Method for producing fluorine-containing carboxylate

Abstract

To provide a method for producing a fluorinated carboxylate (4) at high yield, which can be converted into various fluorine compounds.SOLUTION: A method for producing a fluorinated carboxylate (4) includes inducing a reaction between a fluorinated carboxylic fluoride (1) and an alkali metal carbonate (2) in the presence of an ether compound (3).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing a fluorine-containing carboxylate. [Background technology]

[0002] The following general formula (1): FSO2CFXCF2OCF(CF2Y)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).

[0003] 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.

[0004] 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 for 3 hours while maintaining the temperature at 30° C. or lower and then for 1 hour at 40° C. It also discloses that the obtained fluorine-containing carboxylate (4) can be converted into various useful fluorine compounds. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2002 / 062749 [Non-patent literature]

[0006] [Non-Patent Document 1] Journal of Fluorine Chemistry, Vol. 127 (2006), pp. 1087-1095 Summary of the Invention [Problem to be solved by the invention]

[0007] In Patent Document 1, 96.0 g of fluorinated carboxylate (4) where X=F, Y=F, M=Na is obtained from 103.8 g of fluorinated carboxylic acid fluoride (1) where X=F, Y=F. Although the purity is not described, the yield is calculated to be 87% assuming that the purity is almost 100%, and a production method that can obtain a higher yield is desired.

[0008] In Non-Patent Document 1, the production of a fluorine-containing carboxylate (4) in which X=F, Y=F, and M=Na is described. 19 Although the analysis was carried out only by F-NMR and there was no description regarding the amount of the fluorine-containing carboxylate (4) produced, it is believed that there is still room for improvement in terms of the yield.

[0009] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a fluorine-containing carboxylate (4) which can be converted into various fluorine compounds in a good yield. [Means for solving the problem]

[0010] Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result have found 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 compound (3) (hereinafter also referred to as "compound (3)"), thereby completing the present invention.

[0011] 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): FSO2CFXCF2OCF(CF2Y)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 following 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, R1 , R 2 , R 3 are the same or different, and each is a substituted or unsubstituted aliphatic or aromatic hydrocarbon group having 1 to 10 carbon atoms; R 1 and R 3 and p is 0 or 1. The reaction is carried out in the presence of an ether compound (3) represented by the 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 characterized by 。 Effect of the Invention

[0012] According to the present invention, a fluorine-containing carboxylate (4) which can be converted into various fluorine compounds can be produced in a good yield. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Hereinafter, an embodiment of the present invention (hereinafter, referred to as the present embodiment) will be described in detail. However, the present invention is not limited to the present embodiment, and can be modified in various ways within the scope of the present invention.

[0014] 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): FSO2CFXCF2OCF(CF2Y)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 following 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 , R 3 are the same or different, and each is a substituted or unsubstituted aliphatic or aromatic hydrocarbon group having 1 to 10 carbon atoms; R 1 and R 3 and p is 0 or 1. The reaction is carried out in the presence of an ether compound (3) represented by the formula: It is characterized by:

[0015] The compounds (1), (2), and (3), as well as the reaction conditions for producing compound (4) from compound (1), will be described in detail below.

[0016] <Fluorine-containing carboxylic acid fluoride (1) (compound (1))> The fluorine-containing carboxylic acid fluoride (1) is represented by the following general formula (1): FSO2CFXCF2OCF(CF2Y)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.

[0017] As X, a fluorine atom or a trifluoromethyl group is preferable because they are easily available or produced and tend to be economical, and from the same viewpoint, a fluorine atom is more preferable. As Y, a fluorine atom or a chlorine atom is preferable since they are easily available or produced and tend to be economically advantageous, and from the same viewpoint, a fluorine atom is more preferable. It is particularly preferable that the combination of X and Y is a fluorine atom (X=F, Y=F).

[0018] The method for producing compound (1) is not particularly limited, and compound (1) can be produced by a conventionally known 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.

[0019] <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.

[0020] As M, Na, K, or Cs is preferable since they are easily available and tend to be economical, and Na or K is more preferable from the same viewpoint.

[0021] 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 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. Furthermore, since there is a tendency to promote 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.

[0022] <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 , R 3 are the same or different, and each is a substituted or unsubstituted aliphatic or aromatic hydrocarbon group having 1 to 10 carbon atoms; R 1 And, R 3 may be linked; and p is 0 or 1. The compound (3) may be used alone or in combination of two or more kinds.

[0023] R of compound (3) 1 , R 2 , R 3 is an aliphatic or aromatic hydrocarbon group which may be substituted or unsubstituted. Examples of the substituent include, but are not limited to, halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms, nitrile groups (-CN), ether groups (-O-), carbonate groups (-OCO2-), ester groups (-CO2-), carbonyl groups (-CO-), sulfide groups (-S-), sulfoxide groups (-SO-), sulfone groups (-SO2-), and urethane groups (-NHCO2-). R 1 , R 2 , R 3 From the viewpoint of increasing the reactivity between compound (1) and compound (2), the aliphatic hydrocarbon group may be either substituted or unsubstituted, and is more preferably an unsubstituted aliphatic hydrocarbon group because it is easily available and tends to be economically advantageous.

[0024] R of compound (3) 1 , R 2 , R 3 has 1 to 10 carbon atoms. When p is 0, the reactivity of compound (1) and compound (2) tends to increase. 1 , R 3 The number of carbon atoms in R is preferably 6 or less, and from the same viewpoint, more preferably 5 or less. 1 , R 3 When the materials are not linked, they tend to be easy to obtain and economical. 1 , R 3 The number of carbon atoms in R is preferably 1 or more. 1 , R 3 When R is connected, it tends to be easy to obtain and economical. 1 , R 3 The number of carbon atoms is preferably 2 or more. In addition, when p is 1, the reactivity of compound (1) and compound (2) tends to increase. 1 , R 3 The number of carbon atoms in R is preferably 6 or less, and from the same viewpoint, it is more preferably 4 or less. R is easily available and tends to be economical. 1 , R 3The number of carbon atoms in the alkyl group is more preferably 2 or less, and from the same viewpoint, it is particularly preferably 1. Since the reactivity of compound (1) and compound (2) tends to increase, R 2 The number of carbon atoms in R is preferably 2 or more, and from the same viewpoint, it is preferably 6 or less, and more preferably 4 or less. 2 The number of carbon atoms in R is more preferably 3 or less. Since the reactivity of compound (1) and compound (2) tends to be increased and the economical efficiency tends to be improved, R 2 It is particularly preferable that the carbon number is 2.

[0025] 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.

[0026] 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.

[0027] 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 the 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 the dehydrating agent after filtration or the like may be used.

[0028] <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.

[0029] 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. However, 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 further more preferable that β / α is 5 or less.

[0030] <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 because the reactivity between compound (1) and compound (2) tends to be enhanced. From the same viewpoint, δ / γ is more preferably 0.8 or more, and further preferably δ / γ is 1 or more.

[0031] 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. However, 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 further more preferable that δ / γ is 5 or less.

[0032] <Reaction of compound (1) with compound (2)> The reaction temperature of compound (1) and compound (2) is not particularly limited as long as it is a commonly used reaction temperature, but since the reactivity of compound (1) and compound (2) tends to be high, the reaction temperature is preferably −40° C. or higher, and more preferably −20° C. or higher. From the same viewpoint and also because it tends to be economically advantageous when adjusting the temperature industrially, the reaction temperature is further preferably 0° C. or higher.

[0033] The upper limit of the reaction temperature between compound (1) and compound (2) is not particularly limited, but since there is a tendency for volatilization of compound (1) to be suppressed and the yield of fluorinated carboxylate (4) to be increased, it is preferably 160° C. or lower, more preferably 100° C. or lower. Since there is a tendency for side reactions in the reaction between compound (1) and compound (2) to be suppressed, it is further preferably 80° C. or lower, particularly preferably 60° C. or lower. The reaction temperature of the compound (1) and the compound (2) does not have to be constant so long as it is within the above range, and may be changed during the reaction.

[0034] The reaction time of compound (1) and compound (2) is not particularly limited as long as it is within a range generally used, but since the stability of the yield of compound (4) is further increased, it is preferably 0.5 hours or more, and more preferably 1 hour or more. Since an excessive reaction time tends to result in a more economical production method, 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.

[0035] 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 under standard conditions is low, so that when compound (1) and / or compound (3) are liquefied and not reused, pressurization to 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.

[0036] 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 it tends to be a more economical production method. The reaction atmosphere may be used alone or in combination of a plurality of reaction atmospheres.

[0037] The order in which compounds (1), (2), and (3) are added is not particularly limited. However, 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, preferred methods include a method of gradually adding a mixture of compound (1) and compound (3) to compound (2), a method of gradually adding compound (2) to a mixture of compound (1) and compound (3), a method of gradually adding a mixture of compound (2) and compound (3) to compound (1), and a method of gradually adding compound (1) to a mixture of compound (2) and compound (3).

[0038] INDUSTRIAL APPLICABILITY As described above, the present invention makes it possible to produce the fluorine-containing carboxylate (4) which can be converted into various fluorine compounds in a higher yield than conventional methods. EXAMPLES

[0039] The present invention is not limited to the following examples, so long as they do not depart from the gist of the present invention.

[0040] Working Example , reference example The analytical methods used in the comparative examples are as follows.

[0041] <Nuclear magnetic resonance analysis (NMR):19 Molecular structure analysis using F-NMR> Working Example , reference example And for the products obtained in the comparative examples, 19 Molecular structure analysis was carried out using F-NMR under the following measurement conditions. [Measurement conditions] Measurement equipment: JNM-ECZ400S nuclear magnetic resonance equipment (manufactured by JEOL Ltd.) Observation kernel: 19 F Solvent: deuterated chloroform Reference substance: tetramethylsilane (0.00 ppm) Observation frequency: 400MHz ( 1 H) Pulse width: 6.5μsec Wait time: 2 seconds Number of times: 16

[0042] Working Example , reference example The raw materials used in the comparative examples are shown below.

[0043] (Fluorine-containing carboxylic acid fluoride (1) (compound (1)) CF3CF(COF)OCF2CF2SO2F was produced according to the method described in WO 1998 / 43952 and further purified by distillation to obtain CF3CF(COF)OCF2CF2SO2F with a purity of >99%.

[0044] (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, 99% purity) Cesium carbonate (Aldrich, 99% purity)

[0045] (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, Ltd., 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 (Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) Methyl tert-butyl ether (Tokyo Chemical Industry Co., Ltd.)

[0046] (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)

[0047] [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, CF3CF(COF)OCF2CF2SO2F (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 resulting reaction mixture was filtered, and the filtrate was 19F-NMR analysis was performed. As a result of the analysis, it was found that sodium fluorine-containing 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 fluorine-containing 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 fluorine-containing carboxylate (5). In this example, 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)

[0048] [ reference Example 2] Except for using 1,2-dimethoxyethane instead of 4-methyltetrahydropyran, a fluorinated carboxylic acid sodium salt (5) was produced in the same manner as in Example 1. Analysis revealed that a fluorinated carboxylic acid sodium salt (5) was produced (amount produced: 3.08 g, product mass: 8.42 mmol, production rate: 97.1%). Also, this reference In the example, β / α was 1.0 and γ / δ was 1.0.

[0049] [Example 3] Except for using cyclopentyl methyl ether instead of 4-methyltetrahydropyran, a fluorinated carboxylic acid sodium salt (5) was produced in the same manner as in Example 1. Analysis revealed that a fluorinated carboxylic acid sodium salt (5) was produced (amount produced: 2.93 g, product mass: 8.00 mmol, production rate: 92.3%). In this example, β / α was 1.0 and γ / δ was 1.0.

[0050] [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. Analysis revealed 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 example, β / α was 1.0 and γ / δ was 1.0.

[0051] [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 example, β / α was 1.0 and γ / δ was 1.0.

[0052] [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 example, β / α was 1.0 and γ / δ was 1.0.

[0053] [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. Analysis revealed 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 example, β / α was 1.0 and γ / δ was 1.0.

[0054] [Example 8] A fluorinated potassium carboxylate (KO2CCF(CF3)OCF2CF2SO2F) 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 example, β / α was 1.0 and γ / δ was 1.0.

[0055] [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 example, β / α was 1.0 and γ / δ was 1.0.

[0056] [Example 10] A fluorine-containing cesium carboxylate (CsO2CCF(CF3)OCF2CF2SO2F) 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 example, β / α was 1.0 and γ / δ was 1.0.

[0057] [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. Analysis showed 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 example, 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 (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 20°C, and 4-methyltetrahydropyran (5.00 g) was added to the test tube and stirred. Then, CF3CF(COF)OCF2CF2SO2F (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 obtained was filtered, and the filtrate was 19 F-NMR analysis revealed that a fluorine-containing carboxylate sodium salt (5) was produced (amount produced: 1.03 g, product mass: 2.82 mmol, production rate: 97.5%). In this example, β / α was 1.0, and γ / δ was 5.0.

[0058] [Example 13] A heating / cooling stirring apparatus was set to 60° C., and CF3CF(COF)OCF2CF2SO2F (3.00 g, 8.67 mmol) was added dropwise over 10 minutes, followed by stirring for 1 hour and returning to room temperature, after which benzotrifluoride (0.30 g) was added, 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 example, β / α was 1.0 and γ / δ was 1.0.

[0059] [Comparative Example 1] Except for using hexane 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 example, β / α was 1.0 and γ / δ was 1.0.

[0060] [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 example, β / α was 1.0 and γ / δ was 1.0.

[0061] [Comparative Example 3] Except for using chloroform 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 example, β / α was 1.0 and γ / δ was 1.0.

[0062] [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), 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, acetonitrile (3.38 g) was added to the test tube, and the mixture was stirred. Then, CF3CF(COF)OCF2CF2SO2F (3.00 g, 8.67 mmol) was added dropwise over 10 minutes, and the mixture was stirred for 1 hour. The heating / cooling stirrer was set to 40°C, and the mixture was stirred for another 1 hour. After returning to room temperature, benzotrifluoride (0.30 g) was added for analysis, and the mixture was stirred. The reaction mixture obtained was filtered, and the filtrate was 19 F-NMR analysis revealed 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 example, β / α was 1.0, and γ / δ was 1.1.

[0063] [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 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 tetraethylene glycol dimethyl ether (3.24 g) was added to the test tube and stirred. Then, CF3CF(COF)OCF2CF2SO2F (3.00 g, 8.67 mmol) was added dropwise over 10 minutes, and stirred for 3 hours. The heating / cooling stirrer was set to 40°C, and stirred for another 1 hour. After returning 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 19F-NMR analysis revealed 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 example, β / α was 1.1, and γ / δ was 1.1. [Industrial Applicability]

[0064] 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

[Claim 1] The following general formula (4): FSO ２ CFXCF ２ OCF(CF ２ Y)CO ２ M (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): M ２ CO ３ (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 , R ３ are each an aliphatic or aromatic hydrocarbon group which may be the same or different and may be substituted or unsubstituted, having 1 to 10 carbon atoms; R １ and R ３ 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: