Method for producing fluorine-containing vinyl compound salt

Abstract

To provide a novel method for producing a fluorine-containing vinyl compound salt from a fluorine-containing cyclic compound in good yield.SOLUTION: The method for producing a fluorine-containing vinyl compound salt (5) comprises reacting a fluorine-containing cyclic compound (1) with a phosphate compound such as trisodium phosphate, a borate compound such as lithium tetraborate, and / or a silicate compound such as sodium silicate. (In general formula (5), X represents F, Cl or a trifluoromethyl group; Y represents F, Cl, Br or I; and M represents Na, K, Rb or Cs.)SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing a salt of a fluorine-containing vinyl compound. [Background technology]

[0002] The following general formula (1): [ka] (In the above general formula (1), 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.) Using a fluorine-containing cyclic compound (1) represented by the following formula (hereinafter, also referred to as "compound (1)"), The following general formula (5): [ka] (In the above general formula (5), 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 vinyl compound salt (5) represented by the following formula (hereinafter, also referred to as "compound (5)") (Patent Documents 1 and 2).

[0003] Patent Document 1 discloses a method for obtaining a fluorine-containing vinyl compound salt (5) that satisfies the condition "X=F, Y=F" in the above general formula (5) by reacting a fluorine-containing cyclic compound (1) that satisfies the condition "X=F, Y=F" in the above general formula (1) with sodium methoxide at room temperature overnight in the presence of dehydrated ether, removing the solvent, and drying the resulting product.

[0004] Patent Document 2 discloses a method for obtaining a fluorine-containing vinyl compound salt (5) which satisfies the condition "X=F, Y=F" in the above general formula (5) by reacting a fluorine-containing cyclic compound (1) which satisfies the condition "X=F, Y=F" in the above general formula (1) with various silanol compounds (e.g., sodium trimethylsilanolate). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] U.S. Pat. No. 3,560,568 [Patent Document 2] International Publication No. 2019 / 176425 Summary of the Invention [Problem to be solved by the invention]

[0006] As described above, Patent Document 1 discloses a method for obtaining the target fluorine-containing vinyl compound salt (5) that satisfies the conditions of "X=F, Y=F" by reacting a fluorine-containing cyclic compound (1) that satisfies the conditions of "X=F, Y=F" with sodium methoxide. Moreover, as described in Patent Document 2, when the fluorine-containing vinyl compound salt (5) that satisfies the conditions of "X=F, Y=F" is actually synthesized using the method of Patent Document 1, the amount of the target compound produced is reduced (see paragraph

[0010] of Patent Document 2). Furthermore, in view of the fact that the method described in Patent Document 1 produces a small amount of fluorinated vinyl compound salt (5) as described above, to the best of the inventors' knowledge, the method for obtaining fluorinated vinyl compound salt (5) described in Patent Document 2 is the only method by which fluorinated vinyl compound salt (5) can be obtained in high yield. However, the silanol compound (R 1 R 2 R 3 Si(OM) [M is an alkyl metal or an alkyl earth metal, R 1 ~R 3are each independently a hydrocarbon group having 1 to 10 carbon atoms which may be substituted, or OM.]) is known to have the following equilibrium reaction (J. Am. Chem. Soc. 1953, 75, pp. 5615-5618). [ka] (In the formula, R is an alkyl group.) Therefore, depending on the environment in which the silanol compound is present, the silanol compound may be converted to (R 3 Si) 2 O, which may decrease the purity of the silanol compound or the amount of the silanol compound in the system. For this reason, there has been a demand for the development of a new method for producing a fluorinated vinyl compound salt (5) from a fluorinated cyclic compound (1) in a good yield without using the silanol compound.

[0007] The present invention has been made in consideration of the above circumstances, and an object of the present invention is to provide a novel process for producing a fluorinated vinyl compound salt (5) from a fluorinated cyclic compound (1) in good yield. [Means for solving the problem]

[0008] As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that the above-mentioned object can be achieved by reacting a fluorine-containing cyclic compound (1) with a specific salt that is generally readily available and can be stably handled, and have thus completed the present invention. The specific salt is at least one compound selected from the group consisting of a phosphate compound (2) (hereinafter also referred to as "compound (2)") having a structural unit represented by the following general formula (2a), a borate compound (3) (hereinafter also referred to as "compound (3)") represented by the following general formula (3), and a silicate compound (4) (hereinafter also referred to as "compound (4)") represented by the following general formula (4). [ka] (In the above general formula (2a), M 2is Li, Na, K, Rb, or Cs, n is an integer of 1 or more, and when n is an integer of 2 or more, there are a plurality of M 2 may be the same or different.) [ka] (In the above general formula (3), M 4 is Li, Na, K, Rb, or Cs. [ka] (In the above general formula (4), M 5 is Li, Na, K, Rb, or Cs.

[0009] That is, the present invention is as follows. [1] The present invention relates to a fluorine-containing cyclic compound (1) represented by the following general formula (1): The method for producing a fluorine-containing vinyl compound salt (5) represented by the following general formula (5) comprises reacting one or more salts selected from the group consisting of a phosphate compound (2) represented by the following general formula (2a), a borate compound (3) represented by the following general formula (3), and a silicate compound (4) represented by the following general formula (4). The following general formula (1): [ka] (In the above general formula (1), 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.) The following general formula (2a): [ka] (In the above general formula (2a), M 2 is Li, Na, K, Rb, or Cs, n is an integer of 1 or more, and when n is an integer of 2 or more, there are a plurality of M 2 may be the same or different.) The following general formula (3): [ka] (In the above general formula (3), M 4 is Li, Na, K, Rb, or Cs. The following general formula (4): [ka] (In the above general formula (4), M 5 is Li, Na, K, Rb, or Cs. The following general formula (5): [ka] (In the above general formula (5), 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.) [2] In the method for producing the fluorinated vinyl compound salt (5) of the present embodiment, it is preferable that the ratio ((β+γ+δ) / α) of the sum of the amount of substance (β) of the phosphate compound (2), the amount of substance (γ) of the borate compound (3) and the amount of substance (δ) of the silicate compound (4) relative to the amount of substance (α) of the fluorinated cyclic compound (1) is 0.5 to 10. [3] In the method for producing the fluorinated vinyl compound salt (5) of the present embodiment, it is preferable to react the fluorinated cyclic compound (1) with the phosphate compound (2), the borate compound (3) and / or the silicate compound (4) in the presence of at least one additive selected from the group consisting of ether compounds, nitrile compounds, amide compounds, and sulfo compounds. [4] In the method for producing a fluorinated vinyl compound salt (5) of this embodiment, the additive is preferably 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, 1,2-dimethoxypropane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol di It is preferable that the organic solvent is one or more compounds selected from the group consisting of methyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, acetonitrile, propionitrile, butyronitrile, isobutyronitrile, 2-methylbutyronitrile, cyclohexanecarbonitrile, benzonitrile, adiponitrile, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-methylpyrrolidone, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, dibutyl sulfoxide, ethyl methyl sulfone, ethyl isopropyl sulfone, sulfolane, and 3-methylsulfolane. [5] In the method for producing a fluorinated vinyl compound salt (5) of the present embodiment, it is preferable that the ratio (θ / (ε+δ+η)) of the mass (θ) of the additive to the sum of the mass (ε) of the phosphate compound (2), the mass (ζ) of the borate compound (3), and the mass (η) of the silicate compound (4) is 0.5 to 100. Effect of the Invention

[0010] According to the present invention, there is provided a novel process by which a fluorinated vinyl compound salt (5) can be produced in good yield from a fluorinated cyclic compound (1). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] 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.

[0012] The manufacturing method of this embodiment is as follows: The following general formula (1): [ka] (In the above general formula (1), 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 cyclic compound (1) represented by the following formula: The following general formula (2a): [ka] (In the above general formula (2a), M 2 is Li, Na, K, Rb, or Cs, n is an integer of 1 or more, and when n is an integer of 2 or more, there are a plurality of M 2 may be the same or different.) (2) a phosphate compound having a structural unit represented by The following general formula (3): [ka] (In the above general formula (3), M 4 is Li, Na, K, Rb, or Cs. and / or a borate compound (3) represented by the formula: The following general formula (4): [ka] (In the above general formula (4), M 5 is Li, Na, K, Rb, or Cs. The method comprises reacting a silicate compound (4) represented by the formula: The following general formula (5): [ka] In the above general formula (5), 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 vinyl compound salt (5) represented by the following formula:

[0013] The compound (1) and its salts (=compounds (2), (3), and (4)), as well as the reaction conditions for producing the fluorine-containing vinyl compound salt (5) from the compound (1), will be described in detail below.

[0014] [Fluorine-containing cyclic compound (1) (also referred to as compound (1)] The fluorine-containing cyclic compound (1) in this embodiment is represented by the following general formula (1): [ka] (In the above general formula (1), 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.

[0015] In the above general formula (1), X is preferably a fluorine atom or a trifluoromethyl group because they are easily available or produced and tend to be economical, and from the same viewpoint, a fluorine atom is more preferable. In the above general formula (1), Y is preferably a fluorine atom or a chlorine atom because they are easily available or produced and tend to be economical, 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).

[0016] The method for producing the fluorine-containing cyclic compound (1) of this embodiment is not particularly limited, and can be produced by a conventionally known method. For example, compound (1) that satisfies the condition of "X = F, Y = F" in the general formula (1) above can be produced by the method described in International Publication No. 2019 / 176425. Compound (1) can also be purchased, for example, from Synquest Laboratories.

[0017] [salts] In this embodiment, the target fluorinated vinyl compound salt (5) is produced by reacting the fluorinated cyclic compound (1) with a predetermined salt, which is at least one selected from the group consisting of the compounds (2), (3) and (4). Each of the compounds (2) to (4) will be described below. <Phosphate compound (2) (also referred to as compound (2))> The phosphate compound (2) in this embodiment is represented by the following general formula (2a): [ka] (In the above general formula (2a), M 2 are each independently Li, Na, K, Rb, or Cs, and n is an integer of 1 or more. When n is an integer of 2 or more, 2 may be the same or different. The phosphate compound (2) in this embodiment is represented by the following general formula (2b): [ka] (In the above general formula (2b), M 1 , M 2 and M 3 are each independently Li, Na, K, Rb, or Cs, and n is an integer of 1 or more. 1 , M 2 and M 3 may be the same or different.) It is preferable that the formula is represented by the formula: The phosphate compound (2) may be used alone or in combination of two or more kinds.

[0018] In the above general formula (2a), M 2 is Li, Na, K, Rb, or Cs. Among these, M is selected because it is easy to obtain and tends to be economical. 2 is preferably Li, Na, or K, more preferably Li or Na, and even more preferably Na. When n in the above general formula (2a) is 2 or more, 2 may be the same or different. In the above general formula (2b), M 1 , M 2 and M 3 are independent of each other, may be the same or different, and are any of Li, Na, K, Rb, and Cs. Among these, M is preferred because it is easily available and tends to be economical. 1 , M 2 and M 3 are each independently preferably Li, Na, or K, more preferably Li or Na, and even more preferably Na. In addition, when n in the above general formula (2b) is 2 or more, there are multiple M 2 may be the same or different.

[0019] In the above general formulas (2a) and (2b), n is an integer of 1 or more. There is no particular limitation on n as long as it is an n possessed by a generally available compound (2), but the upper limit of n in the above general formulas (2a) and (2b) is preferably 25 or less, more preferably 3 or less. Since the reactivity between compound (1) and compound (2) tends to increase, n in the above general formulas (2a) and (2b) is more preferably 2 or less, particularly preferably 1.

[0020] Specific examples of the phosphate compound (2) in the present embodiment include trilithium phosphate, trisodium phosphate, tripotassium phosphate, trirubidium phosphate, tricesium phosphate, tetralithium diphosphate, tetrasodium diphosphate, tetrapotassium diphosphate, tetrarubidium diphosphate, tetracesium diphosphate, pentalithium triphosphate, pentasodium triphosphate, pentapotassium triphosphate, pentarubidium triphosphate, pentasium triphosphate, lithium hexametaphosphate, sodium hexametaphosphate, potassium hexametaphosphate, rubidium hexametaphosphate, cesium hexametaphosphate, lithium metaphosphate, sodium metaphosphate, potassium metaphosphate, rubidium metaphosphate, and cesium metaphosphate. In the present embodiment, the phosphate compound (2) is preferably trilithium phosphate, trisodium phosphate, tripotassium phosphate, tetralithium diphosphate, tetrasodium diphosphate, tetrapotassium diphosphate, pentalithium triphosphate, pentasodium triphosphate, pentapotassium triphosphate, lithium hexametaphosphate, sodium hexametaphosphate, potassium hexametaphosphate, lithium metaphosphate, sodium metaphosphate, or potassium metaphosphate, since they are easily available and tend to be economical. Trilithium phosphate, trisodium phosphate, tripotassium phosphate, tetralithium diphosphate, tetrasodium diphosphate, tetrapotassium diphosphate, pentalithium triphosphate, pentasodium triphosphate, or pentapotassium triphosphate is more preferred. Since the reactivity of compound (1) and compound (2) tends to increase, trilithium phosphate, trisodium phosphate, tripotassium phosphate, tetrasodium diphosphate, or tetrapotassium diphosphate is even more preferred, and trilithium phosphate, trisodium phosphate, or tripotassium phosphate is particularly preferred.

[0021] <Borate compound (3) (compound (3))> The borate compound (3) in this embodiment is represented by the following general formula (3): [ka] (In the above general formula (3), M 4 is Li, Na, K, Rb, or Cs. It is expressed as: The borate compound (3) may be used alone or in combination of two or more kinds.

[0022] In the above general formula (3), M 4 is Li, Na, K, Rb, or Cs. Among these, M in the general formula (3) is preferred because it is easily available and tends to be economical. 4 is preferably Li, Na, or K, and more preferably Na or K.

[0023] Specific examples of the borate compound (3) in this embodiment include dilithium tetraborate, disodium tetraborate, dipotassium tetraborate, dirubidium tetraborate, and disesium tetraborate. Dilithium tetraborate, disodium tetraborate, and dipotassium tetraborate are preferred, and disodium tetraborate and dipotassium tetraborate are more preferred, since they are easily available and tend to be economical.

[0024] <Silicate compound (4) (compound (4))> The silicate compound (4) in this embodiment is represented by the following general formula (4): [ka] (In the above general formula (4), M 5 is Li, Na, K, Rb, or Cs. It is expressed as: The silicate compound (4) may be used alone or in combination of two or more kinds.

[0025] In the above general formula (4), M 5 is Li, Na, K, Rb, or Cs. Among these, M in the above general formula (4) is preferred because it is easily available and tends to be economical. 5 is preferably Li, Na, or K, more preferably Na or K, and even more preferably Na.

[0026] Specific examples of the silicate compound (4) in the present embodiment include lithium silicate, sodium silicate, potassium silicate, rubidium silicate, and cesium silicate. As they tend to be easily available and economically advantageous, lithium silicate, sodium silicate, and potassium silicate are preferred, lithium silicate and sodium silicate are more preferred, and sodium silicate is particularly preferred.

[0027] In this embodiment, the compound to be reacted with the fluorine-containing cyclic compound (1) may be any one of the phosphate compound (2), the borate compound (3) and the silicate compound (4), or each of these compounds (phosphate compound (2), borate compound (3) and silicate compound (4)) may be used alone or in combination of two or more kinds. When emphasis is placed on the viewpoint of showing a tendency to improve the yield of the target compound (5), it is preferable to use each of the compound (2) and / or the compound (4) alone or to use a combination of the compound (2) and / or the compound (4), and it is more preferable to use the compound (2).

[0028] In this embodiment, the compound (2), the compound (3), and the compound (4) may be used with reduced water content as necessary. In particular, when producing the target fluorine-containing vinyl compound salt (5) from the compound (1), it is preferable to use the compound (2), the compound (3), and / or the compound (4) with reduced water content, since side reactions can be suppressed and the yield of the fluorine-containing vinyl compound salt (5) tends to be increased. The method for reducing the water content of the compound (2), the compound (3), and / or the compound (4) used in the production method of this embodiment is not particularly limited as long as it is a generally available method, but a method of heating the compounds (2) to (4) is preferable. When the compounds (2) to (4) are heated, they may be heated under vacuum or under a dry gas flow. 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. In this embodiment, the heating temperature is not particularly limited as long as it can reduce the water content of compounds (2) to (4), but since there is a tendency to suppress deterioration of compounds (2), (3) and / or (4), the heating temperature is preferably 300° C. or lower, more preferably 250° C. or lower, and even more preferably 200° C. or lower. Since there is a tendency to promote reduction in water content, the heating temperature is preferably 100° C. or higher, more preferably 120° C. or higher, and even more preferably 150° C. or higher.

[0029] <Additives> In the production method of the fluorinated vinyl compound salt (5) of this embodiment, depending on the types of compound (2), compound (3) and / or compound (4) used, since the reaction between compound (1) and compound (2), compound (3) and / or compound (4) can be promoted by dissolving compound (2), compound (3) and / or compound (4), additives can also be used. In this embodiment, examples of a method for using the additive include a method for mixing the additive with one or more compounds selected from the group consisting of compound (1), compound (2), compound (3), and compound (4), and a method for mixing the additive with a mixture of compound (1) and one or more salts selected from the group consisting of compound (2), compound (3), and compound (4). In the method for producing the fluorine-containing vinyl compound salt (5) of this embodiment, an additive may be used by mixing with one or more compounds selected from the group consisting of compound (1), compound (2), compound (3) and compound (4) as necessary, and examples of the additive include ether compounds, nitrile compounds, amide compounds, sulfo compounds, saturated hydrocarbon compounds, aromatic hydrocarbon compounds, halogenated hydrocarbon compounds, alcohol compounds, ketone compounds, ester compounds, water, etc. Among these, ether compounds, nitrile compounds, amide compounds and sulfo compounds are preferred, and amide compounds and sulfo compounds are more preferred, since they tend to have high solubility in compound (2), compound (3) and / or compound (4). The additives may be used alone or in combination of two or more kinds.

[0030] Specific examples of the additives 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, 1,2-dimethoxypropane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol isopropyl methyl ether. ether compounds such as butyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, and dipropylene glycol dimethyl ether; nitrile compounds such as acetonitrile, propionitrile, butyronitrile, isobutyronitrile, 2-methylbutyronitrile, cyclohexanecarbonitrile, benzonitrile, and adiponitrile; N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-methylpyrrolidone, tetramethylurea, and 1,Amide compounds such as 3-dimethyl-2-imidazolidinone, sulfo compounds such as dimethyl sulfoxide, dibutyl sulfoxide, ethyl methyl sulfone, ethyl isopropyl sulfone, sulfolane, and 3-methyl sulfolane, saturated hydrocarbon compounds such as n-pentane, n-hexane, isohexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane, aromatic hydrocarbon compounds such as benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, naphthalene, tetralin, and biphenyl, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, trichloroethane, tetrachloroethane, pentachloroethane, hexachloroethane, dichloroethylene, trichloroethylene, tetrachloroethylene, dichloropropane, trichloropropane, isopropyl chloride, butyl chloride, hexyl chloride, chlorobenzene, dichlorobenzene, trichlorobenzene, Examples of the volatile organic solvent include halogenated hydrocarbon compounds such as ethanol, chlorotoluene, and chloronaphthalene, alcohol compounds such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, cyclohexanol, and benzyl alcohol, ketone compounds such as acetone, methylacetone, ethyl methyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl hexyl ketone, diethyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, and cyclohexanone, and ester compounds such as ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, hexyl acetate, octyl acetate, cyclohexyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, and benzyl benzoate.

[0031] Since the additive of this embodiment tends to have high solubility in compound (2), compound (3), and / or compound (4), the additive is preferably 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, 1,2-dimethoxypropane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol diisopropyl ... Preferred are butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, acetonitrile, propionitrile, butyronitrile, isobutyronitrile, 2-methylbutyronitrile, cyclohexanecarbonitrile, benzonitrile, adiponitrile, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-methylpyrrolidone, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, dibutyl sulfoxide, ethyl methyl sulfone, ethyl isopropyl sulfone, sulfolane, and 3-methylsulfolane. From a similar viewpoint, the additive of the present embodiment is more preferably diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, acetonitrile, propionitrile, butyronitrile, benzonitrile, adiponitrile, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-methylpyrrolidone, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, dibutyl sulfoxide, ethyl methyl sulfone, ethyl isopropyl sulfone, sulfolane, or 3-methylsulfolane. More preferred are tetraethylene glycol dimethyl ether, adiponitrile, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-methylpyrrolidone, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, dibutyl sulfoxide, ethyl methyl sulfone, ethyl isopropyl sulfone, sulfolane, and 3-methyl sulfolane. Particularly preferred are N,N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and sulfolane.

[0032] In this embodiment, the use of an additive having a lower water content tends to increase the yield of the fluorinated vinyl compound salt (5), so it is preferable to use an additive having a lower water content. The additive with a low water content can be purchased, or a method for reducing the water content of the additive can be used. The method for reducing the water content of the additive of the present embodiment is not particularly limited as long as it is a generally 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. In this embodiment, when a dehydrating agent is used, an additive containing a dehydrating agent may be used as long as it does not affect the reaction between compound (1) and compound (2), compound (3), and / or compound (4), or an additive that does not contain a dehydrating agent after filtration or the like may be used.

[0033] <The ratio (β+γ+δ) / α) of the sum of the amount of substance (β) of compound (2), the amount of substance (γ) of compound (3), and the amount of substance (δ) of compound (4) to the amount of substance (α) of compound (1)> In the method for producing a fluorine-containing vinyl compound salt (5) of this embodiment, the mixing ratio of the fluorine-containing cyclic compound (1) represented by the above general formula (1) to a salt selected from the group consisting of a phosphate compound (2) having a structural unit represented by the above general formula (2a), a borate compound (3) represented by the above general formula (3), and a silicate compound (4) represented by the above general formula (3) is expressed by a mathematical formula (I) which represents the ratio of the sum of the amount of substance (β) of the phosphate compound (2), the amount of substance (γ) of the borate compound (3), and the amount of substance (δ) of the silicate compound (4) to the amount of substance (α) of the fluorine-containing cyclic compound (1): (β+γ+δ) / α preferably satisfies 0.5 or greater, more preferably satisfies 0.8 or greater, and further preferably satisfies 1 or greater. When the value of ((β+γ+δ) / α) in the above formula (I) is 0.5 or more, the yield of the fluorine-containing vinyl compound salt (5) tends to be higher.

[0034] In addition, the upper limit of the above formula (I) is not particularly limited, but since the amount of compound (2), compound (3) and / or compound (4) used is reduced and the production efficiency or cost of the target compound (5) tends to be excellent, it is preferable that (β+γ+δ) / α in the above formula (I) is 10 or less, preferably 7 or less, and more preferably 5 or less.

[0035] <The ratio (θ) of the mass of the additive to the sum of the mass (ε) of compound (2), the mass (ζ) of compound (3), and the mass (η) of compound (4) (θ / (ε+ζ+η))> In the method for producing a fluorinated vinyl compound salt (5) of this embodiment, the mixing ratio of the fluorinated cyclic compound (1) represented by the above general formula (1), the salt selected from the group consisting of a phosphate compound (2) having a structural unit represented by the above general formula (2a), a borate compound (3) represented by the above general formula (3), and a silicate compound (4) represented by the above general formula (4), and an additive added as necessary, is expressed by a mathematical formula (II) which represents the ratio of the mass (θ) of the additive to the sum of the mass (ε) of the phosphate compound (2), the mass (ζ) of the borate compound (3), and the mass (η) of the silicate compound (4): There are no particular limitations on θ / (ε+ζ+η) as long as it is within a range in which compound (1) reacts with compound (2), compound (3), and / or compound (4). In this embodiment, depending on the type of compound (2), compound (3), and / or compound (4), the reaction between compound (1) and compound (2), compound (3), and / or compound (4) can be promoted by dissolving compound (2), compound (3), and / or compound (4). Therefore, θ / (ε+ζ+η) in the above mathematical formula (II) is preferably 0.5 or more, more preferably 1.5 or more, and even more preferably 2 or more.

[0036] In addition, the upper limit of θ / (ε+ζ+η) in the above formula (II) is not particularly limited, but since the amount of additives used is reduced and the production efficiency or cost of the target compound (5) tends to be excellent, the upper limit of θ / (ε+ζ+η) in the above formula (II) is preferably 100 or less, more preferably 50 or less, and even more preferably 10 or less.

[0037] <Reaction of compound (1) with compound (2), compound (3) and / or compound (4)> In this embodiment, the reaction temperature of compound (1) with compound (2), compound (3) and / or compound (4) is not particularly limited as long as it is a commonly used reaction temperature, but since the reactivity of compound (1) with compound (2), compound (3) and / or compound (4) tends to be enhanced, the reaction temperature is preferably −20° C. or higher, and more preferably 0° 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 20° C. or higher. In the present embodiment, the upper limit of the reaction temperature between compound (1) and compound (2), compound (3), and / or compound (4) is not particularly limited; however, depending on the type of compound (1) and / or additive, there is a tendency that volatilization can be suppressed and the yield of compound (5) tends to be increased, and there is a tendency that side reactions in the reaction between compound (1) and compound (2), compound (3), and / or compound (4) can be suppressed. Therefore, the upper limit is preferably 160° C. or lower, more preferably 140° C. or lower, and even more preferably 100° C. or lower. The reaction temperature of compound (1) with compound (2), compound (3) and / or compound (4) does not need to be constant so long as it is within the above range, and may be changed during the reaction.

[0038] In this embodiment, the reaction time of compound (1) with compound (2), compound (3) and / or compound (4) is not particularly limited as long as it is within a generally used range, but since the stability of the yield of compound (5) 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.

[0039] In this embodiment, the reaction pressure of compound (1) with compound (2), compound (3) and / or compound (4) is not particularly limited as long as it is within a range that is usually used, and the reaction is usually carried out under atmospheric pressure. However, depending on the type of compound (1) and / or additive, the vapor pressure at standard conditions is low, so if compound (1) and / or additive are liquefied and not reused, pressurization to atmospheric pressure or higher is an effective means. If compound (1) and / or additive are liquefied and reused, reduced pressure below atmospheric pressure may be used. The reaction pressure of compound (1) with compound (2) and / or compound (3) does not need to be constant so long as it is within the above range, and may be changed during the reaction.

[0040] In this embodiment, the atmosphere for the reaction of compound (1) with compound (2), compound (3) and / or compound (4) is not particularly limited as long as it is a commonly used atmosphere, and typically, air atmosphere, nitrogen atmosphere, argon atmosphere, etc. are used. Among these, nitrogen atmosphere and argon atmosphere are preferred because they tend to produce compound (5) 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.

[0041] In the present embodiment, the order of adding compound (1) to compound (2), compound (3), and / or compound (4) is not particularly limited. However, since the reaction between compound (1) and compound (2), compound (3), and / or compound (4) is an exothermic reaction, and side reactions tend to be suppressed particularly when the amounts of compounds (1), (2), (3), and (4) used are large, a method of gradually adding compound (2), compound (3), and / or compound (4) to compound (1), a method of gradually adding compound (1) to compound (2), compound (3), and / or compound (4), and the like are preferred, and a method of gradually adding compound (1) to compound (2), compound (3), and / or compound (4) is more preferred.

[0042] As described above, the present invention provides a method for producing an alkali metal alkoxide and a silanol compound (e.g., R 1a R 2a R 3a Si(OM) [M is an alkyl metal or an alkyl earth metal, R 1a ~R 3a each independently represents an optionally substituted hydrocarbon group having 1 to 10 carbon atoms or OM.]), the fluorinated vinyl compound salt (5) can be produced in good yield from the fluorinated cyclic compound (1). EXAMPLES

[0043] The present invention is not limited to the following examples, so long as they do not depart from the gist of the present invention.

[0044] The analytical methods used in the examples and comparative examples are as follows.

[0045] <Nuclear magnetic resonance analysis (NMR): 19 Molecular structure analysis using F-NMR> Regarding the products obtained in the examples and 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 material: CFCl 3 (0.00ppm) Observation frequency: 400MHz ( 1 H) Pulse width: 6.5μsec Wait time: 2 seconds Number of times: 16

[0046] The raw materials used in the examples and comparative examples are shown below.

[0047] (Fluorine-containing cyclic compound (1)) According to the method described in WO 2019 / 176425, a fluorine-containing cyclic compound (1.1) represented by the following formula (1.1) was produced. [ka]

[0048] (Phosphate Compounds (2)) Trisodium phosphate (Alfa Aesar anhydrous was used. Hereinafter referred to as "P3N". The molecular formula is Na 3 PO 4 It is.) Trilithium phosphate (manufactured by Toshima Manufacturing Co., Ltd.) was used. Hereinafter, it is also referred to as "P3L". The molecular formula is Li 3 PO 4 It is.) Tripotassium phosphate (anhydrous, manufactured by Alfa Aesar, was used. Hereinafter, this will be referred to as "P3K." The molecular formula is K 3 PO 4 It is.) Tetrasodium diphosphate (anhydrous, manufactured by Alfa Aesar, was used. Hereinafter, this will be referred to as "P4N". The molecular formula is Na 4 P 2 O 7 It is.) Tetrapotassium diphosphate (anhydrous, manufactured by Alfa Aesar, was used. Hereinafter, this will be referred to as "P4K." The molecular formula is K 4 P 2 O 7 It is.)

[0049] (Borate Compound (3)) Lithium tetraborate (Wako special grade anhydrous, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., was used. Hereinafter, this will be referred to as "B2L". The molecular formula is Li 2 B 4 O 7 It is.) Sodium tetraborate (anhydrous, manufactured by Alfa Aesar, was used. Hereinafter, this will be referred to as "B2N". The molecular formula is Na 2 B4 O 7 It is.)

[0050] (Silicate compound (4)) Sodium silicate (anhydrous, manufactured by Nacalai Tesques, Inc., was used. Hereinafter, it is also called "S2N". The molecular formula is Na 2 SiO 3 It is.)

[0051] (Additives) Dimethyl sulfoxide (Wako special grade manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. was used. Hereinafter referred to as "DMSO". The water content was adjusted by adding dried molecular sieve 4A 1 / 16 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), dehydrating, and removing the molecular sieve 4A 1 / 16.) N,N-Dimethylformamide (Wako special grade manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. was used. Hereinafter, this will be referred to as "DMF." The water content was adjusted by adding dried molecular sieve 4A 1 / 16 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), dehydrating, and removing the molecular sieve 4A 1 / 16.) 1,3-Dimethyl-2-imidazolidinone (Wako special grade manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. was used. Hereinafter, this will be referred to as "DMI." The water content was adjusted by adding dried molecular sieve 4A 1 / 16 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), dehydrating, and removing the molecular sieve 4A 1 / 16.) Sulfolane (Tokyo Chemical Industry Co., Ltd., hereafter also referred to as "SFL"). The water content was adjusted by adding dried molecular sieve 3A 1 / 16 (Fujifilm Wako Pure Chemical Industries, Ltd.), dehydrating, and removing the molecular sieve 3A 1 / 16.) Tetraethylene glycol dimethyl ether (Tokyo Chemical Industry Co., Ltd., hereafter also referred to as "TEG." The water content was adjusted by adding dried molecular sieve 3A 1 / 16 (Fujifilm Wako Pure Chemical Industries, Ltd.), dehydrating, and removing the molecular sieve 3A 1 / 16.) Adiponitrile (Wako special grade manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. was used. Hereinafter, it is also referred to as "ADN". The water content was adjusted by adding dried molecular sieve 4A 1 / 16 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), dehydrating, and removing the molecular sieve 4A 1 / 16.)

[0052] (others) 2,2,2-trifluoroethanol (Wako special grade manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. was used.) Benzotrifluoride (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as "BTF") Sodium carbonate (anhydrous, manufactured by Alfa Aesar, was used. Hereinafter, it will be referred to as "CN2". The molecular formula is Na 2 CO 3 It is.) Sodium sulfate (anhydrous, manufactured by Alfa Aesar, was used. Hereinafter, this will be referred to as "RN2". The molecular formula is Na 2 SO 4 It is.) Sodium nitrate (Wako special grade manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. was used. Hereinafter, it is also called "NN1". The molecular formula is NaNO 3 It is.)

[0053] [Example 1] A stirrer and P3N (0.60 g, 3.68 mmol) were placed in a test tube (Radley Discovery Technologies, RP98059, RP98062), and the tube was placed in a heating / cooling stirrer (Tokyo Rikakikai Co., Ltd., PPM-5512 type, cooling water was circulated from the outside when cooling). After vacuuming, the heating / cooling stirrer was set to 100°C and dried for 1 hour. The test tube was placed in a nitrogen atmosphere, and then cooled to room temperature. DMSO (2.55 g) was placed in the test tube, stirred, and then the heating / cooling stirrer was set to 60°C. After the heating / cooling stirrer reached 60°C, the fluorine-containing cyclic compound (1.1) (1.00 g, 3.57 mmol) was dropped and stirred for 4 hours. After cooling to room temperature, BTF (0.1 g) for analysis was added, stirred, and filtered with a chromatodisc (GL Sciences, pore size 0.2 μm), and the obtained filtrate was19 The reaction was analyzed by F-NMR. As a result of the analysis, it was found that a fluorine-containing vinyl compound salt (5.1) represented by the following formula (5.1) was produced (amount produced: 0.84 g, mass of product: 2.78 mmol, production rate: 78.0%). 3 and CF of fluorine-containing vinyl compound salt (5.1) 2 The amount of fluorine-containing vinyl compound salt (5.1) produced was calculated from the integral value of In this example, (β+γ+δ) / α was 1.0, and (θ / (ε+ζ+η)) was 4.2. [ka] 19 F-NMR: δ(ppm) -84.67(2F), -116.41(1F), -118.20(2F), -123.72(1F), -134.78(1F)

[0054] [Example 2] The target fluorine-containing vinyl compound salt (CF=CF 2 OCF 2 CF 2 SO 3 Li) was produced. 19 F-NMR analysis revealed that the fluorine-containing vinyl compound salt (CF=CF 2 OCF 2 CF 2 SO 3 Li) was confirmed (amount produced: 0.80 g, product mass: 2.65 mmol, production rate: 74.3%). In this example, (β+γ+δ) / α was 1.0, and (θ / (ε+ζ+η)) was 6.0.

[0055] [Example 3] The target fluorine-containing vinyl compound salt (CF=CF) was obtained in the same manner as in Example 1, except that P3N was changed to P3K (0.78 g, 3.68 mmol). 2 OCF 2 CF 2 SO3 K) was produced. 19 F-NMR analysis revealed that the fluorine-containing vinyl compound salt (CF=CF 2 OCF 2 CF 2 SO 3 The formation of K) was confirmed (amount formed: 0.86 g, product mass: 2.86 mmol, formation rate: 80.2%). In this embodiment, (β+γ+δ) / α was 1.0, and (θ / (ε+ζ+η)) was 3.3.

[0056] [Example 4] The target fluorine-containing vinyl compound salt (5.1) was produced in the same manner as in Example 1, except that P3N was changed to P4N (0.98 g, 3.68 mmol). 19 F-NMR analysis confirmed the production of a fluorine-containing vinyl compound salt (5.1) (production amount: 0.70 g, product mass: 2.35 mmol, production rate: 65.8%). In this example, (β+γ+δ) / α was 1.0, and (θ / (ε+ζ+η)) was 2.6.

[0057] [Example 5] The target fluorine-containing vinyl compound salt (CF=CF 2 OCF 2 CF 2 SO 3 K) was produced. 19 F-NMR analysis revealed that the fluorine-containing vinyl compound salt (CF=CF 2 OCF 2 CF 2 SO 3 The formation of K) was confirmed (amount formed: 0.72 g, product mass: 2.41 mmol, formation rate: 67.5%). In this example, (β+γ+δ) / α was 1.0, and (θ / (ε+ζ+η)) was 2.1.

[0058] [Example 6] The target fluorine-containing vinyl compound salt (CF=CF 2 OCF 2 CF 2 SO 3 Li) was produced. 19 F-NMR analysis revealed that the fluorine-containing vinyl compound salt (CF=CF 2 OCF 2 CF 2 SO 3 The formation of Li) was confirmed (amount produced: 0.61 g, product mass: 2.04 mmol, production rate: 57.1%). In this example, (β+γ+δ) / α was 1.0, and (θ / (ε+ζ+η)) was 4.1.

[0059] [Example 7] The target fluorine-containing vinyl compound salt (5.1) was produced in the same manner as in Example 1, except that P3N was changed to B2N (0.74 g, 3.68 mmol). 19 F-NMR analysis confirmed the production of a fluorine-containing vinyl compound salt (5.1) (production amount: 0.63 g, product mass: 2.10 mmol, production rate: 58.8%). In this example, (β+γ+δ) / α was 1.0, and (θ / (ε+ζ+η)) was 3.4.

[0060] [Example 8] The target fluorine-containing vinyl compound salt (5.1) was produced in the same manner as in Example 1, except that P3N was changed to S2N (0.45 g, 3.68 mmol). 19 F-NMR analysis confirmed the production of a fluorine-containing vinyl compound salt (5.1) (production amount: 0.69 g, product mass: 2.31 mmol, production rate: 64.6%). In this example, (β+γ+δ) / α was 1.0, and (θ / (ε+ζ+η)) was 5.7.

[0061] [Example 9] The target fluorine-containing vinyl compound salt (5.1) was produced in the same manner as in Example 1, except that DMSO was changed to DMF (2.55 g). 19 F-NMR analysis confirmed the production of a fluorine-containing vinyl compound salt (5.1) (production amount: 0.80 g, product mass: 2.68 mmol, production rate: 75.1%). In this example, (β+γ+δ) / α was 1.0, and (θ / (ε+ζ+η)) was 4.2.

[0062] [Example 10] The target fluorine-containing vinyl compound salt (5.1) was produced in the same manner as in Example 1, except that DMSO was changed to DMI (2.55 g). 19 F-NMR analysis confirmed the production of the fluorine-containing vinyl compound salt (7) (production amount: 0.82 g, product mass: 2.73 mmol, production rate: 76.4%). In this example, (β+γ+δ) / α was 1.0, and (θ / (ε+ζ+η)) was 4.2.

[0063] [Example 11] The target fluorine-containing vinyl compound salt (5.1) was produced in the same manner as in Example 1, except that DMSO was changed to SFL (2.55 g). 19 F-NMR analysis confirmed the production of a fluorine-containing vinyl compound salt (5.1) (production amount: 0.81 g, product mass: 2.71 mmol, production rate: 75.8%). In this example, (β+γ+δ) / α was 1.0, and (θ / (ε+ζ+η)) was 4.2.

[0064] [Example 12] The target fluorine-containing vinyl compound salt (5.1) was produced in the same manner as in Example 1, except that DMSO was changed to TEG (2.55 g). 19 F-NMR analysis confirmed the production of a fluorine-containing vinyl compound salt (5.1) (production amount: 0.73 g, product mass: 2.45 mmol, production rate: 68.5%). In this example, (β+γ+δ) / α was 1.0, and (θ / (ε+ζ+η)) was 4.2.

[0065] [Example 13] The target fluorine-containing vinyl compound salt (7) was produced in the same manner as in Example 1, except that DMSO was changed to ADN (2.55 g). 19 F-NMR analysis confirmed the production of a fluorine-containing vinyl compound salt (5.1) (production amount: 0.75 g, product mass: 2.49 mmol, production rate: 69.8%). In this example, (β+γ+δ) / α was 1.0, and (θ / (ε+ζ+η)) was 4.2.

[0066] [Example 14] A stirrer and P3N (2.87 g, 17.5 mmol) were placed in a test tube (Radley Discovery Technologies, RP98059, RP98062), and the tube was placed in a heating / cooling stirrer (Tokyo Rikakikai Co., Ltd., PPM-5512 type, cooling water was circulated from the outside when cooling). After vacuuming, the heating / cooling stirrer was set to 100°C and dried for 1 hour. The test tube was placed in a nitrogen atmosphere, and then cooled to room temperature. DMSO (12.1 g) was placed in the test tube, stirred, and then the heating / cooling stirrer was set to 60°C. After the heating / cooling stirrer reached 60°C, the fluorine-containing cyclic compound (1.1) (1.00 g, 3.57 mmol) was dropped and stirred for 1 hour. After cooling to room temperature, BTF (0.1 g) for analysis was added, stirred, and filtered with a chromatodisc (GL Sciences, pore size 0.2 μm), and the obtained filtrate was 19 F-NMR analysis revealed that a fluorine-containing vinyl compound salt (5.1) was produced (amount produced: 0.77 g, product mass: 2.57 mmol, production rate: 72.1%). In this embodiment, (β+γ+δ) / α was 4.9, and (θ / (ε+ζ+η)) was 4.2.

[0067] [Example 15] The target fluorine-containing vinyl compound salt (5.1) was produced in the same manner as in Example 1, except that the amount of DMSO was changed to 5.73 g. 19 F-NMR analysis confirmed the production of a fluorine-containing vinyl compound salt (5.1) (production amount: 0.82 g, product mass: 2.72 mmol, production rate: 76.2%). In this example, (β+γ+δ) / α was 1.0, and (θ / (ε+ζ+η)) was 9.5.

[0068] [Comparative Example 1] The fluorine-containing cyclic compound (1.1) was reacted in the same manner as in Example 1, except that P3N was changed to CN2 (0.39 g, 3.68 mmol). 19 As a result of F-NMR analysis, the fluorine-containing vinyl compound salt (5.1) was not detected. In addition, in this comparative example, (β+γ+δ) / α was 1.0, and (θ / (ε+ζ+η)) was 6.5.

[0069] [Comparative Example 2] The fluorine-containing cyclic compound (1.1) was reacted in the same manner as in Example 1, except that P3N was changed to RN2 (0.52 g, 3.68 mmol). 19 As a result of F-NMR analysis, no fluorine-containing vinyl compound salt (5.1) was detected. In addition, in this comparative example, (β+γ+δ) / α was 1.0, and (θ / (ε+ζ+η)) was 4.9.

[0070] [Comparative Example 3] The fluorine-containing cyclic compound (1.1) was reacted in the same manner as in Example 1, except that P3N was changed to NN1 (0.31 g, 3.68 mmol). 19 As a result of F-NMR analysis, the fluorine-containing vinyl compound salt (5.1) was not detected. In addition, in this comparative example, (β+γ+δ) / α was 1.0, and (θ / (ε+ζ+η)) was 8.2.

[0071] [Comparative Example 4] The fluorine-containing cyclic compound (1.1) was reacted in the same manner as in Example 1, except that the amount of CN2 was changed to 1.85 g (17.5 mmol) and the amount of DMSO was changed to 12.1 g. 19 As a result of F-NMR analysis, the fluorine-containing vinyl compound salt (5.1) was not detected. In addition, in this comparative example, (β+γ+δ) / α was 4.9, and (θ / (ε+ζ+η)) was 6.5. [Industrial Applicability]

[0072] According to the present invention, a fluorine-containing vinyl compound salt (5) can be produced in a good yield from a fluorine-containing cyclic compound (1) by utilizing a phosphate compound (2), a borate compound (3) and / or a silicate compound (4) which are generally available and can be handled stably. Therefore, the present invention can be suitably used in the production of raw materials for various fluorine-containing compounds, ion exchange resins, ion exchange membranes, salt electrolysis membranes, fuel cell membranes, membranes for redox flow batteries, membranes for water electrolysis, etc.

Claims

1. A fluorine-containing cyclic compound (1) represented by the following general formula (1), A method for producing a fluorine-containing vinyl compound salt (5) represented by the following general formula (5), comprising reacting a phosphate compound (2) with one or more salts selected from the group consisting of a borate compound (3) represented by the following general formula (3) and a silicate compound (4) represented by the following general formula (4), wherein the phosphate compound (2) is one or more salts selected from the group consisting of trisodium phosphate, trilithium phosphate, tripotassium phosphate, tetrasodium diphosphate and tetrapotassium diphosphate. The following general formula (1): [Formula 1] (In the above general formula (1), 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.) The following general formula (3): [chemical 2] (In the above general formula (3), M 4 is Li or Na.) The following general formula (4): [C3] (In the above general formula (4), M 5 is Na.) The following general formula (5): [C4] (In the above general formula (5), 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.)

2. The method for producing a fluorine-containing vinyl compound salt (5) according to claim 1, wherein a ratio ((β+γ+δ) / α) of the sum of the amount of substance (β) of the phosphate compound (2), the amount of substance (γ) of the borate compound (3) and the amount of substance (δ) of the silicate compound (4) to the amount of substance (α) of the fluorine-containing cyclic compound (1) is 0.5 to 10.

3. A method for producing a fluorine-containing vinyl compound salt (5) according to claim 1 or 2, comprising reacting the fluorine-containing cyclic compound (1) with the phosphate compound (2), the borate compound (3) and / or the silicate compound (4) in the presence of one or more additives selected from the group consisting of dimethyl sulfoxide, N,N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, sulfolane, tetraethylene glycol dimethyl ether and adiponitrile.

4. The method for producing a fluorine-containing vinyl compound salt (5) according to claim 3, wherein a ratio (θ / (ε+ζ+η)) of the mass (θ) of the additive to the sum of the mass (ε) of the phosphate compound (2), the mass (ζ) of the borate compound (3), and the mass (η) of the silicate compound (4) is 0.5 to 100.

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