WO2024111489A1 - Production method for fluorine-containing compound - Google Patents

Abstract

A production method for a fluorine-containing compound wherein an organic compound having at least one atom or bond that can be fluorinated is fluorinated in an organic solvent into which fluorine gas has been introduced, the organic solvent contains a compound having a halogen atom and a C-H bond or a double bond, and the amount of the said compound having a halogen atom and a C-H bond or a double bond is at least a 0.1-fold equivalent with respect to the organic compound having at least one atom or bond that can be fluorinated.

Description

Method for producing fluorine-containing compound

This disclosure relates to a method for producing a fluorine-containing compound.

There are many industrially useful fluorine-containing compounds, and various manufacturing methods have been developed. One method for fluorinating compounds having a fluorinatable structure is to carry out a fluorination reaction in a liquid phase using fluorine gas (see, for example, Patent Document 1). Patent Document 1 describes a method for increasing the fluorination conversion rate by adding an auxiliary to the reaction system.

International Publication No. 2000/056694

According to the present inventors, when fluorinating a fluorine-containing compound using the method of Patent Document 1, there was room for improvement, as it required a step of adding an auxiliary agent separately from the raw materials and organic solvent, required a step of removing the auxiliary agent from the product, made it difficult to separate the auxiliary agent, and impurities remained in the system if the auxiliary agent was not removed. In view of these circumstances, the present disclosure relates to the provision of a method for producing a fluorine-containing compound that can fluorinate with a good conversion rate and allows for simplified steps.

The present disclosure includes the following aspects.
<1> A method for producing a fluorinated product comprising: fluorinating an organic compound having at least one fluorinatable atom or bond in an organic solvent into which fluorine gas has been introduced;
the organic solvent contains a compound having a halogen atom and a C—H bond or a double bond,
the amount of the compound having a halogen atom and a C—H bond or a double bond is 0.1 equivalents or more relative to the amount of the organic compound having at least one fluorinatable atom or bond.
<2> The method for producing a fluorine-containing compound according to <1>, wherein Ct, expressed as Ct=Ch+2Cd, is 0.01 to 100 mmol, where Ch (mmol) is the amount of hydrogen atoms per mL of the organic solvent, and Cd (mmol) is the amount of double bonds per mL of the organic solvent.
<3> The method for producing a fluorine-containing compound according to <1> or <2>, wherein the organic solvent contains the compound having a halogen atom and a C—H bond or a double bond, and a perhalogeno compound.
<4> The method for producing a fluorine-containing compound according to <3>, wherein the content of the compound having a halogen atom and a C-H bond or a double bond in the organic solvent is 1 mass% or more relative to the total amount of the compound having a halogen atom and a C-H bond or a double bond and the perhalogeno compound.
<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.
<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 a C—H bond or a double bond includes at least one selected from the group consisting of a hydrocarbon, an ether compound, an ester compound, and a ketone compound.
<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 a C—H bond or a double bond includes at least one selected from the group consisting of chloroolefins, hydrochloroolefins, hydrochlorofluoroolefins, hydrofluoroethers, hydrofluorocarbons, hydrochlorofluorocarbons, and hydrobromocarbons.
<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 fluorinable atom or bond, the fluorinable atom 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 fluorinable bond is a carbon-carbon unsaturated double bond or a carbon-carbon unsaturated triple bond.

The present disclosure provides a method for producing a fluorine-containing compound that can be fluorinated with a good conversion rate and simplifies the process.

Below, the form for carrying out the embodiment of the present disclosure will be described in detail. However, the embodiment of the present disclosure is not limited to the following embodiment. In the following embodiment, the components (including element steps, etc.) are not essential unless specifically stated. The same applies to the numerical values and their ranges, and they do not limit the embodiment of the present disclosure.

In the present disclosure, the term "step" includes not only a step that is independent of other steps, but also a step that cannot be clearly distinguished from other steps as long as the purpose of the step is achieved.
In the present disclosure, the numerical range indicated using "to" includes the numerical values before and after "to" as the minimum and maximum values, respectively.
In the present disclosure, each component may contain multiple types of the corresponding substance. When multiple substances corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified.
In this disclosure, "organic group" refers to a group that contains essentially a carbon atom.
In the present disclosure, the "hydrocarbon group" may be any of linear, branched, and cyclic, and may be any of saturated aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, and aromatic hydrocarbon groups.
In this disclosure, "partially halogenated" means that only a portion of the halogenatable sites on a compound are halogenated.
In the present disclosure, when a compound is represented by a specific formula (X), the compound represented by the formula (X) may be referred to as compound (X).

[Method of producing fluorine-containing compound]
The method for producing a fluorine-containing compound of the present disclosure (hereinafter also referred to as "the present production method") comprises fluorinating an organic compound having at least one fluorinatable atom or bond (hereinafter also referred to as "starting compound") in an organic solvent into which fluorine gas has been introduced, the organic solvent containing a compound having a halogen atom and a C-H bond or a double bond (hereinafter also referred to as "specific solvating compound"), and the amount of the specific solvating compound is 0.1 equivalents or more relative to the starting compound. Hereinafter, the fluorine-containing compound produced by the present production method (i.e., the product obtained by fluorinating the starting compound) is also referred to as the "target compound". Note that the starting compound and the specific solvating compound are different compounds.

This production method includes a fluorination step in a liquid phase (hereinafter, also referred to as "liquid-phase fluorination"). In general, in liquid-phase fluorination, an organic solvent that is not reactive to fluorine gas, such as CF ₂ ClCFCl ₂ (also referred to as "R-113") or perfluorotributylamine, is used as a solvent. This is to prevent side reactions and a decrease in the efficiency of fluorination due to the fluorination of the solvent. However, when only an organic solvent that is not reactive to fluorine gas is used, the conversion rate of fluorination is low, so the conversion rate is improved by adding an auxiliary such as benzene or toluene to the reaction system. On the other hand, the present inventors have found that when liquid-phase fluorination is performed using a specific solvent compound as a solvent, a good fluorination conversion rate can be obtained without using an auxiliary. The reason for this is not necessarily clear, but is presumed to be as follows. Since the specific solvent compound has a C-H bond or a double bond in its structure, the solvent itself is fluorinated in the liquid-phase fluorination step. It is considered that fluorine radicals are generated in this process, which promotes the fluorination of the raw material compound and improves the conversion rate. For this reason, it is presumed that the target compound can be obtained at a high conversion rate even without adding an auxiliary. According to the present production method, for example, it is possible to omit an auxiliary addition step, a removal step, etc., and to reduce impurities associated with the mixing of an auxiliary. In addition, if a compound that can be converted into a desired fluorine-containing compound is used as the specific solvent compound, it is also possible to obtain the desired fluorine-containing compound.

(Raw material compound)
The raw material compound for the liquid phase fluorination is an organic compound having at least one fluorinatable atom or bond. The raw material compound may be either a commercially available compound or a synthesized compound.
Atoms that can be fluorinated include hydrogen atoms bonded to carbon atoms, chlorine atoms bonded to carbon atoms, bromine atoms bonded to carbon atoms, and iodine atoms bonded to carbon atoms.
Fluorinizable bonds include carbon-carbon unsaturated double bonds and carbon-carbon unsaturated triple bonds.
The number of fluorinable atoms or bonds in the raw material compound may be at least 1. From the viewpoint of excellent solubility, the number of fluorinable atoms is preferably 1 to 1,000, more preferably 1 to 500. From the viewpoint of increasing the purity of the fluorinated product, the number of fluorinable bonds is preferably 1 to 30, more preferably 1 to 20.

The number of carbon atoms in the raw material compound may be selected depending on the target compound, and is preferably 4 or more, and in one embodiment, 4 to 1,000 is more preferable, 4 to 500 is even more preferable, 4 to 100 is particularly preferable, 4 to 50 is extremely preferable, and 4 to 20 is even more preferable.

In one embodiment, from the viewpoint of improving the yield of the target compound, the raw material 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 even more preferably has a fluorine atom. From the viewpoint of improving the solubility in the solvent and the yield of the target compound, the fluorine content in the raw material compound (i.e., the proportion of fluorine atoms in the molecule) is preferably 30% by mass or more, more preferably 30 to 84% by mass, and even more preferably 30 to 76% by mass.

The raw material compounds include aliphatic hydrocarbons, aromatic hydrocarbons, ether compounds, ester compounds, amide compounds, thioether compounds, and thioester compounds. These compounds may be partially halogenated or may not be halogenated. The raw material compounds may be compounds that contain a heteroatom or heteroatom group in the carbon skeleton of these compounds that is not changed by the fluorination reaction. Hereinafter, for the sake of convenience, raw material compounds that have both an ester bond and an ether bond will be classified as ester compounds.

The carbon number of the aliphatic hydrocarbon, which is the raw material compound, is preferably 4 or more, and in one embodiment, 4 to 1,000 is more preferable, 4 to 500 is even more preferable, 4 to 100 is particularly preferable, 4 to 50 is extremely preferable, and 4 to 20 is even more preferable. 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 it is preferable that it does not have one.

The number of carbon atoms in the aromatic hydrocarbon raw material compound is preferably 4 or more, and in one embodiment, 4 to 1,000 is more preferable, 4 to 500 is even more preferable, 4 to 100 is particularly preferable, 4 to 50 is extremely preferable, and 4 to 20 is even more preferable. 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.

The number of carbon atoms in the amide compound, which is the raw material compound, is preferably 4 or more, and in one embodiment, 4 to 1,000 is more preferable, 4 to 500 is even more preferable, 4 to 100 is particularly preferable, 4 to 50 is extremely preferable, and 4 to 20 is even more preferable. The amide compound is a compound having one or more amide groups. The amide compound may be a polyamide compound.

The carbon number of the thioether compound, which is the raw material compound, is preferably 4 or more, and in one embodiment, 4 to 1,000 is more preferable, 4 to 500 is even more preferable, 4 to 100 is particularly preferable, 4 to 50 is extremely preferable, and 4 to 20 is even more preferable. A thioether compound is a compound having one or more thioether bonds. The thioether compound may be a polythioether compound.

The carbon number of the thioester compound, which is the raw material compound, is preferably 4 or more, and in one embodiment, 4 to 1,000 is more preferable, 4 to 500 is even more preferable, 4 to 100 is particularly preferable, 4 to 50 is extremely preferable, and 4 to 20 is even more preferable. The thioester compound is a compound having one or more thioester bonds. The thioester compound may be a polythioester compound.

The carbon number of the ester compound, which is the raw material compound, is preferably 4 or more, and in one embodiment, 4 to 1,000 is more preferable, 4 to 500 is even more preferable, 4 to 100 is particularly preferable, 4 to 50 is extremely preferable, and 4 to 20 is even more preferable. 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.

Examples of the ester compound include a compound represented by the following formula (1) and a compound represented by the following formula (2).
R ^A1 -O-(C=O)-R ^B1 ... (1)
R ^B2 -(C=O)-O-R ^A2 -O-(C=O)-R ^B3 ... (2)

In formulas (1) and (2),
R ^A1 , R ^B1 , R ^B2 , and R ^B3 each independently represent a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogeno (heteroatom-containing monovalent saturated hydrocarbon) group;
R ^A2 is a divalent saturated hydrocarbon group, a halogeno divalent saturated hydrocarbon group, a heteroatom-containing divalent saturated hydrocarbon group, or a halogeno (heteroatom-containing divalent saturated hydrocarbon) group.

In the present disclosure, a "monovalent saturated hydrocarbon group" may be any of a linear alkyl group, a branched alkyl group, and a cycloalkyl group. A "divalent saturated hydrocarbon group" may 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.

In this disclosure, "halogeno" means that one or more hydrogen atoms present in the group are replaced with 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.

In this disclosure, a "halogeno monovalent saturated hydrocarbon group" refers to a group in which one or more hydrogen atoms present in a monovalent saturated hydrocarbon group have been replaced by a halogen atom. A "halogeno divalent saturated hydrocarbon group" refers to a group in which one or more hydrogen atoms present in a divalent saturated hydrocarbon group have been replaced by a halogen atom.

In this disclosure, "heteroatom" means an atom other than a carbon atom or a hydrogen atom, and examples include a nitrogen atom, an oxygen atom, and a sulfur atom.

In the present disclosure, a "heteroatom-containing monovalent saturated hydrocarbon group" refers to a group in which a divalent heteroatom or a divalent group containing a heteroatom is contained in a monovalent saturated hydrocarbon group. A "heteroatom-containing divalent saturated hydrocarbon group" refers to a group in which a divalent heteroatom or a divalent group containing a heteroatom is contained in a divalent saturated hydrocarbon group. Examples of divalent heteroatoms include -O- and -S-. Examples of divalent groups containing a heteroatom include -NH-, -C(=O)-, and _-SO2- .

In this disclosure, the term "halogeno (heteroatom-containing monovalent saturated hydrocarbon) group" refers to a group in which one or more hydrogen atoms in the heteroatom-containing monovalent saturated hydrocarbon group have been replaced with a halogen atom. The term "halogeno (heteroatom-containing divalent saturated hydrocarbon) group" refers to a group in which one or more hydrogen atoms in the heteroatom-containing divalent saturated hydrocarbon group have been replaced with a halogen atom.

In formula (1), it is preferable that at least one of R ^A1 and R ^B1 contains a hydrogen atom. Also, in formula (2), it is preferable that at least one selected from the group consisting of R ^A2 , R ^B2 , and R ^B3 contains a hydrogen atom.

[R ^A1 ]
In formula (1), R ^A1 represents a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogeno (heteroatom-containing monovalent saturated hydrocarbon) group.

Examples of the monovalent saturated hydrocarbon group represented by R ^A1 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, and a cyclohexyl group.

The halogeno monovalent saturated hydrocarbon group represented by R ^A1 is preferably a halogenoalkyl group. The halogen atom contained in the halogeno monovalent saturated hydrocarbon group is preferably a fluorine atom, a chlorine atom or a bromine atom, and more preferably a fluorine atom.

The heteroatom-containing monovalent saturated hydrocarbon group represented by R ^A1 is preferably a monovalent saturated hydrocarbon group containing an ethereal oxygen atom (that is, --O--), and more preferably an alkyl group containing an ethereal oxygen atom.

The halogeno (heteroatom-containing monovalent saturated hydrocarbon) group represented by R ^A1 is preferably a halogeno (heteroatom-containing alkyl group). The halogen atom contained in the halogeno (heteroatom-containing monovalent saturated hydrocarbon) group is preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogeno (heteroatom-containing monovalent saturated hydrocarbon) group is preferably a halogeno monovalent saturated hydrocarbon group containing an ethereal oxygen atom, and more preferably a halogenoalkyl group containing an ethereal oxygen atom.

The carbon number of R ^A1 is preferably 1 to 200, and more preferably 3 to 100, in terms of excellent solubility in a solvent.

In particular, from the viewpoint of excellent solubility in a solvent, R ^is preferably represented by the following formula ( ^A1 ): In other words, R preferably further has an ether bond, and more preferably includes at least one selected from the group consisting of a polyether chain and a fluoropolyether chain.
R ¹¹ O-(R ¹² O) _m1 -R ¹³ - ... (A1)

In formula (A1), R ¹¹ is an alkyl group which may have a fluorine atom, R ¹² is each independently an alkylene group having 1 to 6 carbon atoms which may have a fluorine atom, R ¹³ is an alkylene group having 1 to 6 carbon atoms which may have a fluorine atom, and m1 is an integer from 0 to 500.

In formula (A1), examples of R ¹¹ include an alkyl group and a fluoroalkyl group.

The number of carbon atoms in R ¹¹ is preferably 1 to 100, more preferably 1 to 50, even more preferably 1 to 10, and particularly preferably 1 to 6, from the viewpoint of excellent solubility in a solvent.

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

The fluoroalkyl group represented by R ¹¹ may be a straight-chain fluoroalkyl group, a branched-chain fluoroalkyl group, or a fluoroalkyl group having a ring structure.

Among these, R ¹¹ is preferably an alkyl group, more preferably a linear alkyl group, and even more preferably a linear alkyl group having 1 to 6 carbon atoms.

In formula (A1), -(R ¹² O) _m1 - is preferably represented by the following formula (A2).
-[(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)
however,
R ^f1 is a fluoroalkylene group having 1 carbon atom;
R ^f2 is a fluoroalkylene group having 2 carbon atoms,
R ^f3 is a fluoroalkylene group having 3 carbon atoms,
R ^f4 is a fluoroalkylene group having 4 carbon atoms,
R ^f5 is a fluoroalkylene group having 5 carbon atoms;
R ^f6 is a fluoroalkylene group having 6 carbon atoms.
k1, k2, k3, k4, k5, and k6 each independently represent an integer of 0 or 1 or more, and k1+k2+k3+k4+k5+k6 is an integer of 0 to 500.

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, even more preferably an integer from 5 to 200, and particularly preferably an integer from 10 to 150.

In addition, 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 arrangement. For example, (R ^f5 O) _k5 represents that the number of (R ^f5 O) is k5, and does not represent a block arrangement structure of (R ^f5 O) _k5 . Similarly, the order of (R ^f1 O) to (R ^f6 O) does not represent the bonding order of each unit.

In R ^f3 to R ^f6 , the fluoroalkylene group may be a linear fluoroalkylene group, a branched fluoroalkylene group, or a fluoroalkylene group having a ring structure.

Specific examples of R ^f1 include --CF ₂ -- and --CHF--.

Specific examples of R ^f2 include -CF ₂ CF ₂ -, -CF ₂ CHF-, -CHFCF ₂ -, -CHFCHF-, -CH ₂ CF ₂ -, and -CH ₂ CHF-.

Specific examples of R ^f3 include -CF ₂ CF ₂ CF ₂ -, -CF ₂ CHFCF ₂ -, -CF ₂ CH ₂ CF ₂ -, -CHFCF ₂ CF ₂ -, -CHFCHFCF ₂ -, -CHFCHFCHF-, -CHFCH ₂ CF ₂ -, -CH ₂ CF ₂ CF ₂ -, -CH ₂ CHFCF ₂ -, -CH ₂ CH 2 CF ₂ -, -CH ₂ CF ₂ CHF-, _{-CH 2 CHFCHF-, -CH 2 CH 2 CHF- , -CF} (CF ₃ )-CF ₂ -, -CF(CHF ₂ )-CF ₂ -, -CF(CH ₂ F)-CF ₂ -, -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( _CH2 Examples of such groups include -CH(CH ₃ )-CHF-, -CH(CH 3 )-CHF-, -CH(CF ₃ )-CH ₂ -, -CH(CHF ₂ )-CH ₂ -, and -CH(CH ₂ F)-CH ₂ -.

Specific examples of R ^f4 include -CF ₂ CF ₂ CF _{2 -} , -CF ₂ CF 2 CF _{2 CHF-, -CF 2 CF 2 CF 2 CH 2 - ,} -CF ₂ CHFCF ₂ CF ₂ -, -CHFCHFCF ₂ CF ₂ -, -CH 2 CHFCF ₂ CF ₂ -, -CF ₂ CH ₂ CF ₂ CF ₂ -, -CHFCH 2 CF ₂ CF ₂ -, -CH ₂ CH ₂ CF ₂ CF _{2 -, -CHFCF 2 CHFCF 2 -, -CH 2 CF 2 CHFCF 2 -, -CF 2 CHFCFCF 2 - , and -CF 2 CHFCFCF 2} -, -CHFCHFCHFCF ₂ -, -CH ₂ CHFCHFCF ₂ -, -CF ₂ CH ₂ CHFCF ₂ -, -CHFCH ₂ CHFCF ₂ -, -CH ₂ CH ₂ CHFCF ₂ -, -CF ₂ CH 2 CH ₂ CF ₂ -, -CHFCH ₂ CH ₂ CF ₂ -, -CH ₂ CH ₂ CH ₂ CF ₂ -, -CHFCH ₂ CH ₂ CHF-, -CH ₂ CH _{2 CH 2 CHF-} , and -cycloC ₄ F ₆ -.

Specific examples of R ^f5 include -CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ -, -CHFCF ₂ CF _{2 CF 2 CF 2} -, -CH ₂ CHFCF ₂ CF ₂ CF ₂ -, -CF ₂ CHFCF ₂ CF ₂ CF ₂ -, -CHFCHFCF ₂ CF ₂ CF ₂ -, -CF ₂ CH ₂ CF ₂ CF ₂ CF ₂ -, -CHFCH ₂ CF ₂ CF ₂ CF ₂ -, -CH ₂ CH ₂ CF ₂ CF ₂ CF ₂ -, -CF ₂ CF ₂ CHFCF ₂ CF ₂ -, -CHFCF ₂ CHFCF ₂ Examples include -CF ₂ -, -CH ₂ CF ₂ CHFCF ₂ CF ₂ -, -CH ₂ CF ₂ CF ₂ CF ₂ CH ₂ -, and -cycloC ₅ F ₈ -.

Specific examples of R ^f6 include -CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ -, -CF ₂ CF ₂ CHFCHFCF ₂ CF ₂ -, -CHFCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ -, -CHFCHFCHFCHFCHFCHF-, -CHFCF ₂ CF ₂ CF ₂ CF _{2 CH 2 -} , -CH ₂ CF ₂ CF ₂ CF _{2 CH 2 -} , and -cycloC ₆ F ₁₀ -.
Here, -cycloC ₄ F ₆ - means a perfluorocyclobutanediyl group, a specific example of which is a perfluorocyclobutane-1,2-diyl group, -cycloC ₅ F ₈ - means a perfluorocyclopentanediyl group, a specific example of which is a perfluorocyclopentane-1,3-diyl group, -cycloC ₆ F ₁₀ - means a perfluorocyclohexanediyl group, a specific example of which is a perfluorocyclohexane-1,4-diyl group.

Among these, —(R ¹² O) _m1 — preferably contains at least one selected from the group consisting of structures represented by the following formulas (F1) to (F3), and more preferably contains a structure represented by formula (F2).
-(R ^f1 O) _k1 -(R ^f2 O) _k2 - ... (F1)
-(R ^f2 O) _k2 -(R ^f4 O) _k4 - ... (F2)
-(R ^f3 O) _k3 - ... (F3)
However, the symbols in formulas (F1) to (F3) are the same as those in formula (A2) above.

In formula (F1) and formula (F2), the bonding order of (R ^f1 O) and (R ^f2 O), and (R ^f2 O) and (R ^f4 O) are each arbitrary. For example, (R ^f1 O) and (R ^f2 O) may be arranged alternately, (R ^f1 O) and (R ^f2 O) may be arranged in blocks, or may be arranged randomly. The same applies to formula (F2).
In formula (F1), k1 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. Also, k2 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20.
In formula (F2), k2 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. Also, k4 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20.
In formula (F3), k3 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20.

In formula (A1), examples of R ¹³ include the same as R ^f1 to R ^f6 above.

Of these, R ¹³ is preferably a fluoroalkylene group having 1 to 4 carbon atoms.

Specific examples of R ^A1 include the following structures. * represents a bonding site with --O--, n1 represents an integer of 0 to 60, and n2 represents an integer of 0 to 500. n1 is, for example, 13, and n2 is, for example, 7.

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

Examples of the monovalent saturated hydrocarbon group represented by R ^B1 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, and a cyclohexyl group.

The halogeno monovalent saturated hydrocarbon group represented by R ^B1 is preferably a halogenoalkyl group. The halogen atom contained in the halogeno monovalent saturated hydrocarbon group is preferably a fluorine atom, a chlorine atom, or a bromine atom.

The heteroatom-containing monovalent saturated hydrocarbon group represented by ^R is preferably a monovalent saturated hydrocarbon group containing an ethereal oxygen atom (i.e., -O-), and more preferably an alkyl group containing an ethereal oxygen atom. In other words, R ^preferably further has an ether bond.

The halogeno (heteroatom-containing monovalent saturated hydrocarbon) group represented by R ^B1 is preferably a halogeno (heteroatom-containing alkyl group). The halogen atom contained in the halogeno (heteroatom-containing monovalent saturated hydrocarbon) group is preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogeno (heteroatom-containing monovalent saturated hydrocarbon) group is preferably a halogeno monovalent saturated hydrocarbon group containing an ethereal oxygen atom, and more preferably a halogenoalkyl group containing an ethereal oxygen atom.

The number of carbon atoms in R ^B1 is preferably 1 to 100, more preferably 2 to 50, and even more preferably 3 to 20, from the viewpoint of excellent solubility in a solvent.

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.

Among these, from the viewpoint of excellent solubility in a solvent, R ^B1 is preferably represented by the following formula (B1).
^R21O- ( ^R22O ) _m2 - ^R23 -... (B1)

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

In formula (B1), examples of R ²¹ include an alkyl group and a fluoroalkyl group.

The carbon number of R ²¹ is preferably 1 to 50, more preferably 1 to 10, and even more preferably 1 to 6, from the viewpoint of excellent solubility in a solvent.

The alkyl group represented by ^R21 may be a linear alkyl group, a branched alkyl group, or an alkyl group having a ring structure.
The fluoroalkyl group represented by R ²¹ may be a straight-chain fluoroalkyl group, a branched-chain fluoroalkyl group, or a fluoroalkyl group having a ring structure.

Among these, 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.

In formula (B1), —(R ²² O) _m2 — is preferably represented by the above formula (A2).

In formula (B1), m2 is preferably 0 to 15, more preferably 0 to 10, even more preferably 0 to 4, and particularly preferably 0 to 2.

In formula (B1), examples of R ²³ include the same as R ^f1 to R ^f6 above.

Among these, R ²³ is preferably a fluoroalkylene group having 1 to 3 carbon atoms, and more preferably a perfluoroalkylene group having 1 to 3 carbon atoms.

Specific examples of R ^B1 include the following structures: * represents the bonding site with -O-(C=O)-.

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

Examples of the divalent saturated hydrocarbon group, halogeno divalent saturated hydrocarbon group, heteroatom-containing divalent saturated hydrocarbon group, or halogeno (heteroatom-containing divalent saturated hydrocarbon) group represented by ^R include groups in which one hydrogen atom or one halogen atom has been removed from the monovalent saturated hydrocarbon group, halogeno monovalent saturated hydrocarbon group, heteroatom-containing monovalent saturated hydrocarbon group, or halogeno (heteroatom-containing monovalent saturated hydrocarbon) group represented by R in ^{formula (} 1).

The carbon number of R ^A2 is preferably 1 to 200, and more preferably 3 to 100, in terms of excellent solubility in a solvent.

Among these, from the viewpoint of excellent solubility in a solvent, R ^A2 is preferably represented by the following formula (A5): In other words, R ^A2 preferably further has an ether bond, and more preferably includes at least one selected from the group consisting of a polyether chain and a fluoropolyether chain.
-R ³¹ O-(R ³² O) _m5 -R ³³ - ... (A5)

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

In formula (A5), R ³¹ and R ³³ each independently have the same meaning as R ¹³ in formula (A1).
In formula (A5), examples of -(R ³² O) _m5 - include the same as -(R ¹² O) _m1 - in formula (A1).

Specific examples of R ^A2 include the following structures: * represents a bonding site with —O—, and n2 represents an integer of 0 to 500.

[R ^B2 and R ^B3 ]
In formula (2), R ^B2 and R ^B3 each independently represent a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogeno (heteroatom-containing monovalent saturated hydrocarbon) group.

Examples of the monovalent saturated hydrocarbon group, halogeno monovalent saturated hydrocarbon group, heteroatom-containing monovalent saturated hydrocarbon group, or halogeno (heteroatom-containing monovalent saturated hydrocarbon) group represented by R ^{or R} include groups similar to the monovalent saturated hydrocarbon group, halogeno monovalent saturated hydrocarbon group, heteroatom-containing monovalent saturated hydrocarbon group, or halogeno (heteroatom-containing monovalent saturated hydrocarbon) group represented by R in ^formula (1).

An example of an ester compound is the following compound (T1).

The carbon number of the ether compound, which is the raw material compound, is preferably 4 or more, and in one embodiment, 4 to 1,000 is more preferable, 4 to 500 is even more preferable, 4 to 100 is particularly preferable, 4 to 50 is extremely preferable, and 4 to 20 is even more preferable. The ether compound is a compound having one or more ether bonds. The ether compound may be a polyether compound.

In one embodiment, the ether compound has the structure:
R ^x -O-R ^Y

In the formula,
R ^x and R ^Y are each independently a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogeno (heteroatom-containing monovalent saturated hydrocarbon) group, provided that at least one of R ^x and R ^Y has at least one fluorinable atom or bond.

Details of the monovalent saturated hydrocarbon group, the halogeno monovalent saturated hydrocarbon group, the heteroatom-containing monovalent saturated hydrocarbon group, and the halogeno (heteroatom-containing monovalent saturated hydrocarbon) group are the same as those described in the section on the compound represented by formula (1), which is the raw material compound, that is, the ester compound.

Examples of the monovalent saturated hydrocarbon groups represented by ^Rx and ^Ry each independently include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, and a cyclohexyl group.

The halogeno monovalent saturated hydrocarbon groups represented by R ^x and R ^Y are each independently preferably a halogenoalkyl group. The halogen atom contained in the halogeno monovalent saturated hydrocarbon group is preferably a fluorine atom, a chlorine atom, or a bromine atom, and more preferably a fluorine atom.

The heteroatom-containing monovalent saturated hydrocarbon group represented by R ^x and R ^Y is preferably a monovalent saturated hydrocarbon group containing an ethereal oxygen atom (i.e., —O—), and more preferably an alkyl group containing an ethereal oxygen atom.

The halogeno (heteroatom-containing monovalent saturated hydrocarbon) groups represented by ^Rx and ^Ry are each preferably independently a halogeno (heteroatom-containing alkyl) group. The halogen atom contained in the halogeno (heteroatom-containing monovalent saturated hydrocarbon) group is preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogeno (heteroatom-containing monovalent saturated hydrocarbon) group is preferably a halogeno monovalent saturated hydrocarbon group containing an ethereal oxygen atom, and more preferably a halogenoalkyl group containing an ethereal oxygen atom.

The carbon number of R ^x and R ^Y is each independently preferably 1 to 1,000, more preferably 1 to 500, and even more preferably 1 to 300, from the viewpoint of excellent solubility in a solvent.

Specific examples of raw material compounds include the following compounds listed in WO 2000/056694 and WO 2002/004397. In the formula, Cy represents a cyclohexyl group, Ph represents a phenyl group, and n, m, p, k, and r represent integers of 1 or more.

_{CF3CF2COOCH2CH2CH3 , ​ ​ ​
CF3CF2COOCH2CH ( OCH2CH2CH3 ) CH3 , ​
CF3CF2COOCH2CH ( OCH2CH2CHClCH2Cl ) CH3 , ​
CF3CF2COO ( CH2 ) 4OCHClCH2Cl
CF3CF2COO} ( _{CH2 ) 5OCHClCH2Cl ,
CF3} ( _{CF3CF2CF2O )} CFCOO( _{CH2 ) 4OCHClCH2Cl ,
CF3} ( _{CF3CF2CF2O )} CFCOO _{( CH2} ) _{5OCHClCH2Cl ,
CF3 ( CF2ClCFClCF2CF2O ) CFCOOCH2CH ( OCH2CH2CHClCH2Cl} ) _{CH3 ,
CF2ClCFClOCF2CF2CF2COO ( CH2 ) 4OCHClCH2Cl , ​
CClF2COOCH2CH2Cl , ​
CBrF2COOCH2CH2Br , ​
CF2BrCF2OCF} ( _CF3 ) _{COOCH2CH ( OCH2CH2Br} ) _{CH3 ,
CF2ClCFClCF2CF ( CF3} )OCF( _CF3 )COOCH2CH[OCH( _{CH3 ) CHClCH2Cl} ] _CH3 ,
_{CH2ClCHClCH2COOCH2CF2CFClCF2Cl , ​ ​ ​
CF3 ( CH3CH2CH2O ) CFCOOCH2CF ( OCF2CF2CF3 )} CF3 _,
CF3 ( _{CH3CH2CH2O ) CFCOOCH2CF ( OCH2CH2CH3 ) CF3 .}

_CF3 ( _{CF3CF2CF2O ) CFCOOCH2CH ( OCH2CH2CH3 ) CH3 ,
CF3 ( CF3CF2CF2O} ) _{CFCOOCH2CH ( OCH2CH2CHClCH2Cl ) CH3 ,
CF3} ( _CF3CF2CF2O ) _{CFCOOCH2CH ( OCH2Cy} ) _{CH3 ,
CF3} ( _{CF3CF2CF2O ) CFCOOCH2CH ( OCH2Ph} ) _CH3 ,
_CF3 ( _{CF3CF2CF2O ) CFCOOCH2CH} (O( _CH2 ) _{9CH3 ) CH3 ,
CF3} ( _{CF3CF2CF2O )} CFCOO _{( CH2 ) 3OCH2Ph} ,
_CF3 ( _{CF3CF2CF2O ) CFCOO} ( _{CH2 ) 3OCH2CH} = _CH2 ,
_{CF3CF2COOCH2CH2CHClCH2Cl , ​ ​ ​
CF2ClCFClCF2COOCH2CH2CHClCH2Cl , ​ ​ ​
CF2ClCF2CFClCOOCH2CH2CHClCH2Cl , ​ ​ ​}

_{CF3CF2COO ( CH2 ) nOCOCF2CF3 ,
CF3CF2COO} [ _CH2CH ( _{CH3 )} O] _m ( _{CH2 ) pOCOCF2CF3 ,
CF3CF2COO ( CH2CH2O ) k} ( _{CH2 ) rOCOCF2CF3 ,
CF3CF2COO} ( _CH2 ) _{2O ( CH2 ) 2OCOCF2CF3 ,
CF3CF2CF2OCF ( CF3} ) _COOCH2CH ( _CH3 ) _O ( _CH2 )5OCOCF _{( CF3 ) OCF2CF2CF3 ,
CF3CF2COO} ( _CH2 ) _{2O ( CH2} ) _2OCH ( _{CH3 ) CH2OCOCF2CF3 .}

_{CH3CH2OCH2CH2OCH2CH2OCOCCF ( CF3 ) OCF2CF ( CF3 ) OCF2CF2CF3 . ​ ​}

From the viewpoint of improving the yield of the target compound, the boiling point of the raw material compound is preferably 30°C or higher, more preferably 50°C or higher, and more preferably 100°C or higher. From the same viewpoint, the boiling point of the raw material compound is preferably 500°C or lower, more preferably 400°C or lower, and even more preferably 300°C or lower. From the above viewpoint, the boiling point of the raw material compound is preferably 30 to 500°C, more preferably 50 to 400°C, and even more preferably 100 to 300°C. In this disclosure, "boiling point" refers to the boiling point at normal pressure (760 mmHg).

The number average molecular weight (Mn) of the raw material compound is preferably 100 to 100,000, more preferably 100 to 20,000, further preferably 300 to 10,000, and particularly preferably 400 to 6,000. When Mn is equal to or greater than the lower limit, the decomposition reaction in the gas phase during liquid phase fluorination is easily suppressed. When Mn is equal to or less than the upper limit, the purification of the target compound is easily performed. Mn is the number average value of the molecular weight of each molecule calculated from the molecular structure identified by ¹ H-NMR and ¹⁹ F-NMR.

(Target compound)
The target compound, a fluorine-containing compound, is a compound in which a fluorinatable atom or bond of a raw material compound is fluorinated. In liquid-phase fluorination, a fluorine-containing compound having a structure corresponding to the carbon skeleton of the raw material compound is produced. However, when the raw material compound has carbon-carbon unsaturated bonds, a fluorine atom may be added to one or more of the unsaturated bonds to change the bonding state.

Examples of the target compound include fluorinated compounds of the compounds exemplified in the section on raw material compounds. Thus, examples of the target compound include fluorinated aliphatic hydrocarbons, aromatic hydrocarbons, ether compounds, ester compounds, amide compounds, thioether compounds, thioester compounds, etc. The target compound may also be a compound containing a heteroatom or a heteroatom group in the carbon skeleton of these compounds that is not changed by the fluorination reaction.
Among these, specific examples of useful target compounds include perfluoroalkanes, perfluoroether compounds, chlorofluorocarbons, and chlorofluoroether compounds.

The term "target compound" does not necessarily mean a final target product. The target fluorine-containing compound may be useful as it is or may be chemically converted into another compound.
When the starting compound is an ester compound represented by the formula (1), the target compound is preferably a compound represented by the following formula (6): When the starting compound is a compound represented by the formula (2), the target compound is preferably a compound represented by the following formula (7):
R ^AF1 -O-(C=O)-R ^BF1 ... (6)
R ^BF2 -(C=O)-OR ^AF2 -O-(C=O)-R ^BF3 ... (7)
In formulas (6) and (7),
R ^AF1 , R ^BF1 , R ^AF2 , R ^BF2 , and R ^BF3 are groups corresponding to R ^A1 , R ^B1 , R ^A2 , R ^B2 , and R ^B3 , respectively;
when R ^A1 , R ^B1 , R ^A2 , R ^B2 and R ^B3 are each independently a group not containing a hydrogen atom, R ^AF1 , R ^BF1 , R ^AF2 , R ^BF2 and R ^BF3 are the same group as R ^A1 , R ^B1 , R ^A2 , R ^B2 and R ^B3 ;
When R ^A1 , R ^B1 , R ^A2 , R ^B2 , and R ^B3 are each independently a group containing a hydrogen atom, R ^AF1 , R ^BF1 , R ^AF2 , R ^BF2 , and R ^BF3 are groups in which all hydrogen atoms present in R ^A1 , R ^B1 , R ^A2 , R ^B2 , and R ^B3 have been replaced with fluorine atoms.

[R ^AF1 ]
In formula (6), R ^AF1 is a group corresponding to R ^A1 .
When R ^A1 contains a hydrogen atom, R ^AF1 is a group in which all hydrogen atoms present in R ^A1 are substituted with fluorine atoms. When R ^A1 does not contain a hydrogen atom, R ^AF1 is the same group as R ^A1 .
From the viewpoint of excellent solubility in a solvent, R ^AF1 is preferably represented by the following formula (A3).
^R14O- ( ^R15O ) _m3 - ^R16- ... (A3)

In formula (A3), R ¹⁴ is a perfluoroalkyl group, R ¹⁵ is 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.

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

In formula (A3), -(R ¹⁵ O) _m3 - corresponds to -(R ¹² O) _m1 - in formula (A1). When R ¹² contains a hydrogen atom, R ¹⁵ is a group in which all hydrogen atoms contained in R ¹² are substituted with fluorine atoms. When R ¹² does not contain a hydrogen atom, R ¹⁵ is the same as R ¹² .

In formula (A3), —(R ¹⁵ O) _m3 — is preferably represented by the following formula (A4).
-[(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)
however,
R ^ff1 is a perfluoroalkylene group having 1 carbon atom;
R ^ff2 is a perfluoroalkylene group having 2 carbon atoms,
R ^ff3 is a perfluoroalkylene group having 3 carbon atoms,
R ^ff4 is a perfluoroalkylene group having 4 carbon atoms,
R ^ff5 is a perfluoroalkylene group having 5 carbon atoms,
R ^ff6 is a perfluoroalkylene group having 6 carbon atoms.
k7, k8, k9, k10, k11, and k12 each independently represent an integer of 0 or 1 or more, and k7+k8+k9+k10+k11+k12 is an integer of 0 to 500.

In formula (A4), R ^ff1 to R ^ff6 correspond to R ^f1 to 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 substituted with fluorine atoms. When R ^f1 does not contain a hydrogen atom, R ^ff1 is the same as R ^f1 . ^The same applies to R ^ff2 to R ^ff6 .

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

Among these, —(R ¹⁵ O) _m3 — preferably contains at least one selected from the group consisting of structures represented by the following formulae (G1) to (G3), and more preferably contains a structure represented by formula (G2).
-(R ^ff1 O) _k7 -(R ^ff2 O) _k8 - ... (G1)
-(R ^ff2 O) _k8 -(R ^ff4 O) _k10 - ... (G2)
-(R ^ff3 O) _k9 - ... (G3)
However, the symbols in formulas (G1) to (G3) are the same as those in formula (A4) above.

In formula (G1) and formula (G2), the bonding order of ( ^Rff1O ) and ( ^Rff2O ), and ( ^Rff2O ) and ( ^Rff4O ) are each arbitrary. For example, ( ^Rff1O ) and ( ^Rff2O ) may be arranged alternately, ( ^Rff1O ) and ( ^Rff2O ) may be arranged in blocks, or may be arranged randomly. The same applies to formula (G2).
In formula (G1), k7 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. Furthermore, k8 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20.
In formula (G2), k8 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. Also, k10 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20.
In formula (G3), k9 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20.

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

Examples of R ¹⁶ include the same as R ^ff1 to R ^ff6 above.

Of these, R ¹⁶ is preferably a perfluoroalkylene group having 1 to 3 carbon atoms.

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

Specific examples of R ^AF1 include the following structures, in which * represents a bonding site with --O--, n1 represents an integer of 0 to 60, and n2 represents an integer of 0 to 500. n1 is, for example, 13, and n2 is, for example, 7.

[R ^BF1 ]
In formula (6), R ^BF1 is a group corresponding to R ^B1 .
When R ^B1 contains a hydrogen atom, R ^BF1 is a group in which all hydrogen atoms present in R ^B1 are substituted with fluorine atoms. When R ^B1 does not contain a hydrogen atom, R ^BF1 is the same group as R ^B1 .
From the viewpoint of excellent solubility in a solvent, R ^BF1 is preferably represented by the following formula (B2).
R ²⁴ O-(R ²⁵ O) _m4 -R ²⁶ - ... (B2)

In formula (B2), R ²⁴ is a perfluoroalkyl group, R ²⁵ is each 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 of 0 to 20.

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 substituted with fluorine atoms. When R ²¹ does not contain a hydrogen atom, R ²⁴ is the same as R ²¹ .

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 of the hydrogen atoms contained in R ²² are substituted with fluorine atoms. When R ²² does not contain a hydrogen atom, R ²⁵ is the same as R ²² .

In formula (B2), —(R ²⁵ O) _m4 — is preferably represented by the above formula (A4).

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 substituted with fluorine atoms. When R ²³ does not contain a hydrogen atom, R ²⁶ is the same as R ²³ .

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

Specific examples of R ^BF1 include the following structures, in which * represents the bonding site with -O-(C=O)-.

[R ^AF2 ]
In formula (7), R ^AF2 is a group corresponding to R ^A2 .
When R ^A2 contains a hydrogen atom, R ^AF2 is a group in which all hydrogen atoms present in R ^A2 are substituted with fluorine atoms. When R ^A2 does not contain a hydrogen atom, R ^AF2 is the same group as R ^A2 .

From the viewpoint of excellent solubility in a solvent, R ^AF2 is preferably represented by the following formula (A6): That is, R ^AF2 preferably further has an ether bond.
^-R34O- ( ^R35O ) _m6 - ^R36- ... (A6)

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.

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 in which all hydrogen atoms contained in R ³¹ are substituted 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 in which all hydrogen atoms contained in R ³³ are substituted with fluorine atoms. When R ³³ does not contain a hydrogen atom, R ³⁶ is the same as R ³³ .

In formula (A6), -(R ³⁵ O) _m6 - corresponds to -(R ³² O) _m5 - in formula (A5). When R ³² contains a hydrogen atom, R ³⁵ is a group in which all hydrogen atoms contained in R ³² are substituted with fluorine atoms. When R ³² does not contain a hydrogen atom, R ³⁵ is the same as R ³² .

In formula (A6), R ³⁴ and R ³⁶ each independently have the same meaning as R ³¹ and R ³³ in formula (A5).
In formula (A6), examples of -(R ³⁵ O) _m6 - include the same as -(R ³² O) _m5 - in formula (A5).

Specific examples of R ^AF2 include the following structures: * represents a bonding site with --O--, and n2 represents an integer of 0 to 500.

[ ^RBF2 and ^RBF3 ]
In formula (7), R ^{3 BF2} and R ^{3 BF3} are groups corresponding to R ^{3 B2} and R ^{3 B3} , respectively.
When R ^B2 contains a hydrogen atom, R ^BF2 is a group in which all hydrogen atoms present in R ^B2 are substituted with fluorine atoms. When R ^B2 does not contain a hydrogen atom, R ^BF2 is the same group as R ^B2 .
When R ^B3 contains a hydrogen atom, R ^BF3 is a group in which all hydrogen atoms present in R ^B3 are substituted with fluorine atoms. When R ^B3 does not contain a hydrogen atom, R ^BF3 is the same group as R ^B3 .

Examples of the group represented by R ^{3 BF2} or R ^{3 BF3} include the same groups as the group represented by R ^{3 BF1} in formula (6).

When the starting compound is an ether compound represented by the above-mentioned R ^x -OR ^Y , the target compound is preferably a compound represented by the following formula:
R ^XF -OR ^YF
In the formula, R ^XF and R ^YF are groups corresponding to R ^X and R ^Y , respectively;
When R ^X and R ^Y are each independently a group not containing a hydrogen atom, R ^XF and R ^YF are the same group as R ^X and R ^Y ;
When R ^{1 X} and R 1 ^Y are each independently a group containing a hydrogen atom, R ^{1 XF} and R 1 ^YF are groups in which all hydrogen atoms present in R ^{1 X} and R 1 ^Y have been substituted with fluorine atoms.

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

(Organic solvent)
In the liquid phase fluorination, an organic solvent is used as a solvent in the liquid phase. The organic solvent includes a specific solvate. In addition to the specific solvate, the organic solvent may or may not include a compound other than the specific solvate. From the viewpoint of excellent conversion rate in the liquid phase fluorination, the content of the specific solvate relative to the total amount of the organic solvent is preferably 1 mass% or more, more preferably 10 mass% or more, even more preferably 20 mass% or more, and may be 50 mass% or more. From the viewpoint of suppressing heat generation, the content may be 90 mass% or less, 80 mass% or less, or 70 mass% or less. From the above viewpoint, the content may be 1 to 90 mass%, 10 to 80 mass%, 20 to 70 mass%, or 50 to 70 mass%.

In one embodiment, the organic solvent may contain a specific solvent compound and a perhalogeno compound. By using such a mixed solvent, heat generation can be suppressed. From the viewpoint of excellent conversion rate in liquid-phase fluorination, the content of the specific solvent compound relative to the total amount of the specific solvent compound and the perhalogeno compound is preferably 1 mass% or more, more preferably 10 mass% or more, and even more preferably 20 mass% or more. From the viewpoint of suppressing heat generation, the content may be 90 mass% or less, 80 mass% or less, or 70 mass% or less. From the above viewpoint, the content may be 1 to 90 mass%, 10 to 80 mass%, 20 to 70 mass%, or 50 to 70 mass%.
Examples of the perhalogeno compound include perfluoroalkanes, perfluoroether compounds, chlorofluorocarbons, chlorofluoroether compounds, perfluoroamines, etc. More specifically, examples of the perhalogeno compounds include those exemplified as fluorine-containing compounds other than the specific solvent compounds described below.

The organic solvent should preferably have high solubility for the raw material compounds overall, and should preferably be capable of dissolving 1% or more by mass of the raw material compounds at 25°C, and more preferably be capable of dissolving 5% or more by mass.

When the amount of hydrogen atoms per mL of the organic solvent is Ch (mmol) and the amount of double bonds is Cd (mmol), Ct expressed as Ct=Ch+2Cd is preferably 0.01 to 100 mmol, more preferably 0.01 to 50 mmol. When Ct is equal to or greater than the lower limit, the conversion rate of fluorination is excellent. When Ct is equal to or less than the upper limit, the reaction heat can be suppressed, and the decomposition reaction of the raw material compound can be suppressed.
When the organic solvent contains only a specific solvate, the Ct represents the Ct for the specific solvate, and when the organic solvent contains a specific solvate and other compounds, the Ct represents an average value calculated by multiplying the Ct of each compound contained in the organic solvent by its volume ratio.

From the viewpoint of improving the yield, the boiling point of the organic solvent (the boiling point of the specific solvent compound in the case of a single specific solvent compound, and the boiling points of each compound in the case of a mixed solvent) is preferably 10 to 500°C, more preferably 30 to 250°C, and even more preferably 50 to 150°C.

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

The total amount of organic solvents is preferably 1 time by mass or more, more preferably 5 times by mass or more, and even more preferably 10 times by mass or more, relative to the raw material compounds. The total amount of organic solvents may be 100 times by mass or less, 50 times by mass or less, or 20 times by mass or less, relative to the raw material compounds. The total amount of organic solvents may be 1 to 100 times by mass, 5 to 50 times by mass, or 10 to 20 times by mass, relative to the raw material compounds.

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, even 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).

-Specific solvent compounds-
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 either a C-H bond or a double bond, or may have both.

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

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 equal to or greater than the lower limit, the conversion rate is excellent, and if the number is equal to or less than the upper limit, the reaction heat can be suppressed, and the decomposition reaction of the raw material compound can be suppressed.

If 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 even more preferably 1.

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

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, even more preferably 100 to 10,000, and particularly preferably 100 to 5,000. When there is a molecular weight distribution, the molecular weight represents the mass average molecular weight (Mw).

The specific solvent compound is preferably a compound that, as a single compound, has high solubility for the raw material compound, preferably a compound that can dissolve 1% by mass of the raw material compound, and more preferably a compound that can dissolve 5% by mass or more.

Examples of the specific solvent compound include hydrocarbons, ether compounds, ester compounds, and ketone compounds, with hydrocarbons and ether compounds being preferred.
Examples of the hydrocarbon include those having a carbon number of 2 to 100, preferably 2 to 50, more preferably 2 to 20, and even more preferably 2 to 10. The hydrocarbon may be saturated or unsaturated, and may be linear, branched, or cyclic.
The ether compound may be an ether compound having a carbon number of 2 to 100, preferably 2 to 50, more preferably 2 to 20, and even more preferably 2 to 10. The number of ether bonds in the ether compound may be one or more.
The ester compound may be an ester compound having a carbon number of 2 to 100, preferably 2 to 50, more preferably 2 to 20, and even more preferably 2 to 10. The number of ester bonds in the ester compound may be one or more.
The ketone compound may have a carbon number of 2 to 100, preferably 2 to 50, more preferably 2 to 20, and even more preferably 2 to 10. The number of carbonyl groups in the ketone compound may be one or more.
The specific solvent compound may be used alone or in combination of two or more kinds.

Specific examples of the specific solvent compound include chloroolefins, hydrochloroolefins, hydrochlorofluoroolefins, hydrofluoroethers, hydrochlorofluoroethers, hydrofluorocarbons, hydrochlorofluorocarbons, and hydrobromocarbons.
Available specific solvates or mixtures thereof are shown in the table below, in which (Z) stands for Z form and (E) stands for E form.

The specific solvent compound also includes the following compounds.
CH ₂ ClCHClCH ₂ OCF ₂ CHFCl (also referred to as "HCFE-473");
CF ₂ ClCFClCHFOCF ₂ CF ₂ Cl (also referred to as "HCFE-428a, b");
CHFClCFClCF ₂ OCF ₂ CF ₂ Cl (also referred to as "HCFE-428c, d");
CF ₂ ClCHClCF ₂ OCF ₂ CF ₂ Cl (also referred to as "HCFE-428e");
CHFClCFClCHFOCF ₂ CF ₂ Cl (also referred to as "HCFE-437a, b");
CF ₂ ClCHClCHFOCF ₂ CF ₂ Cl (also referred to as "HCFE-437c");
CHFClCFClCH ₂ OCF ₂ CF ₂ Cl (also referred to as "HCFE-446a");
CF ₂ ClCCl ₂ CF ₂ OCF ₂ CHFCl (also referred to as "HCFE-427a, b");
CF ₂ CFClCF ₂ OCF ₂ CF ₂ Cl (also known as "HCFE-429").

In liquid phase fluorination, the amount of the specific solvent compound is 0.1 times the equivalent of the raw material compound or more, preferably 1 times the equivalent or more, more preferably 5 times the equivalent or more, and may be 10 times the equivalent or more. The amount of the specific solvent compound is preferably 200 times the equivalent of the raw material compound or less, more preferably 100 times the equivalent or less, and may be 50 times the equivalent or less. When the amount of the specific solvent compound is equal to or more than the lower limit, the conversion rate of fluorination is excellent. When the amount of the specific solvent compound is equal to or less than the upper limit, it is advantageous when it is desired to reduce the amount of the specific solvent compound used. From the above viewpoint, the amount of the specific solvent compound is preferably 0.1 to 200 times the equivalent of the raw material compound, more preferably 1 to 100 times the equivalent, and may be 5 to 50 times the equivalent, or may be 10 to 50 times the equivalent.

- Organic solvents other than specific solvent compounds -
The organic solvent other than the specific solvent compound is preferably a fluorine-containing compound other than the specific solvent compound, for example, a perfluoroalkane, or an organic compound 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.

The fluorine-containing compound other than the specific solvent compound is preferably a compound that has high solubility in the raw material compound as a single compound, preferably a compound that can dissolve 1% by mass or more of the raw material compound at 25°C, and more preferably a compound that can dissolve 5% by mass or more.

The fluorine-containing compound other than the specific solvent compound may be at least one selected from the group consisting of chlorine-containing solvents and fluorine-containing solvents other than chlorine-containing solvents.
Examples of chlorine-containing solvents include CClF ₂ CClFCF ₂ OCF ₂ CClF ₂ (also referred to as "CFE-419"), 1,2,3,4-tetrachloroperfluorobutane (also referred to as "R-113"), CF ₂ ClCFClCFClOCF ₂ CF ₂ Cl (also referred to as "CFE-418"), and the like.
Examples of fluorine-containing solvents other than chlorine-containing solvents include perfluoroalkanes (FC-72, etc.), perfluoroethers (FC-75, FC-77, etc.), perfluoropolyethers (trade names: Krytox, Fomblin, Galden, Demnum, etc.), inert fluids (trade name: Fluorinert), and perfluorocarboxylic acid fluorides.

Examples of the fluorine-containing compound other than the specific solvent compound include the following acid fluorides.
_CF3CF2CF2OCF ( _{CF3 ) COF
CF3CF2CF2OCF ( CF3 ) CF2OCF} ( _CF3 )COF
_{CF3CF2CF2OCF ( CF3 )} CF2OCF( _{CF3 ) CF2OCF} ( _CF3 )COF
The organic solvent other than the specific solvent compound may be used alone or in combination of two or more kinds.

[Liquid Phase Fluorination Process]
The reaction type of the fluorination reaction may be a batch system or a continuous system, and the continuous system is preferred. The fluorination method may be the fluorination methods 1 and 2 described below. From the viewpoint of excellent conversion, the fluorination method 2 described below is preferably carried out in a continuous system.

Fluorination method 1: A reactor is charged with raw material compounds and a solvent, and stirring is started. The reaction is carried out at a given reaction temperature and pressure while continuously supplying fluorine gas.
Fluorination method 2: A solvent is charged into a reactor and stirring is started. A raw material compound and fluorine gas are continuously and simultaneously fed at a predetermined molar ratio under a predetermined reaction temperature and reaction pressure.

When supplying the raw material compound in fluorination method 2, the raw material compound may be supplied as is without diluting it with a solvent. When diluting the raw material compound with a solvent, the amount of the solvent is preferably at least 1-fold by mass, and more preferably at least 2-fold by mass, relative to the raw material compound.

In liquid-phase fluorination, fluorine gas may be used as is, or a mixed gas in which fluorine gas is diluted with an inert gas may be used. Examples of inert gases include nitrogen gas, helium gas, neon gas, and argon gas. Nitrogen gas or helium gas is preferred, and nitrogen gas is more preferred. From the viewpoint of excellent conversion, the concentration of fluorine gas in the mixed gas is preferably 10% by volume or more, more preferably 15% by volume or more, and even more preferably 20% by volume or more. From the viewpoint of suppressing excessive reactivity, it is preferably 60% by volume or less, more preferably 50% by volume or less, and even more preferably 40% by volume or less. From the above viewpoints, the concentration of fluorine gas in the mixed gas is preferably 10 to 60% by volume, more preferably 15 to 50% by volume, and even more preferably 20 to 40% by volume.

From the viewpoint of achieving a good conversion rate, the amount of fluorine used in the liquid-phase fluorination is preferably an amount that provides an excess equivalent of fluorine relative to the hydrogen atoms in the raw material compound, and more preferably an amount that provides 1.5 equivalents (i.e., 1.5 moles) or more. It is preferable that the amount of fluorine be such that an excess equivalent is maintained from the beginning to the end of the liquid-phase fluorination.

The reaction temperature for the liquid phase fluorination is preferably −60° C. or higher and the boiling point of the raw material compound or lower, and from the viewpoints of reaction yield, selectivity, and ease of industrial implementation, is more preferably −50° C. to 100° C., and further preferably −20° C. to 50° C.
The reaction pressure for the liquid phase fluorination is not particularly limited, but from the viewpoints of excellent conversion rate and ease of industrial implementation, it is preferably 0 to 2 MPa.

The reaction time in liquid phase fluorination (i.e., the time it takes for the raw material compounds to pass through the reaction field) is preferably 200 hours or less, more preferably 190 hours or less, even more preferably 170 hours or less, particularly preferably 150 hours or less, and extremely preferably 100 hours or less. The reaction time is preferably 0.3 hours or more, more preferably 0.6 hours or more, and even more preferably 1 hour or more. If the reaction time is equal to or greater than the lower limit, the reaction is likely to be sufficient, and if it is equal to or less than the upper limit, the production time and cost can be reduced. From the above viewpoint, the reaction time is preferably 0.3 to 200 hours, more preferably 0.6 to 190 hours, even more preferably 1 to 170 hours, particularly preferably 1 to 150 hours, and extremely preferably 1 to 100 hours.

In the fluorination process, the content of the raw material compound in the liquid phase is preferably 10 to 70 mass%, more preferably 20 to 50 mass%.

In order to efficiently proceed with the liquid-phase fluorination and improve the yield, it is preferable to irradiate the reaction system with ultraviolet light. In a batch reaction, it is preferable to irradiate the reaction system with ultraviolet light in the later stages of the liquid-phase fluorination. The ultraviolet light irradiation time is preferably 0.1 to 3 hours.

In order to efficiently proceed with the liquid phase fluorination, a compound having a C-H bond (however, a compound different from the specific solvating compound) or a compound having a carbon-carbon double bond may be added as an auxiliary. Note that when a compound having one specific type of C-H bond or a compound having a carbon-carbon double bond is used in an amount less than 0.1 equivalent relative to the raw material compound, the compound is classified as an auxiliary.
The auxiliary compound having a C-H bond is preferably an aromatic hydrocarbon, more preferably benzene, toluene, etc. The amount of the compound having a C-H bond added is preferably 0.1 mol % or more and less than 10 mol %, more preferably 0.1 to 5 mol %, based on the hydrogen atoms of the raw material compound.
Examples of the auxiliary compound having a carbon-carbon double bond include CF ₃ CF═CF ₂ and CF ₂ ═CF-CF═CF ₂ .
The amount of the compound having a carbon-carbon double bond added is preferably 0.1 mol % or more and less than 10 mol %, more preferably 0.1 to 5 mol %, based on the hydrogen atoms in the raw material compounds.

For example, in a batch reaction, an auxiliary may be added to the reaction system in the later stages of liquid phase fluorination. The auxiliary is preferably added in a state where fluorine is present in the reaction system. When the auxiliary is added, it is preferable to pressurize the reaction system. The pressure during pressurization is preferably 0.01 to 5 MPa.

On the other hand, this manufacturing method does not require the use of auxiliary agents. With this manufacturing method, a suitable yield can be obtained without using auxiliary agents.

When a reaction occurs in which hydrogen atoms are replaced by fluorine atoms during liquid-phase fluorination of raw material compounds, HF is produced as a by-product. To capture HF, it is preferable to either have an HF scavenger present in the reaction system or to bring the HF scavenger into contact with the outlet gas at the reactor gas outlet. For example, NaF is a preferred HF scavenger.

The crude product containing the fluorine-containing compound obtained by liquid-phase fluorination may be used as is in the next step, or may be purified to a high purity. Examples of purification methods include distilling the crude product directly under normal or reduced pressure.

Next, the embodiments of the present disclosure will be described in detail using examples, but the embodiments of the present disclosure are not limited to these examples. In the following examples, Examples 1 to 4 are examples, and Example 5 is a comparative example.

The compounds used as solvents in the examples are as follows.
(HFPO) ₃ ... _{CF3CF2CF2OCF ( CF3} ) _CF2OCF ( _CF3 )C(=O)F, boiling point 113° _C
AE-3000 (product name)...CF ₃ CH ₂ OCF ₂ CHF ₂ , boiling point 56°C, molecular weight 200, specific gravity 1.47 (25°C, g/mL)
AS-300 (trade name)...CF ₂ HCF = CHCl (Z), boiling point 54°C, molecular weight 130.5, specific gravity 1.38 (25°C, g/mL)
(HFPO) ₃ , AE-3000, and AS-300 were all manufactured by AGC.

Example 1
_{CF3CF2OCF2CF2OCF2CF2OCOCF ( CF3 ) OCF2CF ( CF3} ) _OCF2CF2CF3 (target compound _{) was} produced by _the following _method .
CH ₃ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCOCF(CF ₃ )OCF ₂ CF(CF ₃ )OCF ₂ CF ₂ CF ₃ (raw material compound, molecular weight 612) was prepared according to Example 1 (step 1-1) of International Publication No. 2008/026707. 20 g of the raw material compound was dissolved in 200 g of AE-3000, and this was used as a raw material solution. 200 g of AE-3000 was added to a 500 mL SUS316 autoclave and stirred, and nitrogen gas was blown in for 1 hour, and then fluorine gas diluted to 30% by volume with nitrogen gas was passed through. Thereafter, the raw material solution was injected over 24 hours while blowing in fluorine gas diluted to 30% by volume with nitrogen gas at a flow rate of 25.01 L/hour at 25°C. After stirring at 25° C. for 1 hour, nitrogen gas was blown in for 2 hours, and the resulting crude liquid was concentrated with an evaporator. The product was quantified by ¹⁹ F-NMR and ¹ H-NMR to determine the conversion rate. The conversion rate is given by the following formula.
Conversion rate (%) = {1 - (number of fluorinated atoms per molecule of product) / (number of fluorinable atoms per molecule of starting compound)} x 100

Example 2
Except for using AS-300 instead of AE-3000, the raw material compound was fluorinated in the same manner as in Example 1. The product was quantitatively determined by ¹⁹ F-NMR and ¹ H-NMR to determine the conversion rate.

Example 3
The raw material compound was fluorinated in the same manner as in Example 1, except that a solvent in which AE-3000 and (HFPO) ₃ were mixed in a ratio of 1:99 (mass ratio) was used instead of AE-3000. The product was quantified by ¹⁹ F-NMR and ¹ H-NMR to determine the conversion rate.

Example 4
The raw material compound was fluorinated in the same manner as in Example 1, except that a solvent in which AE-3000 and (HFPO) ₃ were mixed in a ratio of 10:90 (mass ratio) was used instead of AE-3000. The product was quantified by ¹⁹ F-NMR and ¹ H-NMR to determine the conversion rate.

Example 5
Except for using (HFPO) ₃ instead of AE-3000, the raw material compound was fluorinated in the same manner as in Example 1. The product was quantified by ¹⁹ F-NMR and ¹ H-NMR to determine the conversion rate.

The conditions and conversion rates for each example are shown in Table 2.

As shown in Table 2, in Examples 1 to 4, in which the raw material compounds were fluorinated using the specific solvent compounds AE-3000 and AS-300 as the solvent, a high conversion rate was obtained without the use of an auxiliary agent. This shows that if a specific solvent compound is used, a fluorine-containing compound can be produced at a high conversion rate without the use of an auxiliary agent. In addition, a good conversion rate was obtained when a mixed solvent of a specific solvent compound and a perhalogeno compound was used.

The disclosed method for producing a fluorine-containing compound allows for fluorination with a good conversion rate, and simplifies the process. The obtained fluorine-containing compound can be derived into a fluorine-containing compound having various functional groups (e.g., a hydroxyl group, an ethylenically unsaturated group, an epoxy group, a carboxy group, etc.). In addition, the obtained fluorine-containing compound and fluorine-containing compounds that can be derived from the fluorine-containing compound can be used as a surface treatment agent, emulsifier, rubber, surfactant, solvent, heat transfer medium, pharmaceuticals, agricultural chemicals, lubricants, intermediates thereof, etc.

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 herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims (8)

The method includes fluorinating an organic compound having at least one fluorinatable atom or bond in an organic solvent into which fluorine gas has been introduced,
the organic solvent contains a compound having a halogen atom and a C—H bond or a double bond,
the amount of the compound having a halogen atom and a C—H bond or a double bond is 0.1 equivalents or more relative to the amount of the organic compound having at least one fluorinatable atom or bond. The method for producing a fluorine-containing compound according to claim 1, wherein Ct, expressed as Ct = Ch + 2Cd, is 0.01 to 100 mmol, where Ch (mmol) is the amount of hydrogen atoms per mL of the organic solvent, and Cd (mmol) is the amount of double bonds per mL of the organic solvent. The method for producing a fluorine-containing compound according to claim 1 or 2, wherein the organic solvent contains a compound having a halogen atom and a C-H bond or a double bond, and a perhalogeno compound. The method for producing a fluorine-containing compound according to claim 3, wherein the content of the compound having a halogen atom and a C-H bond or a double bond relative to the total amount of the compound having a halogen atom and a C-H bond or a double bond and the perhalogeno compound in the organic solvent is 1 mass% or more. The method for producing a fluorine-containing compound according to claim 1 or 2, which does not include the addition of an auxiliary agent. The method for producing a fluorine-containing compound according to claim 1 or 2, wherein the compound having a halogen atom and a C-H bond or a double bond includes at least one selected from the group consisting of a hydrocarbon, an ether compound, an ester compound, and a ketone compound. The method for producing a fluorine-containing compound according to claim 1 or 2, wherein the compound having a halogen atom and a C-H bond or a double bond includes at least one selected from the group consisting of chloroolefins, hydrochloroolefins, hydrochlorofluoroolefins, hydrofluoroethers, hydrofluorocarbons, hydrochlorofluorocarbons, and hydrobromocarbons. The method for producing a fluorine-containing compound according to claim 1 or 2, wherein in the organic compound having at least one fluorinable atom or bond, the fluorinable atom 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 fluorinable bond is a carbon-carbon unsaturated double bond or a carbon-carbon unsaturated triple bond.