluorinate the starting compound in the same manner as in Example 1. Use 19 F-NMR and 1 H-NMR to quantify the product and determine the conversion rate.

[0362] [Example 4]

[0363] Use a solvent prepared by mixing AE-3000 and (HFPO)3 at a ratio of 10:90 (mass ratio) to replace AE-3000. Otherwise, fluorinate the starting compound in the same manner as in Example 1. Use 19 F-NMR and 1 H-NMR to quantify the product and determine the conversion rate.

[0364] [Example 5]

[0365] Use (HFPO)3 to replace AE-3000. Otherwise, fluorinate the starting compound in the same manner as in Example 1. Use 19 F-NMR and 1 H-NMR to quantify the product and determine the conversion rate.

[0366] The conditions and conversion rates in each example are shown in Table 2.

[0367] [Table 2]

[0368]

[0369] As shown in Table 2, in Examples 1 to 4 in which AE-3000 and AS-300, which are specific solvent compounds, are used as solvents to fluorinate the raw material compounds, high conversion rates can be obtained even without using an auxiliary agent. From this, it can be known that: if a specific solvent compound is used, a fluorine-containing compound can be produced with a high conversion rate even without using an auxiliary agent. In addition, when a mixed solvent of a specific solvent compound and a perhalogenated compound is used, a good conversion rate can also be obtained.

[0370] Industrial applicability

[0371] The method for producing a fluorine-containing compound of the present application can perform fluorination with a good conversion rate and can simplify the process. The obtained fluorine-containing compound can be derived into fluorine-containing compounds having various functional groups (such as hydroxyl group, ethylenically unsaturated group, epoxy group, carboxyl group, etc.). In addition, the obtained fluorine-containing compound and the fluorine-containing compound that can be derived from the fluorine-containing compound can be used in surface treatment agents, emulsifiers, rubbers, surfactants, solvents, heat media, pharmaceuticals, pesticides, lubricating oils, their intermediates, etc.

[0372] The disclosure of Japanese Patent Application No. 2022-185988, filed on November 21, 2022, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as the case where each document, patent application, and technical standard is specifically and separately described and incorporated by reference.

Claims

1. A method for manufacturing a fluorine-containing compound, comprising: In an organic solvent into which fluorine gas is introduced, an organic compound having at least one atom or bond capable of being fluorinated is fluorinated. The organic solvent contains a compound having a halogen atom and having a C-H bond or a double bond. The amount of the compound having a halogen atom and having a C-H bond or a double bond is 0.1 equivalent or more relative to the organic compound having at least one atom or bond capable of being fluorinated.

2. The method for producing a fluorine-containing compound according to claim 1, wherein, When the amount of substance of hydrogen atoms in each 1 mL of the organic solvent is Ch (mmol) and the amount of substance of double bonds is Cd (mmol), Ct represented by Ct = Ch + 2Cd is 0.01 to 100 mmol.

3. The method for producing a fluorine-containing compound according to claim 1 or 2, wherein, The organic solvent contains the compound having a halogen atom and having a C-H bond or a double bond and a perhalogenated compound.

4. The method for producing a fluorine-containing compound according to claim 3, wherein, The content ratio of the compound having a halogen atom and having a C-H bond or a double bond in the organic solvent is 1% by mass or more relative to the total amount of the compound having a halogen atom and having a C-H bond or a double bond and the perhalogenated compound.

5. The method for producing a fluorine-containing compound according to claim 1 or 2, which does not include the addition of an auxiliary agent.

6. The method for producing a fluorine-containing compound according to claim 1 or 2, wherein, The compound having a halogen atom and having a C-H bond or a double bond includes at least one selected from the group consisting of hydrocarbons, ether compounds, ester compounds, and ketone compounds.

7. The method for producing a fluorine-containing compound according to claim 1 or 2, wherein, The compound having a halogen atom and having a C-H bond or a double bond includes at least one selected from the group consisting of chloroolefins, hydrochlorofluoroolefins, hydrochlorofluorohydrocarbons, hydrofluoroethers, hydrofluorocarbons, hydrochlorofluorocarbons, and hydrobromocarbons.

8. The method for producing a fluorine-containing compound according to claim 1 or 2, wherein, In the organic compound having at least one atom or bond capable of being fluorinated, the atom capable of being fluorinated is a hydrogen atom bonded to a carbon atom, a chlorine atom bonded to a carbon atom, a bromine atom bonded to a carbon atom, or an iodine atom bonded to a carbon atom, and the bond capable of being fluorinated is a carbon-carbon unsaturated double bond or a carbon-carbon unsaturated triple bond.

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