JP2024074671A - Method for producing fluorine-containing compound - Google Patents

Abstract

[Problem] To provide a method for producing a fluorine-containing compound which is excellent in the yield of the target fluorine-containing compound. [Solution] A method for producing a fluorine-containing compound, comprising: fluorinating an organic compound having one or more fluorinatable atoms or bonds in a vessel containing a liquid phase containing an organic solvent and an organic solvent, and a gas phase containing a mixed gas containing fluorine gas, the organic compound having one or more fluorinatable atoms or bonds being fluorinated, the gas phase containing a halogen-containing organic compound in the fluorination of the organic compound having one or more fluorinatable atoms or bonds, and the molar fraction of the halogen-containing organic compound in the gas phase being 0.065 or less. [Selected Figures] None

Description

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

Various methods are known for fluorinating a compound having one or more fluorinable atoms or bonds, such as hydrogen atoms, and for example, a method of fluorination using fluorine gas is known. Patent Document 1 discloses a method of fluorinating a compound having one or more fluorinable atoms or bonds by supplying fluorine gas to a vessel such as an autoclave that contains a compound having one or more fluorinable atoms or bonds and a liquid phase containing an organic solvent.

International Publication No. 2000/056694

In the fluorination method disclosed in Patent Document 1, the boiling point of a compound having one or more fluorinatable atoms is increased to suppress the compound having one or more fluorinatable atoms from vaporizing and decomposing due to contact with fluorine gas, thereby improving the yield of the target product (a fluorine-containing compound).
However, the present inventors have found that there is room for further improvement in suppressing the decomposition of compounds having one or more fluorinatable atoms, and that the yield of the target product can be further improved.

The problem that one embodiment of the present disclosure aims to solve is to provide a method for producing a fluorine-containing compound that has an excellent yield of the target fluorine-containing compound.

The present disclosure includes the following aspects.
<1> In a vessel containing a liquid phase including an organic compound having one or more fluorinable atoms or bonds and an organic solvent, and a gas phase including a mixed gas including fluorine gas, the organic compound having one or more fluorinable atoms or bonds is fluorinated;
In the fluorination of the organic compound having one or more fluorinatable atoms or bonds, the gas phase contains a halogen-containing organic compound, and the molar fraction of the halogen-containing organic compound in the gas phase is 0.065 or less.
A method for producing a fluorine-containing compound.
<2> The method for producing a fluorine-containing compound according to the above <1>, wherein in the fluorination of the organic compound having one or more fluorinatable atoms or bonds, the content of the fluorine gas relative to the total volume of the mixed gas is 70 volume % or less.
<3> The method for producing a fluorine-containing compound according to the above <1> or <2>, wherein after the fluorination of the organic compound having one or more fluorinatable atoms or bonds, the mixed gas is discharged from the vessel, and the content of the fluorine gas relative to the total volume of the discharged mixed gas is 60 volume% or less.
<4> The method for producing a fluorine-containing compound according to any one of <1> to <3> above, wherein the organic solvent has a boiling point of 50 to 500° C. or higher.
<5> The method for producing a fluorine-containing compound according to any one of <1> to <4> above, wherein the halogen-containing organic compound contains fluorine.
<6> The method for producing a fluorine-containing compound according to any one of <1> to <5> above, wherein the organic solvent is a perhalogeno compound.
<7> The method for producing a fluorine-containing compound according to any one of <1> to <6> above, wherein the organic solvent has 4 or more carbon atoms.

According to one embodiment of the present disclosure, a method for producing a fluorine-containing compound can be provided that provides an excellent yield of the target fluorine-containing compound.

Embodiments of the present disclosure are described in detail below. However, the embodiments of the present disclosure are not limited to the following embodiments. In the following embodiments, the components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values and their ranges, and do not limit the embodiments of the present disclosure.

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 of each component means the total content of the multiple substances present in the composition, unless otherwise specified.

[Method of producing fluorine-containing compounds]
The method for producing a fluorine-containing compound according to the present disclosure (hereinafter also referred to as "the production method") comprises fluorinating an organic compound having one or more fluorinatable atoms or bonds (hereinafter also referred to as "specific organic compound") in a vessel containing a liquid phase containing an organic solvent and an organic solvent, and a gas phase containing a fluorine-containing mixed gas,
In the fluorination of the specific organic compound, the gas phase contains a halogen-containing organic compound, and the molar fraction of the halogen-containing organic compound in the gas phase is 0.065 or less.

According to the present production method, the yield of the target fluorine-containing compound can be improved. The reason why the above effect is exhibited is not clear, but is presumed to be as follows.
In this production method, a specific organic compound is fluorinated in a vessel containing a liquid phase and a gas phase. During fluorination, the molar fraction of the halogen-containing organic compound in the gas phase is 0.065 or less. This can prevent the temperature of the gas phase from becoming excessively high, thereby suppressing decomposition of the specific organic compound, and it is estimated that the yield of the target fluorine-containing compound is improved.

From the viewpoint of improving the yield of the fluorine-containing compound, the above molar fraction is preferably 0.050 or less, more preferably 0.035 or less, and even more preferably 0.030 or less. The lower limit of the above molar fraction is not particularly limited and may be 0.

In this disclosure, the molar fraction of the halogen-containing organic compound is determined by dividing the vapor pressure of the halogen-containing organic compound in a container during the fluorination of the specific organic compound by the pressure in the container during the fluorination of the specific organic compound.

The molar fraction of the halogen-containing organic compound can be adjusted by the boiling point, molecular weight, carbon number, structure, amount used, etc. of the specific organic compound used, the temperatures of the liquid and gas phases, the structure of the organic solvent used, the amount of fluorine gas used, etc.

(Liquid Phase)
From the viewpoint of improving the yield of the fluorine-containing compound, the specific organic compound is preferably dissolved in an organic solvent.
From the viewpoint of improving the yield of the fluorine-containing compound, the specific organic compound is dissolved in the organic solvent at 25° C. in an amount of preferably 1% by mass or more, and more preferably 5% by mass or more.

From the viewpoint of improving the yield of the fluorine-containing compound, the temperature of the liquid phase in the fluorination of the specific organic compound is preferably from 10 to 80°C, more preferably from 15 to 70°C, and even more preferably from 15 to 40°C.
The temperature of the liquid phase is measured by a thermometer placed in the liquid phase portion of the container.

-Specific organic compounds-
The specific organic compound has one or more fluorinable atoms or bonds.
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.
Fluorinable bonds include carbon atoms in carbon-carbon unsaturated double bonds and carbon-carbon unsaturated triple bonds.

From the viewpoint of improving the yield of the fluorine-containing compound, the boiling point of the specific organic compound is preferably 30° C. or higher, more preferably from 50 to 500° C. or higher, and even more preferably from 70 to 450° C. or higher.
In this disclosure, the "boiling point" refers to the boiling point at normal pressure, which is 0.1 MPa.
In this disclosure, the boiling point is measured in a manner similar to that prescribed in the boiling point measurement method for Class 4 hazardous materials under the Fire Service Act.

From the viewpoint of improving the yield of the fluorine-containing compound, the carbon number of the specific organic compound is preferably 4 or more, more preferably 4 to 1,000, and even more preferably 4 to 500.

From the viewpoint of improving the yield of the fluorine-containing compound, the molecular weight of the specific organic compound is preferably 200 or more, more preferably 400 to 50,000, and even more preferably 400 to 25,000.
When the molecular weight has a distribution, the molecular weight is expressed as a weight average molecular weight (Mw), which is measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent.

From the viewpoint of improving the yield of the fluorine-containing compound, the viscosity of the specific organic compound is preferably 2,000 mPa·s or less, and more preferably 1,000 mPa·s or less.
The lower limit of the viscosity of the organic compound is not particularly limited, but can be 0.1 mPa·s or more.
In this disclosure, viscosity is measured in accordance with JIS Z 8803 (2011).

From the viewpoint of improving solubility in organic solvents and the yield of fluorine-containing compounds, it is preferable that the specific organic compound has fluorine atoms. From the viewpoint of improving solubility in organic solvents and the yield of fluorine-containing compounds, the content of fluorine atoms relative to the total mass of the specific organic compound is preferably 5 to 80%, and more preferably 10 to 70%.

Specific organic compounds include fluoroalkane compounds, fluoroether compounds, fluoropolyether compounds, chlorofluorocarbon compounds, chlorofluoroether compounds, chlorofluoropolyether compounds, etc.

Specific examples of the specific organic compound are listed below, but are not limited to these.
_{CF3O ( CF2CFHOCF2CF2CF2CF2CH2O ) nCF2CFHOCF2CF2CF2CF2CH2OCOCF ( CF3 ) OCF2CF2CF3 , ​ ​ ​ ​ ​ ​
CH2ClCHClCH2OCF2CHFCl , ​
CF3CF2CF2OCF ( CF3 ) COOCH2CH2CH2CH2OCOCF ( CF3 ) OCF2CF2CF3 , ​ ​
CH3CH2OCH2CH2OCH2CH2OCOCCF ( CF3 ) OCF2CF ( CF3 ) OCF2CF2CF3 , ​ ​
( CF3 ) 2CFCOOCH2CH2CH2CH2CH2OCOCF ( CF3 ) 2 .}

In addition to the specific organic compounds described above, raw material ester compounds having one or more fluorinable atoms or bonds represented by the following chemical formula (1) or (2) can be used.
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 are substituted with 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 are substituted with a halogen atom.

In this disclosure, "heteroatom" means an atom other than a carbon atom or a hydrogen atom, and examples of such atoms 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 500, more preferably 1 to 200, and even more preferably 3 to 100, from the viewpoint of excellent solubility in a solvent.

Among these, 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 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 carbon number of 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 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.

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
These include (CHF ₂ )-CF ₂ -, -CH(CH ₂ F)-CF ₂ -, -CH(CH ₃ )-CF ₂ -, -CH(CF ₃ )-CHF-, -CH(CHF ₂ )-CHF-, -CH(CH ₂ F)-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 is ^preferably represented by the following formula ( ^A5 ): 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 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 a raw material ester compound is compound T1 below.

Further examples of the raw material ester compound include CH ₃ —O(CF ₂ CFHO-CF ₂ CF ₂ CF ₂ CH ₂ O) _n1 -C(═O)-CF(CF ₃ )OCF ₂ CF ₂ CF _3. Here, n1 represents a number of 1 or more, preferably 1 to 50, more preferably 1 to 40, and even more preferably 1 to 30.

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

The number average molecular weight (Mn) of the raw material ester compound 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. 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 the average molecular weight is equal to or less than the upper limit, the purification of the fluorine-containing 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.

The specific organic compound may be a commercially available product or may be synthesized by a conventional method.

- Organic solvents -
From the viewpoint of improving the yield of the fluorine-containing compound, the organic solvent is preferably a (per)halogeno compound, more preferably a (per)fluoro compound.
From the viewpoint of improving the yield of the fluorine-containing compound, the organic solvent is preferably a perhalogeno compound, more preferably a perfluoro compound.
In the present disclosure, the term "(per)halogeno compound" includes halogeno compounds having one or more halogenatable atoms or bonds (partially halogenated compounds) and halogeno compounds having no halogenatable atoms or bonds (perhalogeno compounds).

From the viewpoint of improving the yield of the fluorine-containing compound, it is preferable that the organic solvent has one or more atoms selected from the group consisting of a chlorine atom, a nitrogen atom, and an oxygen atom.

Examples of the organic solvent include (per)fluoroalkane compounds, (per)fluoroether compounds, (per)fluoropolyether compounds, chloro(per)fluorocarbon compounds, chloro(per)fluoroether compounds, chloro(per)fluoropolyether compounds, and inert fluid (e.g., Fluorinert, manufactured by 3M) compounds.
In the present disclosure, the term "(per)fluoro compound" includes a fluoro compound having one or more fluorinable atoms or bonds (partially fluorinated compounds) and a fluoro compound having no fluorinable atoms or bonds (perfluoro compounds).

From the viewpoint of improving the yield of the fluorine-containing compound, the boiling point of the organic solvent is preferably 50°C or higher, more preferably 50 to 500°C, even more preferably 50 to 300°C, and particularly preferably 50 to 250°C.

From the viewpoint of improving the yield of the fluorine-containing compound, the carbon number of the organic solvent is preferably 4 or more, more preferably 4 to 1,000, even more preferably 4 to 500, particularly preferably 4 to 100, and most preferably 4 to 50.

From the viewpoint of improving the yield of the fluorine-containing compound, the molecular weight of the organic solvent is preferably 200 or more, more preferably 200 to 50,000, even more preferably 200 to 25,000, particularly preferably 200 to 10,000, and most preferably 200 to 1,000.
When the molecular weight has a distribution, the molecular weight indicates the mass average molecular weight Mw.

From the viewpoint of improving the yield of the fluorine-containing compound, the viscosity of the organic solvent is preferably 0.5 to 2,000 mPa·s, more preferably 0.5 to 1,000 mPa·s, and even more preferably 1 to 500 mPa·s.

From the viewpoint of improving the yield of the fluorine-containing compound, the vapor pressure of the organic solvent in the vessel is preferably 0.009 MPa or less, more preferably 0.007 MPa or less, even more preferably 0.006 MPa or less, particularly preferably 0.005 MPa or less, and most preferably 0.003 MPa or less.
The lower limit of the vapor pressure is not particularly limited, and can be 0.001 MPa or more.
In the present disclosure, the vapor pressure of the organic solvent in the container is measured by a vapor pressure measuring device (for example, a vapor pressure measuring device manufactured by Japan Science Core Co., Ltd.) at the temperature of the organic solvent during the fluorination of the specific organic compound.

Specific examples of the organic solvent are listed below, but are not limited to these.
_{CF2ClCF2OCF2CFClCF2Cl , ​ ​
CF3CF2CF2OCF ( CF3 )} CF2OCF( _{CF3 )} COF,
_{CF3CF2CF2OCF ( CF3 )} CF2OCF( _{CF3 ) CF2OCF} ( _CF3 )COF
_{CF3CF2OCF2CF2OCF2CF2OCOCF ( CF3 ) OCF2CF ( CF3 ) OCF2CF2CF3 , ​ ​
( CF3 ) 2CFCOOCF2CF2CF2CF2CF2OCOCF ( CF3 ) 2 ,
CF2ClCFClCFClCF2Cl ,
CF3CF2CF2OCF} ( _{CF3 )} COF _{,
CF3CF2CF2OCF ( CF3 )} CF2OCF( _{CF3 )} COF,
_{CF3CF2CF2OCF ( CF3 )} CF2OCF( _{CF3 ) CF2OCF} ( _CF3 )COF

In addition to the organic solvents described above, solvents described in WO 02/004397, WO 02/010107, JP 2003-508374 A, WO 01/094285, WO 00/56694, etc. can also be used.

The organic solvent may be the same compound as the halogen-containing organic compound. The organic solvent may be the same compound as the fluorine-containing compound, or may be a different compound.

The organic solvent may be commercially available or may be synthesized by a conventional method.

(gas phase)
The gas phase comprises a gas mixture including fluorine gas.
In the fluorination of the specific organic compound, the gas phase contains a halogen-containing organic compound, and the molar fraction of the halogen-containing organic compound in the gas phase is 0.065 or less.

From the viewpoint of improving the yield of the fluorine-containing compound, it is preferable that the temperature of the gas phase in the fluorination of the specific organic compound is appropriately changed depending on the molar fraction of the halogen-containing organic compound, the fluorine gas content of the mixed gas in the fluorination of the specific organic compound, etc. Specifically, it is preferably 10 to 80°C, more preferably 15 to 70°C, and even more preferably 15 to 40°C.
The temperature of the gas phase is measured by a thermometer installed in the gas phase portion inside the vessel.

-Mixed gas-
The mixed gas contains fluorine gas.
From the viewpoint of improving the yield of the fluorine-containing compound, in the fluorination of the specific organic compound, the content of the fluorine gas relative to the total volume of the mixed gas is preferably appropriately changed according to the temperature of the gas phase in the fluorination of the specific organic compound. Specifically, it is preferably 99% by volume or less, more preferably 80% by volume or less, and even more preferably 70% by volume or less. The content of the fluorine gas may be 100% by volume.
The lower limit of the content is not particularly limited, and can be 1 volume % or more.

In the present production method, the mixed gas may be discharged from the vessel after the specific organic compound is fluorinated. The content of fluorine gas relative to the total volume of the mixed gas discharged from the vessel is preferably appropriately changed according to the molar fraction of the halogen-containing organic compound, the temperature of the gas phase in the fluorination of the specific organic compound, etc. Specifically, it is preferably 60% by volume or less, more preferably 50% by volume or less, even more preferably 30% by volume or less, and particularly preferably 20% by volume or less.
The lower limit of the content is not particularly limited, and can be 0.1 volume % or more.

The mixed gas may contain an inert gas, such as nitrogen gas, helium gas, neon gas, or argon gas.
From the viewpoint of improving the yield of the fluorine-containing compound, the content of the inert gas relative to the total volume of the mixed gas is preferably 1 vol % or more, more preferably 20 vol % or more, and even more preferably 30 vol % or more.
The upper limit of the content is not particularly limited, and can be 99% by volume or less.

--Halogen-containing organic compounds--
The halogen-containing organic compound may have one or more atoms selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, a fluorine atom is preferred.
The halogen-containing organic compound may be a (per)halogeno compound or a (per)fluoro compound. The halogen-containing organic compound is preferably a perhalogeno compound, and more preferably a perfluoro compound.

In one embodiment, the halogen-containing organic compound is a compound that is produced by vaporizing an organic solvent.

- Fluorine-containing compounds -
The fluorine-containing compound produced by the present production method is a fluoride of a specific organic compound, and is preferably a perfluoro compound.

Examples of fluorine-containing compounds include perfluoroalkane compounds, perfluoroether compounds, perfluoropolyether compounds, chloroperfluorocarbon compounds, chloroperfluoroether compounds, and chloroperfluoropolyether compounds.

Specific examples of the fluorine-containing compound are listed below, but the invention is not limited thereto.
_{CF3O ( CF2CF2OCF2CF2CF2CF2CF2O ) nCF2CF2OCF2CF2CF2CF2CF2OCOCF ( CF3 ) OCF2CF2CF3 , ​ ​ ​ ​ ​ ​ ​ ​
CF2ClCFClCF2OCF2CF2Cl , ​ ​
CF3CF2CF2OCF ( CF3 ) COOCF2CF2CF2CF2OCOCF ( CF3 ) OCF2CF2CF3 , ​ ​
CF3CF2OCF2CF2OCF2CF2OCOCF ( CF3 ) OCF2CF ( CF3 ) OCF2CF2CF3 , ​ ​
( CF3 ) 2CFCOOCF2CF2CF2CF2CF2OCOCF ( CF3 ) 2 .}
In addition to the above, fluorinated organic compounds represented by formula (1) may also be used.

-container-
The container is not particularly limited as long as it can contain a liquid phase containing the specific organic compound and the organic solvent, and a gas phase containing a mixed gas containing fluorine gas. An autoclave or the like can be used as the container.
The container may have a supply port for supplying the mixed gas, and may have an exhaust port for exhausting the mixed gas.
The discharge section may be provided with a cooler for cooling the mixed gas to form a condensate, and the container may have a liquid return pipe for returning the condensate to the container.
The vessel may have a layer filled with a scavenger for scavenging HF produced as a by-product in the fluorination of the specific organic compound. In one embodiment, the vessel may have a first cooler, an HF scavenger layer, and a second cooler connected to the discharge section. Examples of HF scavengers include NaF, KF, and trialkylamines.

The fluorination of the specific organic compound may be carried out by a batch method or a continuous method. From the viewpoint of improving the yield of the fluorine-containing compound, the continuous method is preferred.

An embodiment of the continuous fluorination method of a specific organic compound includes a method in which an organic solvent is supplied to a vessel, and then a mixture of the organic solvent and the specific organic compound, and a mixed gas are supplied to the vessel. Note that the mixed gas may be separately supplied to the vessel before supplying the mixture and the mixed gas, which can improve the yield of the fluorine-containing compound.
Another embodiment of the continuous method for fluorinating a specific organic compound includes a method in which a mixture of an organic solvent and a specific organic compound is supplied to a vessel, and then the mixed gas is supplied to the vessel.

From the viewpoint of improving the yield of the fluorine-containing compound, the amount of fluorine used to fluorinate the specific organic compound per mole of fluorinatable atoms contained in the specific organic compound is preferably 50 to 2,000 moles, more preferably 100 to 1,000 moles, and even more preferably 100 to 800 moles.

From the viewpoint of improving the yield of the fluorine-containing compound, the fluorination of the specific organic compound is preferably carried out under pressurized conditions. The pressure in the vessel during pressurization is preferably 0.01 to 5 MPa, more preferably 0.05 to 3 MPa, and even more preferably 0.1 to 1 MPa.
The pressure is measured by a pressure gauge installed in the gas phase portion of the container.

From the viewpoint of improving the yield of the fluorine-containing compound, it is preferable to carry out the fluorination of the specific organic compound in the presence of at least one of a C-H bond-containing compound and a carbon-carbon double bond-containing compound.

C--H bond-containing compounds include benzene, toluene, and the like.
The amount of the C—H bond-containing compound relative to the fluorinable atoms of the specific organic compound is preferably 0.1 to 10 mol %, more preferably 0.1 to 5 mol %.

Examples of the carbon-carbon double bond-containing compound include hexafluoropropylene and hexafluorobutadiene.
The amount of the carbon-carbon double bond-containing compound relative to the fluorinable atoms in the specific organic compound is preferably from 0.1 to 100 mol %, more preferably from 0.1 to 50 mol %.

In order to improve the yield of fluorine-containing compounds, ultraviolet light may be irradiated during the fluorination of specific organic compounds.

In the present production method, after the fluorination of the specific organic compound, a liquid phase containing the fluorine-containing compound produced by the fluorination of the specific organic compound and the organic solvent may be separated from a mixed gas containing fluorine gas.
In the present production method, the separated liquid phase may be concentrated and recovered. The liquid phase may be concentrated using an evaporator or the like.
In this production method, the separated mixed gas may be cooled to form a condensed liquid, which may be returned to the vessel.

Hereinafter, the embodiments of the present disclosure will be described in detail with reference to examples. However, the embodiments of the present disclosure are not limited to these. In this disclosure, Examples 1 to 12 are examples, and Examples 13 and 14 are comparative examples.

(Compounds Used)
Specific organic compound 1: _{CF3O ( CF2CFHOCF2CF2CF2CF2CH2O} ) _{nCF2CFHOCF2CF2CF2CF2CH2OCOCF} ( _CF3 ) _{OCF2CF2CF3 (} average value of n _{: 13} , viscosity _: 500 mPa· _s , molecular weight _: 4,236), synthesized _{by the method} described in Example 6-2 of WO2013/ ₁₂₁₉₈₄ .
Specific organic compound 2: CH ₂ ClCHClCH ₂ OCF ₂ CHFCl (boiling point 84° C., viscosity 4.4 mPa·s, molecular weight 246), synthesized by the method described in J. Org. Chem. 1961, 26, 6, 2085-2088.
Specific organic compound ₃ : _CF3CF2CF2OCF ( _CF3 ) _{COOCH2CH2CH2CH2OCOCF} ( _CF3 ) _{OCF2CF2CF3 (} boiling point 410°C, viscosity ₇₈₁ mPa·s, molecular weight _{714 )} , synthesized _by the _method described in Example 6-1 of WO2015/029839.
Specific organic compound 4: _{CH3CH2OCH2CH2OCH2CH2OCOCF ( CF3 )} OCF2CF _{( CF3} ) _OCF2CF2CF3 (boiling point ₂₅₅ °C, viscosity 660mPa·s, molecular weight ₆₁₂ ), synthesized _by the _method described in ₍ step 1-1) of WO2008/026707.
Specific organic compound 5: (CF ₃ ) ₂ CFCOOCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ OCOCF(CF ₃ ) ₂ (boiling point 241° C., viscosity 748 mPa·s, molecular weight 496), synthesized by the method described in Example 1-1 of WO 2015/029839.
CFE-419: 1,2-dichloro-1,1,2,3,3-pentafluoro-3-[2-chloro-1,1,2,2-tetrafluoroethoxy]-propane (CF ₂ ClCF ₂ OCF ₂ CFClCF ₂ Cl). Boiling point 115.5° C., viscosity 1.9 mPa·s.
(HFPO) ₃ : B1698 manufactured by Tokyo Chemical Industry Co., Ltd. 2,4,4,5,7,7,8,8,9,9,9-Undecafluoro-2,5-bistrifluoromethyl-3,6-dioxane-nonanoyl fluoride (CF ₃ CF ₂ CF ₂ OCF(CF ₃ )CF ₂ OCF(CF ₃ )COF). Boiling point: 114° C., viscosity: 2.2 mPa·s.
(HFPO) ₄ : PC6220K manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Perfluoro(2,5,8-trimethyl-3,6,9-trioxadodecanoyl)fluoride (CF ₃ CF ₂ CF ₂ OCF(CF ₃ )CF ₂ OCF(CF ₃ )CF ₂ OCF(CF ₃ )COF). Boiling point 166°C, viscosity 2.5 mPa·s.
EEA _{-FE: CF3CF2OCF2CF2OCF2CF2OCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3 ( boiling point 205 ° C} , _{viscosity 462} mPa· _s ), synthesized _by the _method described in (step 1-2) of WO2008/026707.
BVE-FE: (CF ₃ ) ₂ CFCOOCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ OCOCF(CF ₃ ) ₂ (boiling point 189° C., viscosity 606 mPa·s), synthesized by the method described in Example 1-2 of WO 2015/029839.

(Example 1)
An autoclave (made of nickel, internal volume 500 mL) equipped with a benzene solution inlet was prepared, and a cooler A maintained at 0°C, a NaF pellet packed layer, and a cooler B maintained at -10°C were installed in series at the gas outlet of the autoclave.
In addition, a liquid return pipe was provided for returning the condensate obtained in the cooler B to the autoclave.
A tank filled with an aqueous KOH solution was placed at the gas outlet of the autoclave.

302 g of CFE-419 was fed into the autoclave and stirred while maintaining the temperature at 22°C. Nitrogen gas was blown into the autoclave at 22°C for 1 hour, and then fluorine gas diluted to 30% by volume with nitrogen gas was blown in at 22°C and a flow rate of 2.0 L/hour for 1 hour.

A solution A was obtained by dissolving 8.4 g of specific organic compound 1 in 84.0 g of CFE-419.
Solution A was injected into the autoclave over a period of 5.3 hours while blowing in fluorine gas diluted to 30% by volume with nitrogen gas at a flow rate of 2.0 L/hour.

The vapor pressure of CFE-419 at 22° C. (0.003 MPa) and the pressure inside the autoclave (0.1 MPa [abs]) were substituted into the following formula to determine the molar fraction of the halogen-containing organic compound in the gas phase, which was 0.034.
The vapor pressure of the organic solvent was measured at 22° C., which is the temperature of the organic solvent in the fluorination of the specific organic compound.
In Example 1, both the organic solvent and the halogen-containing organic compound are CFE-419.
Molar fraction of halogen-containing organic compound=(vapor pressure of organic solvent in vessel during fluorination of specific organic compound/pressure in vessel during fluorination of specific organic compound)

The KOH aqueous solution filled in a tank installed at the gas outlet of the autoclave was titrated with 1N HCl to determine the fluorine gas concentration in the mixed gas discharged from the gas outlet, which was found to be 15% by volume.

Benzene was added to CFE-419 to prepare a benzene solution A having a benzene concentration of 0.017% by volume.
9 mL of benzene solution A was injected into the autoclave through the benzene solution injection port, and the benzene solution injection port was then closed.
Next, fluorine gas diluted to 30% by volume with nitrogen gas was blown in at a flow rate of 2.0 L/hour while stirring for 1 hour. Next, nitrogen gas was blown in for 1 hour.

The liquid phase in the autoclave was concentrated by an evaporator, and the fluorine-containing compound contained in the liquid phase was identified by ^19F -NMR. It was confirmed that the peak derived from the hydrogen atom of specific organic compound 1 had disappeared (conversion rate >99.9%), and 9.85 g of the fluorine-containing compound was recovered (yield 99.5%). The structure of the fluorine-containing compound and the results of ^19F -NMR are shown below.
_{Fluorine - containing compound : CF3O ( CF2CF2OCF2CF2CF2CF2CF2O ) nCF2CF2OCF2CF2CF2CF2CF2OCOCF ( CF3 ) OCF2CF2CF3 ​ ​ ​ ​}
Average number of units (n): 13
^19F -NMR (282.7MHz, solvent _CDCl3 , standard _CFCl3 ) δ (ppm): -55.2 (3F), -80.0 (1F), -82.0 to -82.5 (6F), -84.1 (54F), -86.7 to -87.8 (3F), -89.3 (54F), -91.3 (2F), -126.5 (56F), -130.4 (2F), -132.4 (1F)

(Example 2)
Fluorination was carried out in the same manner as in Example 1, except that the liquid phase temperature and the gas phase temperature in the fluorination were changed as shown in Table 1. The addition rate and yield are shown in Table 2.
The vapor pressure of CFE-419 at 32° C. is 0.005 MPa.

(Example 3)
A solution C was obtained by dissolving 8.4 g of specific organic compound 2 in 84.1 g of CFE-419.
Fluorination was carried out in the same manner as in Example 1, except that solution A was changed to solution C, fluorine gas diluted to 30% by volume with nitrogen gas was changed to fluorine gas diluted to 20% by volume with nitrogen gas, and the liquid phase temperature and gas phase temperature in the fluorination were changed as shown in Table 1. The addition rate and yield are shown in Table 2.

As in Example 1, the structure of the fluorine-containing compound and the results of ¹⁹ F-NMR are shown below.
_{Fluorine -} containing compound _{: CF2ClCFClCF2OCF2CF2Cl}
^19F -NMR (282.7MHz, solvent _CDCl3 , standard _CFCl3 ) δ(ppm): -62.5(2F), -73.9(2F), -82.5(2F), -84.1(2F), -125.6(1F)

(Example 4)
A solution D was obtained by dissolving 8.4 g of specific organic compound 3 in 84.1 g of (HFPO) ₃ .
Benzene was added to (HFPO) ₃ to prepare a benzene solution B having a benzene concentration of 0.017% by volume.
Fluorination was carried out in the same manner as in Example 1, except that CFE-419 was changed to (HFPO) ₃ , solution A was changed to solution D, benzene solution A was changed to benzene solution B, fluorine gas diluted to 30% by volume with nitrogen gas was changed to fluorine gas diluted to 20% by volume with nitrogen gas, and the liquid phase temperature and gas phase temperature in fluorination were changed as shown in Table 1. The addition rate and yield are shown in Table 2.
In Example 4, the organic solvent and the halogen-containing organic compound were both (HFPO) ₃ .
The vapor pressure of (HFPO) ₃ at 25°C is 0.002 MPa.

As in Example 1, the structure of the fluorine-containing compound and the results of ¹⁹ F-NMR are shown below.
_{Fluorine -} containing compound _{: CF3CF2CF2OCF ( CF3 ) COOCF2CF2CF2CF2CF2OCOCF ( CF3 ) OCF2CF2CF3}
^19F -NMR (282.7MHz, solvent _CDCl3 , standard _CFCl3 ) δ (ppm): -80.5 (6F), -80.9 (4F), -83.1 (6F), -122.6 (4F), -126.6 (4F), -130.7 (4F), -145.2 (2F)

(Example 5)
Fluorination was carried out in the same manner as in Example 4, except that fluorine gas diluted to 20% by volume with nitrogen gas was changed to fluorine gas diluted to 30% by volume with nitrogen gas, and the liquid phase temperature and gas phase temperature in the fluorination were changed as shown in Table 1. The addition rate and yield are shown in Table 2.
The vapor pressure of (HFPO) ₃ at 15°C is 0.002 MPa.

(Example 6)
A solution F was obtained by dissolving 8.4 g of specific organic compound 4 in 84.0 g of EEA-FE.
Benzene was added to EEA-FE to prepare a benzene solution C having a benzene concentration of 0.017% by volume.
Fluorination was carried out in the same manner as in Example 1, except that CFE-419 was changed to EEA-FE, solution A was changed to solution F, benzene solution A was changed to benzene solution C, fluorine gas diluted to 30% by volume with nitrogen gas was changed to fluorine gas diluted to 60% by volume with nitrogen gas, and the liquid phase temperature and gas phase temperature in fluorination were changed as shown in Table 1. The addition rate and yield are shown in Table 2.
In Example 6, both the organic solvent and the halogen-containing organic compound are EEA-FE.
The vapor pressure of EEA-FE at 25° C. is 0.001 MPa.

As in Example 1, the structure of the fluorine-containing compound and the results of ¹⁹ F-NMR are shown below.
_{Fluorine - containing} compound _{: CF3CF2OCF2CF2OCF2CF2OCOCF ( CF3} ) _{OCF2CF ( CF3 ) OCF2CF2CF3}
^19F -NMR (282.7MHz, solvent _CDCl3 , standard _CFCl3 ) δ (ppm): -81.7 (3F), -80.8 (3F), -82.0 (3F), -82.6 (2F), -85.6 (2F), -86.3 (2F), -89.6 (3F), -91.6 (6F), -92.2 (2F), -130.6 (2F), -131.8 (1F), -145.3 (1F)

(Example 7)
A solution G was obtained by dissolving 8.3 g of specific organic compound 5 in 84.1 g of BVE-FE.
Benzene was added to BVE-FE to prepare a benzene solution D having a benzene concentration of 0.017% by volume.
Fluorination was carried out in the same manner as in Example 1, except that CFE-419 was changed to BVE-FE, solution A was changed to solution G, benzene solution A was changed to benzene solution D, and the liquid phase temperature and gas phase temperature in the fluorination were changed as shown in Table 1. The addition rate and yield are shown in Table 2.
In Example 7, both the organic solvent and the halogen-containing organic compound were BVE-FE.
The vapor pressure of BVE-FE at 50° C. is 0.001 MPa.

As in Example 1, the structure of the fluorine-containing compound and the results of ¹⁹ F-NMR are shown below.
_{Fluorine -} containing compound _: ( _{CF3 ) 2CFCOOCF2CF2CF2CF2CF2CF2OCOCF ( CF3} ) ₂
^19F -NMR (282.7MHz, solvent _CDCl3 , standard _CFCl3 ) δ (ppm): -74.3 (12F), -86.1 (4F), -122.6 (2F), -125.7 (4F), -181.9 (2F)

(Example 8)
Fluorination was carried out in the same manner as in Example 7, except that fluorine gas diluted to 30% by volume with nitrogen gas was changed to fluorine gas diluted to 50% by volume with nitrogen gas, and the liquid phase temperature and gas phase temperature in the fluorination were changed as shown in Table 1. The addition rate and yield are shown in Table 2.
The vapor pressure of BVE-FE at 40° C. is 0.007 MPa.

(Example 9)
A solution I was obtained by dissolving 8.4 g of a specific organic compound 3 in 84.1 g of (HFPO) ₄ .
Benzene was added to (HFPO) ₄ to prepare a benzene solution E having a benzene concentration of 0.017% by volume.
Fluorination was carried out in the same manner as in Example 1, except that CFE-419 was changed to (HFPO) ₄ , solution A was changed to solution I, benzene solution A was changed to benzene solution E, fluorine gas diluted to 30% by volume with nitrogen gas was changed to fluorine gas diluted to 45% by volume with nitrogen gas, and the liquid phase temperature and gas phase temperature in fluorination were changed as shown in Table 1. The addition rate and yield are shown in Table 2.
In Example 9, both the organic solvent and the halogen-containing organic compound were (HFPO) ₄ .
The vapor pressure of (HFPO) ₄ at 21°C is 0.0002 MPa.

(Example 10)
Fluorination was carried out in the same manner as in Example 9, except that fluorine gas diluted to 45% by volume with nitrogen gas was changed to fluorine gas diluted to 10% by volume with nitrogen gas, and the liquid phase temperature and gas phase temperature in the fluorination were changed as shown in Table 1. The addition rate and yield are shown in Table 2.

The vapor pressure of (HFPO) ₄ at 70°C is 0.003 MPa.

(Example 11)
CF ₂ ClCFClCFClCF ₂ Cl was synthesized according to the method described in US Patent Application Publication No. 2,914,514.
The boiling point of CF ₂ ClCFClCFClCF ₂ Cl is 151° C. and the viscosity is 2.4 mPa·s.
A solution K was obtained by dissolving 8.4 g of specific organic compound 3 in 84.1 g of CF ₂ ClCFClCFClCF ₂ Cl.
Benzene was added to CF ₂ ClCFClCFClCF ₂ Cl to prepare a benzene solution F having a benzene concentration of 0.015 g/mL.
Fluorination was carried out in the same manner as in Example 1, except that CFE-419 was changed to CF ₂ ClCFClCFClCF ₂ Cl, solution A was changed to solution K, benzene solution A was changed to benzene solution F, fluorine gas diluted to 30% by volume with nitrogen gas was changed to fluorine gas diluted to 20% by volume with nitrogen gas, and the liquid phase temperature and gas phase temperature in fluorination were changed as shown in Table 1. The addition rate and yield are shown in Table 2.
In Example 11, both the organic solvent and the halogen-containing organic compound are CF ₂ ClCFClCFClCF ₂ Cl.
The vapor pressure of CF ₂ ClCFClCFClCF ₂ Cl at 44° C. is 0.003 MPa.

(Example 12)
Fluorination was carried out in the same manner as in Example 11, except that the liquid phase temperature and the gas phase temperature in the fluorination were changed as shown in Table 1. The addition rate and yield are shown in Table 2.
The vapor pressure of CF ₂ ClCFClCFClCF ₂ Cl at 52° C. is 0.005 MPa.

(Example 13)
Fluorination was carried out in the same manner as in Example 1, except that fluorine gas diluted to 30% by volume with nitrogen gas was changed to fluorine gas diluted to 20% by volume with nitrogen gas, and the liquid phase temperature and gas phase temperature in the fluorination were changed as shown in Table 1. The addition rate and yield are shown in Table 2.
The vapor pressure of CFE-419 at 45° C. is 0.008 MPa.

(Example 14)
Fluorination was carried out in the same manner as in Example 1, except that CFE-419 was changed to (HFPO) ₃ , solution A was changed to solution D, benzene solution A was changed to benzene solution B, fluorine gas diluted to 30% by volume with nitrogen gas was changed to fluorine gas diluted to 20% by volume with nitrogen gas, and the liquid phase temperature and gas phase temperature in fluorination were changed as shown in Table 1. The addition rate and yield are shown in Table 2.
The vapor pressure of (HFPO) ₃ at 44°C is 0.007 MPa.

It can be seen that the methods for producing fluorine-containing compounds in Examples 1 to 12, in which the molar fraction of halogen-containing organic compounds in the gas phase is 0.065 or less, have a superior yield of fluorine-containing compounds compared to Examples 13 to 14, in which the molar fraction exceeds 0.065.

The method for producing a fluorine-containing compound disclosed herein can produce a fluorine-containing compound with a higher fluorination yield than conventional methods. 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, an emulsifier, rubber, a surfactant, a solvent, a heat transfer medium, a pharmaceutical, an agricultural chemical, a lubricant, intermediates thereof, etc.

Claims (7)

In a vessel containing a liquid phase containing an organic compound having one or more fluorinable atoms or bonds and an organic solvent, and a gas phase containing a mixed gas containing fluorine gas, the organic compound having one or more fluorinable atoms or bonds is fluorinated;
In the fluorination of the organic compound having one or more fluorinatable atoms or bonds, the gas phase contains a halogen-containing organic compound, and the molar fraction of the halogen-containing organic compound in the gas phase is 0.065 or less.
A method for producing a fluorine-containing compound. The method for producing a fluorine-containing compound according to claim 1, wherein in the fluorination of an organic compound having one or more fluorinatable atoms or bonds, the content of the fluorine gas relative to the total volume of the mixed gas is 70 volume % or less. The method for producing a fluorine-containing compound according to claim 1 or 2, wherein after fluorination of the organic compound having one or more fluorinatable atoms or bonds, the mixed gas is discharged from the container, and the content of the fluorine gas relative to the total volume of the discharged mixed gas is 60 volume % or less. The method for producing a fluorine-containing compound according to claim 1 or 2, wherein the boiling point of the organic solvent is 50 to 500°C or higher. The method for producing a fluorine-containing compound according to claim 1 or 2, wherein the halogen-containing organic compound contains fluorine. The method for producing a fluorine-containing compound according to claim 1 or 2, wherein the organic solvent is a perhalogeno compound. The method for producing a fluorine-containing compound according to claim 1 or 2, wherein the organic solvent has 4 or more carbon atoms.