JP7621084B2 - Method for producing fluorine-containing carboxylate - Google Patents

Description

The present invention relates to a method for producing a fluorine-containing carboxylate.

The following general formula (1):
FSO ₂ CFXCF ₂ OCF (CF ₂ Y) COF (1)
(In the formula, X is a fluorine atom, a chlorine atom, or a trifluoromethyl group; and Y is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.)
From a fluorine-containing carboxylic acid fluoride (1) (hereinafter also referred to as "compound (1)") represented by the following formula:
The following general formula (4):
_{FSO2CFXCF2OCF ( CF2Y} ) _CO2M (4)
(In the formula, X is a fluorine atom, a chlorine atom, or a trifluoromethyl group; Y is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; and M is Na, K, Rb, or Cs.)
It is known that it is possible to produce a fluorine-containing carboxylate (4) represented by the following formula (hereinafter, also referred to as "compound (4)") (Patent Document 1, Non-Patent Document 1).

Patent Document 1 discloses a method for obtaining a fluorine-containing carboxylate (4) where X = F, Y = F, and M = Na by reacting a fluorine-containing carboxylic acid fluoride (1) where X = F and Y = F with sodium carbonate in the presence of acetonitrile at room temperature for 1 hour and at 40°C for 1 hour, followed by filtration, removal of the solvent, and distillation of the solvent under reduced pressure. It also discloses that the obtained fluorine-containing carboxylate (4) can be converted into various useful fluorine compounds.

Non-Patent Document 1 discloses that a fluorine-containing carboxylate (4) in which X = F, Y = F, and M = Na is produced by reacting a fluorine-containing carboxylic acid fluoride (1) in which X = F and Y = F with sodium carbonate in the presence of tetraethylene glycol dimethyl ether while maintaining the temperature at 30°C or lower for 3 hours and then at 40°C for 1 hour. It also discloses that the obtained fluorine-containing carboxylate (4) can be converted into various useful fluorine compounds.

International Publication No. 2002/062749

Journal of Fluorine Chemistry, Vol. 127 (2006), pp. 1087-1095

In Patent Document 1, 96.0 g of fluorine-containing carboxylate (4) where X = F, Y = F, and M = Na is obtained from 103.8 g of fluorine-containing carboxylic acid fluoride (1) where X = F and Y = F. Although the purity is not disclosed, the yield is calculated to be 87% assuming a purity of almost 100%, and a production method that can obtain a higher yield is desired.

In Non-Patent Document 1, the production of fluorine-containing carboxylate (4) in which X=F, Y=F and M=Na is analyzed by ^19F -NMR only, and there is no description regarding the production amount of fluorine-containing carboxylate (4). However, it is considered that there is room for improvement in terms of the yield.

The present invention has been made in consideration of the above circumstances, and aims to provide a method for producing a fluorine-containing carboxylate (4) in a high yield, which can be converted into various fluorine compounds.

As a result of intensive research aimed at solving the above-mentioned problems, the present inventors discovered that the above-mentioned object can be achieved by reacting a fluorine-containing carboxylic acid fluoride (1) with a specific alkali metal carbonate (2) (hereinafter also referred to as "compound (2)") in the presence of a specific ether-based compound (3) (hereinafter also referred to as "compound (3)"), and thus completed the present invention.

That is, the present invention is as follows.
[1]
The following general formula (4):
_{FSO2CFXCF2OCF ( CF2Y} ) _CO2M (4)
(In the formula, X is a fluorine atom, a chlorine atom, or a trifluoromethyl group; Y is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; and M is Na, K, Rb, or Cs.)
The present invention relates to a method for producing a fluorine-containing carboxylate (4) represented by the following formula:
The following general formula (1):
FSO ₂ CFXCF ₂ OCF (CF ₂ Y) COF (1)
(In the formula, X is a fluorine atom, a chlorine atom, or a trifluoromethyl group; and Y is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.)
A fluorine-containing carboxylic acid fluoride (1) represented by the formula:
The following general formula (2):
_M2CO3 ( ₂ )
(In the formula, M is Na, K, Rb, or Cs.)
and an alkali metal carbonate (2) represented by
The following general formula (3):
R ¹ (OR ² ) _p OR ³ (3)
(In the formula, R ¹ , R ² , and R ³ may be the same or different, and each is a substituted or unsubstituted aliphatic or aromatic hydrocarbon group having 1 to 10 carbon atoms, and R ¹ and R ³ may be linked together; and p is 0 or 1.)
Reacting in the presence of an ether-based compound (3) represented by the following formula (excluding glyme, tetraglyme, and diethylene glycol dimethyl ether) ,
The ether compound is at least one selected from the group consisting of tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, 4-methyltetrahydropyran, cyclopentyl methyl ether, diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, methyl tert-butyl ether, 1,4-dioxane, 1,2-diethoxyethane, ethylene glycol dibutyl ether, and 1,2-dimethoxypropane.
A manufacturing method comprising :

According to the present invention, it is possible to produce fluorine-containing carboxylate (4) in a good yield, which can be converted into various fluorine compounds.

The following describes in detail the form for carrying out the present invention (hereinafter, referred to as the "present embodiment"). However, the present invention is not limited to the present embodiment below, and can be carried out in various modifications within the scope of the gist of the present invention.

The manufacturing method of this embodiment is as follows:
The following general formula (4):
_{FSO2CFXCF2OCF ( CF2Y} ) _CO2M (4)
(In the formula, X is a fluorine atom, a chlorine atom, or a trifluoromethyl group; Y is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; and M is Na, K, Rb, or Cs.)
The present invention relates to a method for producing a fluorine-containing carboxylate (4) represented by the following formula:
The following general formula (1):
FSO ₂ CFXCF ₂ OCF (CF ₂ Y) COF (1)
(In the formula, X is a fluorine atom, a chlorine atom, or a trifluoromethyl group; and Y is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.)
A fluorine-containing carboxylic acid fluoride (1) represented by the formula:
The following general formula (2):
_M2CO3 ( ₂ )
(In the formula, M is Na, K, Rb, or Cs.)
and an alkali metal carbonate (2) represented by
The following general formula (3):
R ¹ (OR ² ) _p OR ³ (3)
(In the formula, R ¹ , R ² , and R ³ may be the same or different, and each is a substituted or unsubstituted aliphatic or aromatic hydrocarbon group having 1 to 10 carbon atoms, and R ¹ and R ³ may be linked together; and p is 0 or 1.)
The reaction is carried out in the presence of an ether compound (3) represented by the following formula:

The following provides details about compounds (1), (2), and (3), as well as the reaction conditions for producing compound (4) from compound (1).

<Fluorine-containing carboxylic acid fluoride (1) (compound (1))>
The fluorine-containing carboxylic acid fluoride (1) is represented by the following general formula (1):
FSO ₂ CFXCF ₂ OCF (CF ₂ Y) COF (1)
(In the formula, X is a fluorine atom, a chlorine atom, or a trifluoromethyl group; and Y is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.)
It is expressed as:
The compound (1) may be used alone or in combination of two or more kinds.

As X, a fluorine atom or a trifluoromethyl group is preferable because they are easily available or produced and tend to be economically advantageous, and from the same viewpoint, a fluorine atom is more preferable.
As Y, a fluorine atom or a chlorine atom is preferable because they are easily available or produced and tend to be economically advantageous, and from the same viewpoint, a fluorine atom is more preferable.
A particularly preferred combination of X and Y is that both are fluorine atoms (X=F, Y=F).

The method for producing compound (1) is not particularly limited, and compound (1) can be produced by a conventional method. For example, compound (1) in which X=F and Y=F can be produced by the method described in International Publication No. 1998/43952. Compound (1) can also be purchased from, for example, Synquest Laboratories.

<Alkali Metal Carbonate (2) (Compound (2))>
The alkali metal carbonate (2) is represented by the following general formula (2):
_M2CO3 ( ₂ )
(In the formula, M is Na, K, Rb, or Cs.)
It is expressed as:
The compound (2) may be used alone or in combination of two or more kinds.

As M, Na, K, or Cs are preferred because they are easily available and tend to be economical, and from the same perspective, Na or K is more preferred.

Compound (2) having a reduced water content can also be used, if necessary.
The method for reducing the water content of compound (2) is not particularly limited as long as it is a commonly available method, and examples of the method include a method of heating, a method of heating under vacuum, and a method of heating under a dry gas flow.
The heating temperature is not particularly limited as long as it is a temperature that can reduce the water content of compound (2), but since there is a tendency to suppress the decomposition of compound (2), it is preferably 600° C. or less. Since excessive heating is suppressed and there is a tendency to be more economical, it is more preferably 300° C. or less, and from the same viewpoint, it is even more preferably 250° C. or less, and particularly preferably 200° C. or less. In addition, since there is a tendency to promote the reduction of the water content, it is preferably 100° C. or more, more preferably 120° C. or more, and even more preferably 150° C. or more.
The dry gas is not particularly limited as long as it is a commonly used dry gas, and examples of the dry gas include dry air and dry nitrogen.

<Ether Compound (3) (Compound (3))>
The ether compound (3) is represented by the following general formula (3):
R ¹ (OR ² ) _p OR ³ (3)
(In the formula, R ¹ , R ² and R ³ may be the same or different, and are either substituted or unsubstituted aliphatic hydrocarbon groups or aromatic hydrocarbon groups having 1 to 10 carbon atoms, and R ¹ and R ³ may be linked together; and p is 0 or 1.)
The compound (3) may be used alone or in combination of two or more kinds.

In the compound (3), R ¹ , R ² and R ³ are each a substituted or unsubstituted aliphatic hydrocarbon group or aromatic hydrocarbon group.
The substituent is not particularly limited, but examples thereof include halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms, nitrile groups (-CN), ether groups (-O-), carbonate groups (-OCO ₂ -), ester groups (-CO ₂ -), carbonyl groups (-CO-), sulfide groups (-S-), sulfoxide groups (-SO-), sulfone groups (-SO ₂ -), and urethane groups (-NHCO ₂ -).
From the viewpoint of increasing the reactivity between compound (1) and compound (2), R ¹ , R ² , and R ³ are preferably a substituted or unsubstituted aliphatic hydrocarbon group, and more preferably an unsubstituted aliphatic hydrocarbon group because they are easily available and tend to be economically superior.

R ¹ , R ² and R ³ in the compound (3) each have 1 to 10 carbon atoms.
When p is 0, the reactivity between compound (1) and compound (2) tends to be increased, so the carbon numbers of R ¹ and R ³ are preferably 6 or less, and from the same viewpoint, more preferably 5 or less. When p is 0 and R ¹ and R ³ are not linked, the carbon numbers of R ¹ and R ³ are preferably 1 or more, so that availability is easy and the cost performance is excellent. When p is 0 and R ¹ and R ³ are linked, the carbon numbers of R ¹ and R ³ are preferably 2 or more, so that availability is easy and the cost performance is excellent.
Furthermore, when p is 1, the reactivity between compound (1) and compound (2) tends to be increased, so the carbon numbers of R ¹ and R ³ are preferably 6 or less, and from the same viewpoint, more preferably 4 or less. Since they tend to be easily available and economically superior, the carbon numbers of R ¹ and R ³ are further preferably 2 or less, and from the same viewpoint, particularly preferably 1.
Since the reactivity of compound (1) and compound (2) tends to be increased, the carbon number of ^R2 is preferably 2 or more, and from the same viewpoint, it is preferably 6 or less, and more preferably 4 or less. Since it tends to be economically advantageous, the carbon number of ^R2 is further preferably 3 or less. Since the reactivity of compound (1) and compound (2) tends to be increased and it tends to be economically advantageous, it is particularly preferable that the carbon number of ^R2 is 2.

Examples of compound (3) include tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, 4-methyltetrahydropyran, cyclopentyl methyl ether, diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, methyl tert-butyl ether, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, ethylene glycol dibutyl ether, and 1,2-dimethoxypropane.

Since the reactivity of compound (1) and compound (2) tends to be increased, tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, 4-methyltetrahydropyran, cyclopentyl methyl ether, diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, dihexyl ether, methyl tert-butyl ether, 1,4-dioxane, 1,2-dimethoxyethane, and 1,2-diethoxyethane are preferred, and from the same viewpoint, tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, 4-methyltetrahydropyran, cyclopentyl methyl ether, diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, methyl tert-butyl ether, 1,4-dioxane, and 1,2-dimethoxyethane are more preferred, and tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyltetrahydropyran, cyclopentyl methyl ether, methyl tert-butyl ether, 1,4-dioxane, and 1,2-dimethoxyethane are even more preferred.

Compound (3) having a reduced water content can also be used, if necessary.
Compound (3) having a low water content can be purchased, or a method for reducing the water content of compound (3) can be used. The method for reducing the water content of compound (3) is not particularly limited as long as it is a commonly available method, and examples thereof include a method using a dehydrating agent and a distillation method.
The dehydrating agent is not particularly limited as long as it is a commonly used dehydrating agent, and examples thereof include sodium hydride, magnesium sulfate, sodium sulfate, calcium sulfate, calcium chloride, zinc chloride, calcium oxide, magnesium oxide, diphosphorus pentoxide, activated alumina, silica gel, and molecular sieves. When a dehydrating agent is used, a compound (3) containing a dehydrating agent may be used as long as it does not affect the reaction between compound (1) and compound (2), or a compound (3) that does not contain a dehydrating agent after filtration or the like may be used.

<Ratio (β/α) of the amount of substance (β) of compound (2) to the amount of substance (α) of compound (1)>
The ratio (β/α) of the amount of substance (β) of compound (2) to the amount of substance (α) of compound (1) is preferably 0.5 or more, more preferably 0.8 or more, since the yield of compound (4) tends to increase and the economic efficiency of the method for producing compound (4) tends to be excellent, and further preferably 1 or more, since the amount of unreacted compound (1) tends to be suppressed.

The upper limit of the ratio (β/α) of the amount of substance (β) of compound (2) to the amount of substance (α) of compound (1) is not particularly limited, but since the amount of compound (2) used is reduced and the method for producing compound (4) tends to be more economical, it is preferable that β/α is 10 or less, and from the same viewpoint, it is more preferable that β/α is 7 or less, and even more preferable that β/α is 5 or less.

<Ratio (δ/γ) of the mass (δ) of compound (3) to the mass (γ) of compound (1)>
The ratio (δ/γ) of the mass (δ) of compound (3) to the mass (γ) of compound (1) is preferably 0.5 or more since the reactivity of compound (1) with compound (2) tends to be increased. From the same viewpoint, δ/γ is more preferably 0.8 or more, and further preferably δ/γ is 1 or more.

The upper limit of the ratio (δ/γ) of the mass (δ) of compound (3) to the mass (γ) of compound (1) is not particularly limited, but since the amount of compound (3) used is reduced and the method for producing compound (4) tends to be more economical, it is preferable that δ/γ is 10 or less, and from the same viewpoint, it is more preferable that δ/γ is 7 or less, and even more preferable that δ/γ is 5 or less.

<Reaction of Compound (1) and Compound (2)>
The reaction temperature of the compound (1) and the compound (2) is not particularly limited as long as it is a reaction temperature that is generally used, but since the reactivity of the compound (1) and the compound (2) tends to be increased, the reaction temperature is preferably −40° C. or higher, and more preferably −20° C. or higher. From the same viewpoint and also because the reaction temperature tends to be economically advantageous when adjusting the temperature industrially, the reaction temperature is further preferably 0° C. or higher.

The upper limit of the reaction temperature between compound (1) and compound (2) is not particularly limited, but since there is a tendency that volatilization of compound (1) can be suppressed and the yield of fluorinated carboxylate (4) tends to be increased, it is preferably 160° C. or lower, and more preferably 100° C. or lower. Since there is a tendency that side reactions in the reaction between compound (1) and compound (2) can be suppressed, it is further preferably 80° C. or lower, and particularly preferably 60° C. or lower.
The reaction temperature of the compound (1) and the compound (2) does not need to be constant so long as it is within the above range, and may be changed during the reaction.

The reaction time between compound (1) and compound (2) is not particularly limited as long as it is within a commonly used range, but is preferably 0.5 hours or more, and more preferably 1 hour or more, because this increases the stability of the yield of compound (4). Avoiding an excessive reaction time tends to result in a more economical production method, so it is preferably 100 hours or less, and from the same viewpoint, it is more preferably 50 hours or less, and even more preferably 20 hours or less.

The reaction pressure of compound (1) and compound (2) is not particularly limited as long as it is within the range of normal use, and the reaction is usually carried out under atmospheric pressure. However, depending on the type of compound (1) and/or compound (3), the vapor pressure at standard conditions is low, so when compound (1) and/or compound (3) are liquefied and not reused, pressurization at atmospheric pressure or higher is an effective means. When compound (1) and/or compound (3) are liquefied and reused, reduced pressure below atmospheric pressure may be used.
The pressure for the reaction of compound (1) and compound (2) does not need to be constant so long as it is within the above range, and may be changed during the reaction.

The atmosphere for the reaction of compound (1) and compound (2) is not particularly limited as long as it is a commonly used atmosphere, and usually, air atmosphere, nitrogen atmosphere, argon atmosphere, etc. are used. Among these, nitrogen atmosphere and argon atmosphere are preferred because they tend to produce compound (4) more safely. In addition, nitrogen atmosphere is more preferred because they tend to be a more economical production method.
The reaction atmosphere may be used alone or in combination of a plurality of reaction atmospheres.

The order in which compounds (1), (2), and (3) are added is not particularly limited, but since the reaction between compound (1) and compound (2) is an exothermic reaction and side reactions tend to be suppressed, particularly when the amounts of compounds (1), (2), and (3) used are large, the following methods are preferred: gradually adding a mixture of compound (1) and compound (3) to compound (2), gradually adding compound (2) to a mixture of compound (1) and compound (3), gradually adding a mixture of compound (2) and compound (3) to compound (1), and gradually adding compound (1) to a mixture of compound (2) and compound (3).

As described above, the present invention makes it possible to produce a fluorine-containing carboxylate (4) that can be converted into various fluorine compounds in a higher yield than conventional methods.

The following are examples that specifically explain this embodiment. The present invention is not limited to the following examples as long as they do not exceed the gist of the present invention.

The analytical methods used in the Examples , Reference Examples and Comparative Examples are as follows.

<Nuclear Magnetic Resonance Analysis (NMR): Molecular Structure Analysis by ¹⁹ F-NMR>
The products obtained in the Examples , Reference Examples and Comparative Examples were subjected to molecular structure analysis using ¹⁹ F-NMR under the following measurement conditions.
[Measurement conditions]
Measurement device: JNM-ECZ400S nuclear magnetic resonance device (manufactured by JEOL Ltd.)
Observed nucleus: ^19F
Solvent: deuterated chloroform Standard substance: tetramethylsilane (0.00 ppm)
Observation frequency: 400MHz ( ^1H )
Pulse width: 6.5 μsec Waiting time: 2 sec Number of integrations: 16

The raw materials used in the Examples , Reference Examples and Comparative Examples are shown below.

(Fluorine-containing carboxylic acid fluoride (1) (compound (1))
According to the method described in WO 1998/43952, CF ₃ CF(COF)OCF ₂ CF ₂ SO ₂ F was produced and further purified by distillation to obtain CF ₃ CF(COF)OCF ₂ CF ₂ SO ₂ F with a purity of >99%.

(Alkali Metal Carbonate (2) (Compound (2))
・Sodium carbonate (Fujifilm Wako Pure Chemical Industries, special grade reagent)
・Potassium carbonate (Fujifilm Wako Pure Chemical Industries, special grade reagent)
Rubidium carbonate (Aldrich, purity 99%)
Cesium carbonate (Aldrich, purity 99%)

(Ether Compound (3) (Compound (3))
4-Methyltetrahydropyran (Tokyo Chemical Industry Co., Ltd.)
・1,2-dimethoxyethane (Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent)
- Cyclopentyl methyl ether (Fujifilm Wako Pure Chemical Industries, special grade reagent)
- Tetrahydrofuran (Fujifilm Wako Pure Chemical Industries, special grade reagent)
・2-Methyltetrahydrofuran (Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent)
・1,4-dioxane (manufactured by Fujifilm Wako Pure Chemical Industries, special grade reagent)
Methyl tert-butyl ether (Tokyo Chemical Industry Co., Ltd.)

(others)
- Hexane (Fujifilm Wako Pure Chemical Industries, special grade reagent)
- Toluene (Fujifilm Wako Pure Chemical Industries, special grade reagent)
- Chloroform (Fujifilm Wako Pure Chemical Industries, special grade reagent)
・Acetonitrile (Fujifilm Wako Pure Chemical Industries, special grade reagent)
- Tetraethylene glycol dimethyl ether (Tokyo Chemical Industry Co., Ltd.)
- Benzotrifluoride (Tokyo Chemical Industry Co., Ltd.)
- Acetone (Fujifilm Wako Pure Chemical Industries, special grade reagent)

[Example 1]
A stirrer and sodium carbonate (0.95 g, 8.93 mmol) were placed in a test tube (Radley Discovery Technologies, RP98059, RP98062), which was then placed in a heating/cooling stirrer (Tokyo Rikakikai Co., Ltd., PPM-5512 model, cooling water was circulated from the outside when cooling), dried under vacuum at 150° C. for 5 hours, returned to room temperature, and placed in a nitrogen atmosphere. The heating/cooling stirrer was set to 30° C., and 4-methyltetrahydropyran (3.00 g) was added to the test tube and stirred. Then, CF ₃ CF(COF)OCF ₂ CF ₂ SO ₂ F (3.00 g, 8.67 mmol) was added dropwise over 10 minutes. After stirring for another 2 hours, the mixture was returned to room temperature. For analysis, benzotrifluoride (0.30 g) was added and stirred. The reaction mixture obtained was filtered, and the filtrate was analyzed by ^19F -NMR. As a result of the analysis, it was found that sodium fluorinated carboxylate (5) represented by the following general formula (5) was produced (amount produced: 3.08 g, mass of product: 8.43 mmol, production rate: 97.2%). In the analysis, the amount of sodium fluorinated carboxylate (5) produced was calculated from the mass of benzotrifluoride, the integral value of _CF3 of benzotrifluoride, and the integral value of _CF3 of sodium fluorinated carboxylate (5).
In this embodiment, β/α was 1.0 and γ/δ was 1.0.
_NaO2CCF ( _{CF3 ) OCF2CF2SO2F} ( ₅ )
¹⁹ F-NMR: δ (ppm) 43.37 (1F), -80.15 (1F), -83.12 (3F), -83.47 (1F), -112.84 (2F), -127.14 (1F)

[ Reference Example 2]
Except for using 1,2-dimethoxyethane instead of 4-methyltetrahydropyran, a fluorinated carboxylate sodium salt (5) was produced in the same manner as in Example 1. Analysis revealed that a fluorinated carboxylate sodium salt (5) was produced (amount produced: 3.08 g, product mass: 8.42 mmol, production rate: 97.1%).
In this reference example, β/α was 1.0 and γ/δ was 1.0.

[Example 3]
Except for using cyclopentyl methyl ether instead of 4-methyltetrahydropyran, a fluorinated carboxylate sodium salt (5) was produced in the same manner as in Example 1. As a result of analysis, it was found that a fluorinated carboxylate sodium salt (5) was produced (amount produced: 2.93 g, product mass: 8.00 mmol, production rate: 92.3%).
In this embodiment, β/α was 1.0 and γ/δ was 1.0.

[Example 4]
Except for using tetrahydrofuran instead of 4-methyltetrahydropyran, a fluorinated carboxylate sodium salt (5) was produced in the same manner as in Example 1. As a result of analysis, it was found that a fluorinated carboxylate sodium salt (5) was produced (amount produced: 2.94 g, product mass: 8.02 mmol, production rate: 92.5%).
In this embodiment, β/α was 1.0 and γ/δ was 1.0.

[Example 5]
Except for using 2-methyltetrahydrofuran instead of 4-methyltetrahydropyran, a fluorinated carboxylate sodium salt (5) was produced in the same manner as in Example 1. Analysis revealed that a fluorinated carboxylate sodium salt (5) was produced (amount produced: 2.92 g, product mass: 7.98 mmol, production rate: 92.1%).
In this embodiment, β/α was 1.0 and γ/δ was 1.0.

[Example 6]
Except for using 1,4-dioxane instead of 4-methyltetrahydropyran, a fluorinated carboxylate sodium salt (5) was produced in the same manner as in Example 1. Analysis revealed that a fluorinated carboxylate sodium salt (5) was produced (amount produced: 2.93 g, product mass: 8.01 mmol, production rate: 92.4%).
In this embodiment, β/α was 1.0 and γ/δ was 1.0.

[Example 7]
Except for using methyl tert-butyl ether instead of 4-methyltetrahydropyran, a fluorinated carboxylate sodium salt (5) was produced in the same manner as in Example 1. As a result of analysis, it was found that a fluorinated carboxylate sodium salt (5) was produced (amount produced: 2.92 g, product mass: 7.97 mmol, production rate: 92.0%).
In this embodiment, β/α was 1.0 and γ/δ was 1.0.

[Example 8]
A fluorinated potassium carboxylate (KO ₂ CCF(CF ₃ )OCF 2 CF 2 SO 2 F) was produced in the same manner as in Example 1, except that potassium carbonate (1.23 g, 8.93 mmol) was used instead of sodium carbonate _and the heating/cooling stirrer was _{set to 10} ° C. Analysis showed that a fluorinated potassium carboxylate was produced (amount produced: 3.23 g _, product mass: 8.44 mmol, production rate: 97.4%).
In this embodiment, β/α was 1.0 and γ/δ was 1.0.

[Example 9]
A fluorine-containing rubidium carboxylate ( _RbO2CCF ( _CF3 )OCF2CF2SO2F) was produced in the same manner as in Example 1, except that rubidium carbonate (2.06 g, 8.93 mmol) was used instead of sodium carbonate and the heating/cooling stirrer was set to _{0 °} C. Analysis showed that a fluorine- _containing rubidium carboxylate was produced (amount produced: 3.53 g, product mass: 8.24 mmol, production rate: 95.1%).
In this embodiment, β/α was 1.0 and γ/δ was 1.0.

[Example 10]
A fluorine-containing cesium carboxylate (CsO ₂ CCF(CF ₃ )OCF 2 CF 2 SO 2 F) was produced in the same manner as in Example 1, except that cesium carbonate (2.91 g, 8.93 mmol) was used instead of sodium carbonate _{and the} heating/cooling _stirrer was set to 0° C. Analysis showed that a fluorine-containing cesium carboxylate was produced (amount produced: 3.93 g, product mass: 8.25 mmol, production rate: 95.2%).
In this embodiment, β/α was 1.0 and γ/δ was 1.0.

[Example 11]
A fluorinated carboxylate sodium salt (5) was produced in the same manner as in Example 1, except that the amount of sodium carbonate used was 4.59 g (43.34 mmol) and the heating/cooling stirrer was set to 20° C. As a result of analysis, it was found that a fluorinated carboxylate sodium salt (5) was produced (amount produced: 3.08 g, product mass: 8.42 mmol, production rate: 97.1%).
In this embodiment, β/α was 5.0, and γ/δ was 1.0.
[Example 12]
A stirrer and sodium carbonate (0.32 g, 2.98 mmol) were placed in a test tube (RP98059, RP98062, manufactured by Radley Discovery Technologies), placed in a heating/cooling stirring device (PPM-5512, manufactured by Tokyo Rikakikai Co., Ltd., cooling water was circulated from the outside when cooling), dried at 150° C. under vacuum for 5 hours, returned to room temperature, and placed in a nitrogen atmosphere. The heating/cooling stirring device was set to 20° C., and 4-methyltetrahydropyran (5.00 g) was added to the test tube and stirred. Then, CF ₃ CF(COF)OCF ₂ CF ₂ SO ₂ F (1.00 g, 2.89 mmol) was added dropwise over 10 minutes. After stirring for another 2 hours, the mixture was returned to room temperature. For analysis, benzotrifluoride (0.10 g) was added and stirred. The reaction mixture was filtered, and the filtrate was analyzed by ¹⁹ F-NMR. As a result of the analysis, it was found that a fluorine-containing carboxylic acid sodium salt (5) was produced (amount produced: 1.03 g, product mass: 2.82 mmol, production rate: 97.5%).
In this embodiment, β/α was 1.0 and γ/δ was 5.0.

[Example 13]
A heating/cooling stirrer was set to 60° C., CF ₃ CF(COF)OCF ₂ CF ₂ SO ₂ F (3.00 g, 8.67 mmol) was added dropwise over 10 minutes, the mixture was stirred for 1 hour, and then benzotrifluoride (0.30 g) was added after returning to room temperature, to produce a fluorine-containing carboxylate sodium salt (5) in the same manner as in Example 1. Analysis showed that a fluorine-containing carboxylate sodium salt (5) was produced (amount produced: 3.05 g, product mass: 8.33 mmol, production rate: 96.1%).
In this embodiment, β/α was 1.0 and γ/δ was 1.0.

[Comparative Example 1]
Except for using hexane instead of 4-methyltetrahydropyran, the same method as in Example 1 was used to produce a fluorinated carboxylate sodium salt (5). As a result of analysis, no fluorinated carboxylate sodium salt (5) was detected.
In this embodiment, β/α was 1.0 and γ/δ was 1.0.

[Comparative Example 2]
Except for using toluene instead of 4-methyltetrahydropyran, a fluorinated carboxylic acid sodium salt (5) was produced in the same manner as in Example 1. As a result of analysis, no fluorinated carboxylic acid sodium salt (5) was detected.
In this embodiment, β/α was 1.0 and γ/δ was 1.0.

[Comparative Example 3]
Except for using chloroform instead of 4-methyltetrahydropyran, the fluorinated carboxylic acid sodium salt (5) was produced in the same manner as in Example 1. As a result of analysis, the fluorinated carboxylic acid sodium salt (5) was not detected.
In this embodiment, β/α was 1.0 and γ/δ was 1.0.

[Comparative Example 4]
The following experiment was carried out with reference to Example 1 of Patent Document 1.
A stirrer and sodium carbonate (0.92 g, 8.67 mmol) were placed in a test tube (Radley Discovery Technologies, RP98059, RP98062), placed in a heating/cooling stirrer (Tokyo Rikakikai Co., Ltd., PPM-5512 type, cooling water was circulated from the outside when cooling), dried under vacuum at 150° C. for 5 hours, returned to room temperature, and placed in a nitrogen atmosphere. The heating/cooling stirrer was set to 30° C., acetonitrile (3.38 g) was added to the test tube, and stirred. Then, CF ₃ CF(COF)OCF ₂ CF ₂ SO ₂ F (3.00 g, 8.67 mmol) was added dropwise over 10 minutes, and stirred for 1 hour. The heating/cooling stirrer was set to 40° C., and stirred for another 1 hour. After returning the mixture to room temperature, benzotrifluoride (0.30 g) was added and stirred for analysis. The reaction mixture obtained was filtered, and the filtrate was analyzed by ¹⁹ F-NMR. As a result of the analysis, it was found that a fluorine-containing carboxylate sodium salt (5) was produced (amount produced: 2.61 g, product mass: 7.13 mmol, production rate: 82.3%).
In this embodiment, β/α was 1.0, and γ/δ was 1.1.

[Comparative Example 5]
With reference to Non-Patent Document 1, the following procedure was carried out.
A stirrer and sodium carbonate (1.06 g, 9.96 mmol) were placed in a test tube (Radley Discovery Technologies, RP98059, RP98062), which was then placed in a heating/cooling stirrer (Tokyo Rikakikai Co., Ltd., PPM-5512 type, cooling water was circulated from the outside when cooling), dried under vacuum at 150° C. for 5 hours, returned to room temperature, and placed in a nitrogen atmosphere. The heating/cooling stirrer was set to 30° C., and tetraethylene glycol dimethyl ether (3.24 g) was added to the test tube and stirred. Subsequently, CF ₃ CF(COF)OCF ₂ CF ₂ SO ₂ F (3.00 g, 8.67 mmol) was added dropwise over 10 minutes, and the mixture was stirred for 3 hours. The heating/cooling stirrer was set to 40° C., and the mixture was further stirred for 1 hour. After returning the mixture to room temperature, benzotrifluoride (0.30 g) and acetone (12.00 g) were added and stirred for analysis. The resulting reaction mixture was filtered, and the filtrate was analyzed by ¹⁹ F-NMR. As a result of the analysis, it was found that a fluorine-containing carboxylate sodium salt (5) was produced (amount produced: 2.37 g, product mass: 6.48 mmol, production rate: 74.7%).
In this embodiment, β/α was 1.1, and γ/δ was 1.1.

According to the production process of the present invention, it is possible to produce, in a higher yield than conventional methods, a fluorine-containing carboxylate (4) which can be converted into various industrially useful fluorine compounds, and therefore the process can be suitably used in the production of raw materials for various fluorine-containing compounds, ion exchange resins, ion exchange membranes, sodium chloride electrolysis membranes, fuel cell membranes, membranes for redox flow batteries, membranes for water electrolysis, etc.

Claims (1)

The following general formula (4):
_{FSO2CFXCF2OCF ( CF2Y} ) _CO2M (4)
(In the formula, X is a fluorine atom, a chlorine atom, or a trifluoromethyl group; Y is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; and M is Na, K, Rb, or Cs.)
The present invention relates to a method for producing a fluorine-containing carboxylate (4) represented by the following formula:
The following general formula (1):
FSO ₂ CFXCF ₂ OCF (CF ₂ Y) COF (1)
(In the formula, X is a fluorine atom, a chlorine atom, or a trifluoromethyl group; and Y is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.)
A fluorine-containing carboxylic acid fluoride (1) represented by the formula:
The following general formula (2):
_M2CO3 ( ₂ )
(In the formula, M is Na, K, Rb, or Cs.)
and an alkali metal carbonate (2) represented by
The following general formula (3):
R ¹ (OR ² ) _p OR ³ (3)
(In the formula, R ¹ , R ² , and R ³ may be the same or different, and each is a substituted or unsubstituted aliphatic or aromatic hydrocarbon group having 1 to 10 carbon atoms, and R ¹ and R ³ may be linked together; and p is 0 or 1.)
Reacting in the presence of an ether-based compound (3) represented by the following formula (excluding glyme, tetraglyme, and diethylene glycol dimethyl ether) ,
The ether compound is at least one selected from the group consisting of tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, 4-methyltetrahydropyran, cyclopentyl methyl ether, diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, methyl tert-butyl ether, 1,4-dioxane, 1,2-diethoxyethane, ethylene glycol dibutyl ether, and 1,2-dimethoxypropane.
A manufacturing method comprising: