Method for producing fluorine-containing ester compound, and composition

Abstract

Disclosed is a method for producing a fluorine-containing ester compound, the method comprising fluorination of an ester compound having at least one atom that can be fluorinated in a liquid that contains the ester compound, wherein: the liquid additionally contains at least one compound that is selected from the group consisting of a compound having a hydroxyl group, a compound having a carboxy group and sodium fluoride; and relative to 100 parts by mass of the ester compound, the content of the compound having a hydroxyl group is 0.5 part by mass or less, the content of the compound having a carboxy group is 2.0 parts by mass or less and the content of the sodium fluoride is 2.0 parts by mass or less.

Description

Method for producing fluorine-containing ester compound and composition

[0001] The present disclosure relates to a method for producing a fluorine-containing ester compound and a composition thereof.

[0002] Many fluorine-containing ester compounds are industrially useful, and various production methods have been developed. For example, Patent Document 1 describes a method for producing a fluorine-containing ester compound by supplying fluorine gas into a liquid containing an ester compound obtained by reacting a compound having a hydroxyl group with a carboxylic acid halide to fluorinate the ester compound.

[0003] WO 2000 / 056694

[0004] When an ester compound is produced by reacting a compound having a hydroxyl group with a carboxylic acid halide, an unreacted compound having a hydroxyl group may remain, or a compound having a carboxyl group may be produced by the reaction of the carboxylic acid halide. In other words, a composition containing an ester compound obtained by the reaction of a compound having a hydroxyl group with a carboxylic acid halide may contain impurities such as a compound having a hydroxyl group or a compound having a carboxyl group. Furthermore, when sodium fluoride is used as a catalyst in the process of producing an ester compound, sodium fluoride may remain as an impurity in the composition containing the obtained ester compound. When an ester compound is fluorinated in a liquid containing a composition containing these impurities, the presence of these impurities in the liquid may affect the yield of the target product in the fluorination reaction.

[0005] An object of one embodiment of the present invention is to provide a method for producing a fluorine-containing ester compound, which allows the target fluorine-containing ester compound to be obtained in high yield, and a composition thereof.

[0006] The present disclosure includes the following aspects: <1> A method for producing a fluorinated ester compound, comprising fluorinating an ester compound having at least one fluorinatable atom in a liquid containing the ester compound, wherein the liquid further contains at least one selected from the group consisting of a compound having a hydroxyl group, a compound having a carboxy group, and sodium fluoride, and wherein the content of the compound having a hydroxyl group is 0.5 parts by mass or less, the content of the compound having a carboxy group is 2.0 parts by mass or less, and the content of the sodium fluoride is 2.0 parts by mass or less, relative to 100 parts by mass of the ester compound. <2> The method for producing a fluorinated ester compound according to <1>, wherein the ester compound contains an ester compound having an ether bond, and the liquid further contains hydrogen fluoride, and the content of the hydrogen fluoride is 3.0 parts by mass or less, relative to 100 parts by mass of the ester compound. <3> The method for producing a fluorine-containing ester compound according to <1>, wherein at least one selected from the group consisting of the content of the compound having a hydroxyl group, the content of the compound having a carboxy group, and the content of the sodium fluoride is 0.01 parts by mass or more relative to 100 parts by mass of the ester compound. <4> The method for producing a fluorine-containing ester compound according to <2>, wherein at least one selected from the group consisting of the content of the compound having a hydroxyl group, the content of the compound having a carboxy group, the content of the sodium fluoride, and the content of the hydrogen fluoride is 0.01 parts by mass or more relative to 100 parts by mass of the ester compound. <5> The method for producing a fluorine-containing ester compound according to any one of <1> to <4>, wherein the ester compound comprises at least one selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2): Ａ１ -O-(C=O)-R Ｂ１ …(1) R Ｂ２ -(C=O)-OR Ａ２ -O-(C=O)-R Ｂ３ ... (2) In formulas (1) and (2), R Ａ１ , R Ｂ１ , R Ｂ２ , and R Ｂ３are each independently a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogeno (heteroatom-containing monovalent saturated hydrocarbon) group; R Ａ２ <6> The method for producing a fluorine-containing ester compound according to any one of <1> to <5>, wherein R is a divalent saturated hydrocarbon group, a halogeno divalent saturated hydrocarbon group, a heteroatom-containing divalent saturated hydrocarbon group, or a halogeno (heteroatom-containing divalent saturated hydrocarbon) group. <6> The method for producing a fluorine-containing ester compound according to any one of <1> to <5>, wherein the compound having a hydroxyl group includes at least one selected from the group consisting of compounds represented by the following formula (3) and compounds represented by the following formula (4): Ａ３ -OH...(3) HO-R Ａ４ —OH (4) In formulas (3) and (4), R Ａ３ is a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogeno (heteroatom-containing monovalent saturated hydrocarbon) group; R Ａ４ <7> R in the formula (3) is a divalent saturated hydrocarbon group, a halogeno divalent saturated hydrocarbon group, a heteroatom-containing divalent saturated hydrocarbon group, or a halogeno (heteroatom-containing divalent saturated hydrocarbon) group. Ａ３ is R in the formula (1). Ａ１ and R in the formula (4) Ａ４ is R in the formula (2). Ａ２ <8> The method for producing a fluorine-containing ester compound according to any one of <1> to <7>, wherein the compound having a carboxy group includes a compound represented by the following formula (5): Ｂ４ -(C=O)-OH...(5) In formula (5), R Ｂ４ <9> R in the formula (5) is a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogeno (heteroatom-containing monovalent saturated hydrocarbon) group. Ｂ４ is R in the formula (1). Ｂ１ Or R in the formula (2) Ｂ２ The method for producing a fluorine-containing ester compound according to <8>, wherein the compound is the same as

[0007] <10> A composition comprising an ester compound having at least one fluorinatable atom and at least one selected from the group consisting of a compound having a hydroxyl group, a compound having a carboxyl group, and sodium fluoride, wherein the amount of the compound having a hydroxyl group is 0.5 parts by mass or less, the amount of the compound having a carboxyl group is 2.0 parts by mass or less, and the amount of the sodium fluoride is 2.0 parts by mass or less, per 100 parts by mass of the ester compound. <11> The composition according to <10>, wherein the ester compound includes an ester compound having an ether bond, and the composition further contains hydrogen fluoride, wherein the amount of the hydrogen fluoride is 3.0 parts by mass or less, per 100 parts by mass of the ester compound. <12> The composition according to <10>, wherein the amount of at least one selected from the group consisting of the compound having a hydroxyl group, the compound having a carboxyl group, and the sodium fluoride is 0.01 parts by mass or more, per 100 parts by mass of the ester compound. <13> The composition according to <11>, wherein the content of at least one selected from the group consisting of the compound having a hydroxyl group, the compound having a carboxyl group, the sodium fluoride, and the hydrogen fluoride is 0.01 parts by mass or more per 100 parts by mass of the ester compound. <14> The composition according to any one of <10> to <13>, wherein the ester compound includes at least one selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2): The compound having a hydroxyl group includes at least one selected from the group consisting of a compound represented by the following formula (3) and a compound represented by the following formula (4): The compound having a carboxyl group includes a compound represented by the following formula (5): Ａ１ -O-(C=O)-R Ｂ１ …(1) R Ｂ２ -(C=O)-OR Ａ２ -O-(C=O)-R Ｂ３ …(2) R Ａ３ -OH...(3) HO-R Ａ４ -OH ... (4) R Ｂ４ -(C=O)-OH...(5) In formulas (1) to (5), R Ａ１, R Ａ３ , R Ｂ１ , R Ｂ２ , R Ｂ３ , and R Ｂ４ are each independently a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogeno (heteroatom-containing monovalent saturated hydrocarbon) group; R Ａ２ and R Ａ４ are each independently a divalent saturated hydrocarbon group, a halogenated divalent saturated hydrocarbon group, a heteroatom-containing divalent saturated hydrocarbon group, or a halogenated (heteroatom-containing divalent saturated hydrocarbon) group. Ａ３ is R in the formula (1). Ａ１ and R in the formula (4) Ａ４ is R in the formula (2). Ａ２ and R in the formula (5) Ｂ４ is R in the formula (1). Ｂ１ Or R in the formula (2) Ｂ２ The composition according to <14>, which is the same as

[0008] According to the present disclosure, there are provided a method for producing a fluorine-containing ester compound and a composition by which the target fluorine-containing ester compound can be obtained in high yield.

[0009] Hereinafter, modes for carrying out embodiments of the present disclosure will be described in detail. However, the embodiments of the present disclosure are not limited to the following embodiments. In the following embodiments, components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and they do not limit the embodiments of the present disclosure.

[0010] In the present disclosure, a numerical range indicated using "to" means a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the Examples. In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. In the present disclosure, when multiple substances corresponding to each component are present, the amount of each component refers to the total amount of multiple substances unless otherwise specified. In the present disclosure, when a compound is represented by a specific formula (X), the compound represented by the formula (X) may be referred to as compound (X).

[0011] [Method for producing fluorine-containing ester compound] A method for producing a fluorine-containing ester compound according to an embodiment of the present disclosure includes fluorinating an ester compound having at least one fluorinatable atom in a liquid containing the ester compound, wherein the liquid further contains at least one selected from the group consisting of a compound having a hydroxyl group, a compound having a carboxyl group, and sodium fluoride, and the content of the compound having a hydroxyl group is 0.5 parts by mass or less, the content of the compound having a carboxyl group is 2.0 parts by mass or less, and the content of the sodium fluoride is 2.0 parts by mass or less, relative to 100 parts by mass of the ester compound. Hereinafter, the compound having a hydroxyl group will be referred to as an "OH compound," the content of the OH compound relative to 100 parts by mass of the ester compound in the liquid will be referred to as the "OH compound amount," the compound having a carboxyl group will be referred to as the "carboxylic acid compound," the content of the carboxylic acid compound relative to 100 parts by mass of the ester compound in the liquid will be referred to as the "carboxylic acid amount," sodium fluoride will be referred to as "NaF," and the content of sodium fluoride relative to 100 parts by mass of the ester compound in the liquid will be referred to as the "NaF amount."

[0012] As described above, a composition containing an ester compound obtained by the reaction of an OH compound with a carboxylic acid halide may contain, as impurities, an unreacted OH compound, a carboxylic acid compound produced by the reaction of the unreacted carboxylic acid halide, etc. Furthermore, when NaF is used as a catalyst in the process of producing the ester compound, NaF may remain as an impurity in the resulting composition containing the ester compound.

[0013] When an ester compound is fluorinated in a liquid containing a composition containing these impurities, the presence of these impurities in the liquid may affect the yield of the target product in the fluorination reaction. Specifically, when a fluorination reaction is carried out in the presence of an OH compound, the OH compound and fluorine react with a large amount of reaction heat, and the reaction heat may decompose the ester compound, which is the raw material of the fluorination reaction, and the fluorine-containing ester compound, which is the target product. If decomposition of the raw material and the target product occurs frequently, the yield of the target product may decrease. Similarly, when a fluorination reaction is carried out in the presence of a carboxylic acid compound, the carboxylic acid compound and fluorine react with a large amount of reaction heat, and the decomposition of the raw material and the target product may occur frequently, and the yield of the target product may decrease. Furthermore, when a fluorination reaction is carried out in the presence of NaF, the action of NaF may cause decomposition of the ester bond of the raw material ester compound and the target fluorine-containing ester compound. If decomposition of the raw material and the target product occurs frequently, the yield of the target product may decrease.

[0014] In contrast, in the above-mentioned method for producing a fluorinated ester compound, the amount of OH compound is 0.5 parts by mass or less, the amount of carboxylic acid is 2.0 parts by mass or less, and the amount of NaF is 2.0 parts by mass or less, and therefore it is presumed that decomposition of the raw materials and the target product accompanying the fluorination reaction of the ester compound is suppressed, resulting in an increased yield of the target product.

[0015] Furthermore, in the above-mentioned method for producing a fluorine-containing ester compound, the liquid containing the ester compound further contains at least one selected from the group consisting of OH compounds, carboxylic acid compounds, and sodium fluoride. Therefore, the yield of the target product is high. The reason for this is unclear, but is presumed to be as follows. It is thought that the liquid containing at least one selected from the group consisting of OH compounds, carboxylic acid compounds, and sodium fluoride slightly progresses the decomposition reaction of at least one of the raw material and the target product, generating radicals. It is presumed that the slightly generated radicals facilitate the fluorination reaction of the ester compound.

[0016] The method for incorporating at least one compound selected from the group consisting of an OH compound, a carboxylic acid compound, and sodium fluoride into a liquid and adjusting the amount of the OH compound, the amount of carboxylic acid, and the amount of NaF to fall within the above-mentioned ranges is not particularly limited. When an ester compound is produced by reacting an OH compound with a carboxylic acid halide, a composition containing an OH compound, an carboxylic acid, and NaF in an amount greater than the above-mentioned ranges is often obtained. In this case, the OH compound, the carboxylic acid compound, and the sodium fluoride may be removed from the composition containing an OH compound, an carboxylic acid, and NaF in an amount greater than the above-mentioned ranges. This removal process results in a composition containing at least one compound selected from the group consisting of an OH compound, a carboxylic acid compound, and sodium fluoride, and having an OH compound, an carboxylic acid, and NaF in an amount within the above-mentioned ranges. A fluorination reaction may then be carried out in the liquid containing the resulting composition.

[0017] The method for removing OH compounds, carboxylic acid compounds, and sodium fluoride from the composition is not particularly limited, and examples thereof include removal using an adsorbent, removal by filtration, removal by vacuum distillation, removal by centrifugation, removal by extraction, and combinations thereof. In removal using an adsorbent, when the adsorbent is a particulate solid, for example, at least a portion of the OH compounds, carboxylic acid compounds, and sodium fluoride is removed from the composition by passing the composition through a packed tower filled with dry adsorbent. Examples of adsorbents include silica, zeolite, activated carbon, activated alumina, etc., and among these, silica is preferred from the viewpoint of adsorption capacity. Examples of silica include spherical silica gel (product name: M.S.GEL, product number: D75-60A(N), manufacturer: AGC Si-Tech Co., Ltd.).

[0018] The amounts of OH compounds, carboxylic acids, and NaF in the composition may be controlled by adjusting the amounts of OH compounds, carboxylic acids, and sodium fluoride removed, or by adding NaF separately after removal. When an OH compound is added separately to the composition, the OH compound added separately may be the same as or different from the OH compound used in producing the ester compound. When a carboxylic acid compound is added separately to the composition, the carboxylic acid compound added separately may be the same as or different from the carboxylic acid compound obtained by the reaction of the carboxylic acid halide used in producing the ester compound. In other words, when an OH compound is contained in the liquid used to fluorinate an ester compound, the structure other than the hydroxyl group in the OH compound may be the same as or different from the alcohol residue of the ester compound. When a carboxylic acid compound is contained in the liquid used to fluorinate an ester compound, the structure other than the carboxy group in the carboxylic acid compound may be the same as or different from the carboxylic acid residue of the ester compound.

[0019] In one embodiment of the present disclosure, from the viewpoint of obtaining a high yield of the target product, at least one selected from the group consisting of the amount of OH compounds, the amount of carboxylic acid, and the amount of NaF is preferably 0.01 parts by mass or more. Some of the amounts of OH compounds, carboxylic acids, and NaF may be 0.01 parts by mass or more, or all of the amounts of OH compounds, carboxylic acids, and NaF may be 0.01 parts by mass or more.

[0020] In one embodiment of the present disclosure, the ester compound serving as a raw material for the fluorination reaction may include an ester compound having an ether bond. When the ester compound includes an ester compound having an ether bond, the liquid further contains hydrogen fluoride, and the content of the hydrogen fluoride per 100 parts by mass of the ester compound contained in the liquid is preferably 3.0 parts by mass or less. Hereinafter, hydrogen fluoride will also be referred to as "HF," and the content of HF per 100 parts by mass of the ester compound in the liquid will also be referred to as the "HF amount."

[0021] When an ester compound is produced by reacting an OH compound with a carboxylic acid halide, HF is generated as a by-product. Therefore, a composition containing an ester compound obtained by reacting an OH compound with a carboxylic acid halide may contain HF as an impurity. When a fluorination reaction of an ester compound having an ether bond is carried out in the presence of HF, the ether bonds of the raw material ester compound having an ether bond and the target fluorine-containing ester compound having an ether bond may be decomposed by the action of HF. Furthermore, if the decomposition of ether bonds occurs frequently, the yield of the target product decreases. Therefore, it is presumed that by setting the amount of HF within the above range, the decomposition of ether bonds accompanying the fluorination reaction of the ester compound is suppressed, thereby increasing the yield of the target product. Furthermore, it is presumed that the inclusion of HF in the liquid facilitates the fluorination reaction of the ester compound due to radicals generated by the decomposition reaction of the ether bond, thereby increasing the yield of the target product.

[0022] The method for adjusting the amount of HF to the above range while containing HF in the liquid is not particularly limited. When an ester compound is produced by reacting an OH compound with an carboxylic acid halide, a composition having an HF amount greater than the above range is often obtained. In this case, HF may be removed from a composition having an HF amount greater than the above range to obtain a composition containing HF and having an HF amount within the above range, and a fluorination reaction may be carried out in a liquid containing the obtained composition. The amount of HF in the composition may be controlled by adjusting the amount of HF removed, or by separately adding HF after removal. Methods for removing HF from the composition include removal by distillation under reduced pressure and removal using the aforementioned adsorbent.

[0023] When the ester compound contains an ester compound having an ether bond, from the viewpoint of obtaining a high yield of the target product, it is preferable that at least one selected from the group consisting of an OH compound amount, a carboxylic acid amount, a NaF amount, and a HF amount is 0.01 parts by mass or more. A part of the OH compound amount, the carboxylic acid amount, the NaF amount, and the HF amount may be 0.01 parts by mass or more, or all of the OH compound amount, the carboxylic acid amount, the NaF amount, and the HF amount may be 0.01 parts by mass or more.

[0024] <Liquid> The liquid contains at least an ester compound having at least one fluorinatable atom and at least one compound selected from the group consisting of an OH compound, a carboxylic acid compound, and sodium fluoride, and may further contain a solvent, other additives, and the like, as necessary.

[0025] (Ester Compound) The ester compound is not particularly limited as long as it is an organic compound having at least one fluorinable atom and an ester bond. The ester compound may have only one fluorinable atom or may have two or more fluorinable atoms. The number of fluorinable atoms contained in one molecule of the ester compound is, for example, 1 to 1,000, preferably 1 to 500, and more preferably 1 to 100. The ester compound may have only one ester bond (i.e., —O—(C═O)—), or may have two or more ester bonds. From the viewpoint of availability, the number of ester bonds contained in the ester compound is preferably one or two. That is, the ester compound is preferably a monoester compound or a diester compound.

[0026] Examples of the fluorinable atom include a hydrogen atom, a bromine atom, and an iodine atom, and among these, a hydrogen atom is preferred. The ester compound preferably has a hydrogen atom as a fluorinable atom.

[0027] Examples of the ester compound include a compound represented by the following formula (1) and a compound represented by the following formula (2). Ａ１ -O-(C=O)-R Ｂ１ …(1) R Ｂ２ -(C=O)-OR Ａ２ -O-(C=O)-R Ｂ３ …(2)

[0028] In formulas (1) and (2), R Ａ１ , R Ｂ１ , R Ｂ２ , and R Ｂ３ are each independently a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogeno (heteroatom-containing monovalent saturated hydrocarbon) group; R Ａ２ is a divalent saturated hydrocarbon group, a halogeno divalent saturated hydrocarbon group, a heteroatom-containing divalent saturated hydrocarbon group, or a halogeno (heteroatom-containing divalent saturated hydrocarbon) group.

[0029] In the present disclosure, the "monovalent saturated hydrocarbon group" may be any of a linear alkyl group, a branched alkyl group, and a cycloalkyl group. The "divalent saturated hydrocarbon group" may be any of a linear alkylene group, a branched alkylene group, and a cycloalkylene group. The linear alkyl group, branched alkyl group, linear alkylene group, and branched alkylene group may contain an alicyclic structure.

[0030] In the present disclosure, the term "halogeno" means that one or more hydrogen atoms present in a group are substituted with at least one halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Hydrogen atoms may or may not be present in the group.

[0031] In the present disclosure, the term "halogeno monovalent saturated hydrocarbon group" refers to a group in which one or more hydrogen atoms present in a monovalent saturated hydrocarbon group have been substituted with a halogen atom. The term "halogeno divalent saturated hydrocarbon group" refers to a group in which one or more hydrogen atoms present in a divalent saturated hydrocarbon group have been substituted with a halogen atom.

[0032] In the present disclosure, "heteroatom" means an atom other than carbon or hydrogen atoms, and includes, for example, nitrogen, oxygen, and sulfur atoms.

[0033] In the present disclosure, the term "heteroatom-containing monovalent saturated hydrocarbon group" refers to a monovalent saturated hydrocarbon group that contains a divalent heteroatom or a divalent group containing a heteroatom. The term "heteroatom-containing divalent saturated hydrocarbon group" refers to a divalent saturated hydrocarbon group that contains a divalent heteroatom or a divalent group containing a heteroatom. Examples of divalent heteroatoms include -O- and -S-. Furthermore, examples of divalent groups containing heteroatoms include -NH-, -C(=O)-, and -SO. ２ - are listed.

[0034] In this disclosure, the term "halogeno (heteroatom-containing monovalent saturated hydrocarbon) group" refers to a group in which one or more hydrogen atoms in the above heteroatom-containing monovalent saturated hydrocarbon group have been substituted with halogen atoms. The term "halogeno (heteroatom-containing divalent saturated hydrocarbon group) group" refers to a group in which one or more hydrogen atoms in the above heteroatom-containing divalent saturated hydrocarbon group have been substituted with halogen atoms.

[0035] In formula (1), R Ａ１ and R Ｂ１ Preferably, at least one of R Ａ２ , R Ｂ２ , and R Ｂ３ It is preferred that at least one selected from the group consisting of contains a hydrogen atom.

[0036] [R Ａ１ ] In formula (1), R Ａ１ is a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogeno(heteroatom-containing monovalent saturated hydrocarbon) group.

[0037] R Ａ１ Examples of the monovalent saturated hydrocarbon group represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, and a cyclohexyl group.

[0038] R Ａ１ The halogeno monovalent saturated hydrocarbon group represented by the following formula is preferably a halogenoalkyl group: The halogen atom contained in the halogeno monovalent saturated hydrocarbon group is preferably a fluorine atom, a chlorine atom, or a bromine atom, and more preferably a fluorine atom.

[0039] R Ａ１ The heteroatom-containing monovalent saturated hydrocarbon group represented by the formula (I) is preferably a monovalent saturated hydrocarbon group containing an ethereal oxygen atom (that is, —O—), and more preferably an alkyl group containing an ethereal oxygen atom.

[0040] R Ａ１The halogeno (heteroatom-containing monovalent saturated hydrocarbon) group represented by the formula (I) is preferably a halogeno (heteroatom-containing alkyl group). The halogen atom contained in the halogeno (heteroatom-containing monovalent saturated hydrocarbon) group is preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogeno (heteroatom-containing monovalent saturated hydrocarbon) group is preferably a halogeno monovalent saturated hydrocarbon group containing an ethereal oxygen atom, and more preferably a halogenoalkyl group containing an ethereal oxygen atom.

[0041] R Ａ１ The number of carbon atoms is preferably 1 to 200, more preferably 3 to 100, from the viewpoint of excellent solubility in a solvent described later.

[0042] Among them, from the viewpoint of excellent solubility in liquid, R Ａ１ is preferably represented by the following formula (A1): Ａ１ R preferably further has an ether bond, and more preferably contains at least one selected from the group consisting of a polyether chain and a fluoropolyether chain. １１ O-(R １２ O) ｍ１ -R １３ - ... (A1)

[0043] In formula (A1), R １１ is an alkyl group which may have a fluorine atom, and R １２ are each independently an alkylene group having 1 to 6 carbon atoms which may have a fluorine atom, and R １３ represents an alkylene group having 1 to 6 carbon atoms which may have a fluorine atom, and m1 represents an integer of 0 to 500.

[0044] In formula (A1), R １１ Examples of the alkyl group include alkyl groups and fluoroalkyl groups.

[0045] R １１ The number of carbon atoms of is preferably 1 to 100, more preferably 1 to 50, even more preferably 1 to 10, and particularly preferably 1 to 6, from the viewpoint of excellent solubility in a solvent described later.

[0046] R １１The alkyl group represented by the formula (I) may be a linear alkyl group, a branched alkyl group, or an alkyl group having a ring structure.

[0047] R １１ The fluoroalkyl group represented by the formula (I) may be a straight-chain fluoroalkyl group, a branched-chain fluoroalkyl group, or a fluoroalkyl group having a ring structure.

[0048] Among them, R １１ is preferably an alkyl group, more preferably a linear alkyl group, and even more preferably a linear alkyl group having 1 to 6 carbon atoms.

[0049] In formula (A1), -(R １２ O) ｍ１ - is preferably represented by the following formula (A2): -[(R ｆ１ O) ｋ１ (R ｆ２ O) ｋ２ (R ｆ３ O) ｋ３ (R ｆ４ O) ｋ４ (R ｆ５ O) ｋ５ (R ｆ６ O) ｋ６ ]- …(A2) However, R ｆ１ is a fluoroalkylene group having 1 carbon atom, and R ｆ２ is a fluoroalkylene group having 2 carbon atoms, R ｆ３ is a fluoroalkylene group having 3 carbon atoms, R ｆ４ is a fluoroalkylene group having 4 carbon atoms, R ｆ５ is a fluoroalkylene group having 5 carbon atoms, R ｆ６ is a fluoroalkylene group having 6 carbon atoms. k1, k2, k3, k4, k5, and k6 each independently represent an integer of 0 or 1 or more, and k1+k2+k3+k4+k5+k6 is an integer of 0 to 500.

[0050] From the viewpoint of excellent solubility in liquid, k1+k2+k3+k4+k5+k6 is preferably an integer of 1 to 500, more preferably an integer of 1 to 300, still more preferably an integer of 5 to 200, and particularly preferably an integer of 10 to 150.

[0051] In addition, (R ｆ１ O) ~ (R ｆ６ O) may be bonded in any order. k1 to k6 in formula (A2) are each ｆ１ O) ~ (R ｆ６ O), and does not represent the arrangement. For example, (R ｆ５ O) ｋ５ is (R ｆ５ O) is k5, and (R ｆ５ O) ｋ５ Similarly, (R ｆ１ O) ~ (R ｆ６ The order of description of each unit does not represent the bonding order of the units.

[0052] R ｆ３ ~R ｆ６ In the above formula, the fluoroalkylene group may be a linear fluoroalkylene group, a branched fluoroalkylene group, or a fluoroalkylene group having a ring structure.

[0053] R ｆ１ Specific examples of the group include -CF ２ - and -CHF-.

[0054] R ｆ２ Specific examples of the group include -CF ２ CF ２ -, -CF ２ CHF-, -CHFCF ２ -, -CHFCHF-, -CH ２ CF ２ - and -CH ２ Examples include CHF-.

[0055] R ｆ３ Specific examples of the group include -CF ２ CF ２ CF ２ -, -CF ２ CHFCF２ -、-CF ２ CH ２ CF ２ -、-CHFCF ２ CF ２ -、-CHFCHFCF ２ -、-CHFCHFCHF-、-CHFCH ２ CF ２ -、-CH ２ CF ２ CF ２ -、-CH ２ CHFCF ２ -、-CH ２ CH ２ CF ２ -、-CH ２ CF ２ CHF-、-CH ２ CHFCHF-、-CH ２ CH ２ CHF-、-CF(CF ３ )-CF ２ -、-CF(CHF ２ )-CF ２ -、-CF(CH ２ F)-CF ２ -、-CF(CH ３ )-CF ２ -、-CF(CF ３ )-CHF-、-CF(CHF ２ )-CHF-、-CF(CH ２ F)-CHF-、-CF(CH ３ )-CHF-、-CF(CF ３ )-CH ２ -、-CF(CHF ２ )-CH ２ -、-CF(CH ２ F)-CH ２ -、-CF(CH ３ )-CH ２ -、-CH(CF ３ )-CF ２ -、-CH(CHF ２ )-CF ２ -、-CH(CH ２ F)-CF ２ -、-CH(CH ３ )-CF ２ -、-CH(CF ３ )-CHF-、-CH(CHF２ ) -CHF-, -CH(CH ２ F)-CHF-, -CH(CH ３ )-CHF-, -CH(CF ３ )-CH ２ -, -CH(CHF ２ )-CH ２ -, and -CH(CH ２ F)-CH ２ - are included.

[0056] R ｆ４ Specific examples of -CF ２ CF ２ CF ２ CF ２ -, -CF ２ CF ２ CF ２ CHF-, -CF ２ CF ２ CF ２ CH ２ -, -CF ２ CHFCF ２ CF ２ -, -CHFCHFCF ２ CF ２ -, -CH ２ CHFCF ２ CF ２ -, -CF ２ CH ２ CF ２ CF ２ -, -CHFCH<s ２ CF ２ CF ２ -, -CH ２ CH ２ CF ２ CF ２ -, -CHFCF ２ CHFCF ２ -, -CH ２ CF ２ CHFCF ２ -, -CF ２ CHFCHFCF ２ -, -CHFCHFCHFCF ２ -, -CH ２ CHFCHFCF ２ -, -CF ２ CH ２ CHFCF ２ -, -CHFCH２ CHFCF ２ —, —CH ２ CH ２ CHFCF ２ —, —CF ２ CH ２ CH ２ CF ２ —, —CHFCH ２ CH ２ CF ２ —, —CH ２ CH ２ CH ２ CF ２ —, —CHFCH ２ CH ２ CHF—, —CH ２ CH ２ CH ２ CHF—, and —cycloC ４ F ６ — are included.

[0057] R ｆ５ Specific examples of —CF ２ CF ２ CF ２ CF ２ CF ２ —, —CHFCF ２ CF ２ CF ２ CF ２ —, —CH ２ CHFCF ２ CF ２ CF ２ —, —CF ２ CHFCF ２ CF ２ CF ２ —, —CHFCHFCF ２ CF ２ CF ２ —, —CF ２ CH ２ CF ２ CF ２ CF ２ —, —CHFCH ２ CF ２ CF ２ CF ２ —, —CH ２ CH ２ CF ２ CF ２ CF ２ —, —CF２ CF ２ CHFCF ２ CF ２ -, -CHFCF ２ CHFCF ２ CF ２ -, -CH ２ CF ２ CHFCF ２ CF ２ -, -CH ２ CF ２ CF ２ CF ２ CH ２ -, and -cycloC ５ F ８ - are listed.

[0058] R ｆ６ Specific examples of the group include -CF ２ CF ２ CF ２ CF ２ CF ２ CF ２ -, -CF ２ CF ２ CHFCHFCF ２ CF ２ -, -CHFCF ２ CF ２ CF ２ CF ２ CF ２ -, -CHFCHFCHFCHFCHFCHF-, -CHFCF ２ CF ２ CF ２ CF ２ CH ２ -, -CH ２ CF ２ CF ２ CF ２ CF ２ CH ２ -, and -cycloC ６ F １０ Here, -cycloC ４ F ６ - means a perfluorocyclobutanediyl group, and a specific example thereof is a perfluorocyclobutane-1,2-diyl group. ５ F ８- means a perfluorocyclopentanediyl group, and a specific example thereof is a perfluorocyclopentane-1,3-diyl group. ６ F １０ "-" means a perfluorocyclohexanediyl group, and a specific example thereof is a perfluorocyclohexane-1,4-diyl group.

[0059] Among them, -(R １２ O) ｍ１ - preferably includes at least one selected from the group consisting of structures represented by the following formulas (F1) to (F3), and more preferably includes a structure represented by formula (F2): -(R ｆ１ O) ｋ１ - (R ｆ２ O) ｋ２ -...(F1) -(R ｆ２ O) ｋ２ - (R ｆ４ O) ｋ４ -...(F2) -(R ｆ３ O) ｋ３ - (F3) where the symbols in formulas (F1) to (F3) are the same as those in formula (A2) above.

[0060] In formula (F1) and formula (F2), (R ｆ１ O) and (R ｆ２ O), (R ｆ２ O) and (R ｆ４ O) can be bonded in any order. For example, (R ｆ１ O) and (R ｆ２ O) may be arranged alternately, and (R ｆ１ O) and (R ｆ２ O) may be arranged in blocks or randomly. The same applies to formula (F2). In formula (F1), k1 is preferably 1 to 30, more preferably 1 to 20. Also, k2 is preferably 1 to 30, more preferably 1 to 20. In formula (F2), k2 is preferably 1 to 30, more preferably 1 to 20. Also, k4 is preferably 1 to 30, more preferably 1 to 20. In formula (F3), k3 is preferably 1 to 30, more preferably 1 to 20.

[0061] In formula (A1), R １３As the above, R ｆ１ ~R ｆ６ The same can be mentioned.

[0062] Among them, R １３ is preferably a fluoroalkylene group having 1 to 4 carbon atoms.

[0063] R Ａ１ Specific examples of the structure include the following: * represents the bonding site with —O—, n1 represents an integer of 0 to 60, and n2 represents an integer of 0 to 500. n1 is, for example, 13, and n2 is, for example, 7.

[0064]

[0065] [R Ｂ１ ] In formula (1), R Ｂ１ is a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogeno(heteroatom-containing monovalent saturated hydrocarbon) group.

[0066] R Ｂ１ Examples of the monovalent saturated hydrocarbon group represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, and a cyclohexyl group.

[0067] R Ｂ１ A halogenoalkyl group is preferred as the halogeno monovalent saturated hydrocarbon group represented by the following formula: The halogen atom contained in the halogeno monovalent saturated hydrocarbon group is preferably a fluorine atom, a chlorine atom, or a bromine atom.

[0068] R Ｂ１ The heteroatom-containing monovalent saturated hydrocarbon group represented by the formula (I) is preferably a monovalent saturated hydrocarbon group containing an ethereal oxygen atom (i.e., —O—), and more preferably an alkyl group containing an ethereal oxygen atom. Ｂ１ It is preferable that the alkyl group further has an ether bond.

[0069] R Ｂ１The halogeno (heteroatom-containing monovalent saturated hydrocarbon) group represented by the formula (I) is preferably a halogeno (heteroatom-containing alkyl group). The halogen atom contained in the halogeno (heteroatom-containing monovalent saturated hydrocarbon) group is preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogeno (heteroatom-containing monovalent saturated hydrocarbon) group is preferably a halogeno monovalent saturated hydrocarbon group containing an ethereal oxygen atom, and more preferably a halogenoalkyl group containing an ethereal oxygen atom.

[0070] R Ｂ１ The number of carbon atoms of is preferably 1 to 100, more preferably 2 to 50, and even more preferably 3 to 20, from the viewpoint of excellent solubility in a solvent described below.

[0071] R Ｂ１ In terms of excellent solubility in solvents described below, it is preferable that the compound contains at least one fluorine atom and does not contain a hydrogen atom.

[0072] Among these, from the viewpoint of excellent solubility in solvents described later, R Ｂ１ is preferably represented by the following formula (B1): ２１ O-(R ２２ O) ｍ２ -R ２３ - ... (B1)

[0073] In formula (B1), R ２１ is an alkyl group which may have a fluorine atom, and R ２２ are each independently an alkylene group having 1 to 6 carbon atoms which may have a fluorine atom, and R ２３ represents an alkylene group having 1 to 6 carbon atoms which may have a fluorine atom, and m2 represents an integer of 0 to 20.

[0074] In formula (B1), R ２１ Examples of the alkyl group include alkyl groups and fluoroalkyl groups.

[0075] R ２１ The number of carbon atoms of is preferably 1 to 50, more preferably 1 to 10, and even more preferably 1 to 6, from the viewpoint of excellent solubility in a solvent described later.

[0076] R ２１The alkyl group represented by R may be a linear alkyl group, a branched alkyl group, or an alkyl group having a ring structure. ２１ The fluoroalkyl group represented by the formula (I) may be a straight-chain fluoroalkyl group, a branched-chain fluoroalkyl group, or a fluoroalkyl group having a ring structure.

[0077] Among them, R ２１ is preferably a fluoroalkyl group, more preferably a linear fluoroalkyl group, still more preferably a linear fluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably a linear perfluoroalkyl group having 1 to 6 carbon atoms.

[0078] In formula (B1), -(R ２２ O) ｍ２ - is preferably represented by the above formula (A2).

[0079] In formula (B1), m2 is preferably 0 to 15, more preferably 0 to 10, still more preferably 0 to 4, and particularly preferably 0 to 2.

[0080] In formula (B1), R ２３ As the above, R ｆ１ ~R ｆ６ The same can be mentioned.

[0081] Among them, R ２３ is preferably a fluoroalkylene group having 1 to 3 carbon atoms, more preferably a perfluoroalkylene group having 1 to 3 carbon atoms.

[0082] R Ｂ１ Specific examples of the structure include the following: * represents the bonding site with —O—(C═O)—.

[0083]

[0084] [R Ａ２ ] In formula (2), R Ａ２ is a divalent saturated hydrocarbon group, a halogeno divalent saturated hydrocarbon group, a heteroatom-containing divalent saturated hydrocarbon group, or a halogeno (heteroatom-containing divalent saturated hydrocarbon) group.

[0085] R Ａ２The divalent saturated hydrocarbon group, halogeno divalent saturated hydrocarbon group, heteroatom-containing divalent saturated hydrocarbon group, or halogeno (heteroatom-containing divalent saturated hydrocarbon) group represented by the formula (1) includes R Ａ１ and groups in which one hydrogen atom or one halogen atom has been removed from a halogeno (heteroatom-containing monovalent saturated hydrocarbon) group.

[0086] R Ａ２ The number of carbon atoms is preferably 1 to 200, more preferably 3 to 100, from the viewpoint of excellent solubility in a solvent described later.

[0087] Among these, from the viewpoint of excellent solubility in solvents described later, R Ａ２ is preferably represented by the following formula (A5): Ａ２ -R preferably further has an ether bond, and more preferably contains at least one selected from the group consisting of a polyether chain and a fluoropolyether chain. ３１ O-(R ３２ O) ｍ５ -R ３３ - ... (A5)

[0088] In formula (A5), R ３１ and R ３３ are each independently an alkylene group having 1 to 6 carbon atoms which may have a fluorine atom, and R ３２ are each independently an alkylene group having 1 to 6 carbon atoms which may have a fluorine atom; and m5 is an integer of 0 to 500.

[0089] In formula (A5), R ３１ and R ３３ R in formula (A1) １３ In formula (A5), -(R ３２ O) ｍ５ - is -(R １２ O) ｍ１ - and the same as above.

[0090] R Ａ２Specific examples of the structure include the following: * represents the bonding site with —O—, and n2 represents an integer of 0 to 500.

[0091]

[0092] [R Ｂ２ and R Ｂ３ ] In formula (2), R Ｂ２ and R Ｂ３ are each independently a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogeno (heteroatom-containing monovalent saturated hydrocarbon) group.

[0093] R Ｂ２ or R Ｂ３ The monovalent saturated hydrocarbon group, halogeno monovalent saturated hydrocarbon group, heteroatom-containing monovalent saturated hydrocarbon group, or halogeno (heteroatom-containing monovalent saturated hydrocarbon) group represented by the formula (1) includes R Ｂ１ Examples of such a group include a monovalent saturated hydrocarbon group represented by the following formula:

[0094] Examples of the ester compound include the following compound (T1).

[0095]

[0096] The number average molecular weight of the ester compound is not particularly limited, and may be, for example, 100 to 100,000. From the viewpoint of excellent solubility in liquids, it is preferably 100 to 20,000, more preferably 300 to 10,000, and even more preferably 400 to 6,000. The number average molecular weight of the ester compound is １ H-NMR and １９ It is the number average molecular weight of each molecule calculated from the molecular structure identified by F-NMR.

[0097] From the viewpoint of obtaining a high yield of the target product, the content of the ester compound contained in the liquid is preferably 1 to 100 mass%, more preferably 3 to 100 mass%, even more preferably 5 to 100 mass%, particularly preferably 8 to 70 mass%, and extremely preferably 8 to 50 mass%, relative to the total mass of the liquid.

[0098] The method for producing an ester compound is not particularly limited. For example, an ester compound may be obtained by reacting an OH compound with a carboxylic acid halide in an organic solvent. In producing the ester compound, NaF may be used as a catalyst, if necessary. In the reaction between an OH compound and a carboxylic acid halide, the reaction time is, for example, 0.5 to 100 hours, preferably 0.5 to 50 hours. The reaction temperature is, for example, 0 to 200°C, preferably 0 to 100°C.

[0099] (OH Compound) The liquid may contain an OH compound. When the liquid contains an OH compound, the amount of the OH compound is 0.5 parts by mass or less, as described above. Furthermore, from the viewpoint of increasing the yield of the target product, the amount of the OH compound is preferably 0.01 parts by mass or more. The amount of the OH compound is preferably 0.01 to 0.5 parts by mass.

[0100] The OH compound is not particularly limited as long as it is a compound having a hydroxyl group. The OH compound may have only one hydroxyl group, or may have two or more hydroxyl groups. From the viewpoint of availability, the number of hydroxyl groups contained in the OH compound is preferably one or two. The OH compound may or may not have a fluorinable atom, but preferably has one. The OH compound may have only one fluorinable atom, or may have two or more fluorinable atoms. The number of fluorinable atoms contained in one molecule of the OH compound is, for example, 1 to 1,000, preferably 1 to 500, and more preferably 1 to 100.

[0101] Examples of the OH compound include a compound represented by the following formula (3) and a compound represented by the following formula (4). Ａ３ -OH...(3) HO-R Ａ４ -OH ... (4)

[0102] In formulas (3) and (4), R Ａ３ is a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogeno (heteroatom-containing monovalent saturated hydrocarbon) group; R Ａ４is a divalent saturated hydrocarbon group, a halogeno divalent saturated hydrocarbon group, a heteroatom-containing divalent saturated hydrocarbon group, or a halogeno (heteroatom-containing divalent saturated hydrocarbon) group.

[0103] R Ａ３ The monovalent saturated hydrocarbon group, halogeno monovalent saturated hydrocarbon group, heteroatom-containing monovalent saturated hydrocarbon group, or halogeno (heteroatom-containing monovalent saturated hydrocarbon) group represented by the formula (1) includes R Ａ１ Examples of the monovalent saturated hydrocarbon group include a halogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, and a group similar to a halogeno (heteroatom-containing monovalent saturated hydrocarbon) group. Ａ４ The divalent saturated hydrocarbon group, halogeno divalent saturated hydrocarbon group, heteroatom-containing divalent saturated hydrocarbon group, or halogeno (heteroatom-containing divalent saturated hydrocarbon) group represented by the formula (1) includes R Ａ２ Examples of such a group include a divalent saturated hydrocarbon group represented by the following formula:

[0104] When the liquid contains an ester compound represented by formula (1) and an OH compound represented by formula (3), R in formula (3) in the OH compound Ａ３ represents R in formula (1) in the ester compound. Ａ１ When the liquid contains an ester compound represented by formula (2) and an OH compound represented by formula (4), R in formula (4) in the OH compound may be the same as or different from R Ａ４ is R in formula (2) in the ester compound Ａ２ They may be the same as or different from, and are preferably the same as.

[0105] Specific examples of the OH compound represented by formula (3) include the following structures: n1 represents an integer of 0 to 60, and n2 represents an integer of 0 to 500. n1 is, for example, 13, and n2 is, for example, 7.

[0106]

[0107] Specific examples of the OH compound represented by formula (4) include the following structures: n2 represents an integer of 0 to 499.

[0108]

[0109] Examples of the OH compound include the following compound (T2).

[0110]

[0111] The number average molecular weight of the OH compound is not particularly limited, and may be, for example, 50 to 50,000. From the viewpoint of excellent solubility in a solvent described later, the number average molecular weight is preferably 50 to 25,000, and more preferably 50 to 10,000. １ H-NMR and １９ It is the number average molecular weight of each molecule calculated from the molecular structure identified by F-NMR.

[0112] (Carboxylic Acid Compound) The liquid may contain a carboxylic acid compound. When the liquid contains a carboxylic acid compound, the amount of carboxylic acid is 2.0 parts by mass or less, as described above. From the viewpoint of increasing the yield of the target product, the amount of carboxylic acid is preferably 1.7 parts by mass or less, and more preferably 1.5 parts by mass or less. Furthermore, from the viewpoint of increasing the yield of the target product, the amount of carboxylic acid is preferably 0.01 parts by mass or more. The amount of carboxylic acid is preferably 0.01 to 2.0 parts by mass, more preferably 0.01 to 1.7 parts by mass, and even more preferably 0.01 to 1.5 parts by mass.

[0113] The carboxylic acid compound is not particularly limited as long as it is a compound having a carboxy group. The carboxylic acid compound may have only one carboxy group, or may have two or more carboxy groups, and preferably has only one carboxy group. The carboxylic acid compound may or may not have a fluorinable atom.

[0114] Examples of the carboxylic acid compound include compounds represented by the following formula (5): Ｂ４ -(C=O)-OH...(5)

[0115] In formula (5), R Ｂ４is a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogeno(heteroatom-containing monovalent saturated hydrocarbon) group.

[0116] R Ｂ４ The monovalent saturated hydrocarbon group, halogeno monovalent saturated hydrocarbon group, heteroatom-containing monovalent saturated hydrocarbon group, or halogeno (heteroatom-containing monovalent saturated hydrocarbon) group represented by the formula (1) includes R Ｂ１ Examples of such a group include a monovalent saturated hydrocarbon group represented by the following formula:

[0117] When the liquid contains an ester compound represented by formula (1) and a carboxylic acid compound represented by formula (5), R in formula (5) of the carboxylic acid compound Ｂ４ represents R in formula (1) in the ester compound. Ｂ１ When the liquid contains an ester compound represented by formula (2) and a carboxylic acid compound represented by formula (5), R in formula (5) of the carboxylic acid compound may be the same as or different from R Ｂ４ is R in formula (2) in the ester compound Ｂ２ and R Ｂ３ may be the same as one of, the same as both of, or different from both of, R Ｂ２ and R Ｂ３ It is preferable that the value is the same as at least one of the above.

[0118] Specific examples of the carboxylic acid compound represented by formula (5) include the following structures.

[0119]

[0120] The molecular weight of the carboxylic acid compound is not particularly limited, and may be, for example, 40 to 10,000. From the viewpoint of excellent solubility in a solvent described later, the molecular weight is preferably 40 to 5,000, and more preferably 40 to 1,000. １ H-NMR and １９ This is a value calculated from the molecular structure identified by F-NMR.

[0121] (NaF) The liquid may contain NaF. When the liquid contains NaF, as described above, the amount of NaF is 2.0 parts by mass or less. From the viewpoint of increasing the yield of the target product, the amount of NaF is preferably 1.5 parts by mass or less, and more preferably 1.2 parts by mass or less. Furthermore, from the viewpoint of increasing the yield of the target product, the amount of NaF is preferably 0.01 parts by mass or more. The amount of NaF is preferably 0.01 to 2.0 parts by mass, more preferably 0.01 to 1.5 parts by mass, and even more preferably 0.01 to 1.2 parts by mass.

[0122] (HF) The liquid may contain HF. When the ester compound contains an ester compound having an ether bond and the liquid contains HF, as described above, the amount of HF is preferably 3.0 parts by mass or less. From the viewpoint of increasing the yield of the target product, the amount of HF is more preferably 2.8 parts by mass or less. Furthermore, from the viewpoint of increasing the yield of the target product, the amount of HF is preferably 0.01 parts by mass or more. The amount of HF is preferably 0.01 to 3.0 parts by mass, more preferably 0.01 to 2.8 parts by mass.

[0123] (Solvent) The liquid may contain a solvent as needed. The solvent is not particularly limited as long as it can dissolve the ester compound.

[0124] From the viewpoint of excellent solubility of ester compounds and fluorine-containing ester compounds obtained by fluorinating ester compounds, the solvent preferably contains at least one selected from the group consisting of chlorine-containing solvents and fluorine-containing solvents other than chlorine-containing solvents, and more preferably contains a chlorine-containing solvent. The chlorine-containing solvent is a solvent containing chlorine atoms. The chlorine-containing solvent preferably contains fluorine atoms in addition to chlorine atoms.

[0125] Examples of chlorine-containing solvents include CClF ２ CCFCF ２ OCF ２ CClF ２ (CFE-419), CH ２ ClCHClCH ２ OCF ２ CHFCl (HCFE-473), CF ２ ClCFClCHFOCF ２ CF２ Cl (HCFE-428a, b), CFHClCFClCF ２ OCF ２ CF ２ Cl (HCFE-428c, d), CF ２ ClCHClCF ２ OCF ２ CF ２ Cl (HCFE-428e), 1,2,3,4-tetrachloroperfluorobutane (R-113), CF ２ Cl-CFCl-CFCl-O-CF ２ -CF ２ Cl (CFE-418), CClHFCClFCHFOCF ２ CClF ２ (HCFE-437a, b), CClF ２ CClHCHFOCF ２ CClF ２ (HCFE-437c), CClHFCClFCH ２ OCF ２ CClF ２ (HCFE-446a), CF ２ ClCCl ２ CF ２ OCF ２ CFHCl (HCFE-427a,b), CF ２ HClFCF ２ OCF ２ CF ２ Examples of fluorine-containing solvents other than chlorine-containing solvents include perfluoroalkanes (FC-72, etc.), perfluoroethers (FC-75, FC-77, etc.), perfluoropolyethers (trade names: Krytox, Fomblin, Galden, Demnum, etc.), inert fluids (trade name: Fluorinert), and perfluorocarboxylic acid fluorides.

[0126] The boiling point of the solvent is preferably 10 to 500 ° C, more preferably 30 to 250 ° C, and even more preferably 50 to 150 ° C, from the viewpoint of improving the yield of the fluorine-containing compound. The number of carbon atoms in the solvent is preferably 4 or more, more preferably 4 to 1,000, even more preferably 4 to 500, particularly preferably 4 to 100, and most preferably 4 to 50, from the viewpoint of improving the yield of the fluorine-containing compound. The molecular weight of the solvent is preferably 200 or more, more preferably 200 to 50,000, even more preferably 200 to 25,000, particularly preferably 200 to 10,000, and most preferably 200 to 1,000. When there is a molecular weight distribution, the molecular weight represents the weight average molecular weight (Mw). Mw is measured in terms of polystyrene equivalent by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent.

[0127] (Other Additives) The liquid may contain other additives as needed. Examples of other additives include an auxiliary that promotes the fluorination of an ester compound. Examples of auxiliary agents include C-H bond-containing compounds other than ester compounds and carbon-carbon double bond-containing compounds. Examples of C-H bond-containing compounds include benzene and toluene. Examples of carbon-carbon double bond-containing compounds include hexafluoropropylene and hexafluorobutadiene. Of these, aromatic hydrocarbons such as benzene and toluene are preferred as auxiliary agents.

[0128] <Fluorination Reaction> Examples of methods for fluorinating a raw material compound in a liquid include the ECF method, the cobalt fluorination method, and a method of reacting with fluorine. Among these, the method of reacting with fluorine is preferred, as it can advantageously promote the fluorination of the raw material compound.

[0129] In a method of reacting a raw material compound with fluorine in a liquid, for example, a gas containing fluorine gas is introduced into a liquid containing the raw material compound. Hereinafter, as an example of a fluorination reaction, a method of introducing a gas containing fluorine gas into a liquid containing the raw material compound will be described, but the method is not limited thereto.

[0130] The gas introduced into the liquid only needs to contain at least fluorine gas. The gas may consist of fluorine gas or may contain a gas other than fluorine gas. Examples of gases other than fluorine gas include inert gases. Examples of inert gases include nitrogen gas, helium gas, neon gas, and argon gas. Nitrogen gas or helium gas is preferred, and nitrogen gas is preferred from the viewpoint of keeping costs low.

[0131] The content of fluorine gas in the entire gas is preferably 10% by volume or more, more preferably 15% by volume or more, even more preferably 20% by volume or more, and particularly preferably 25% by volume or more, from the viewpoint of increasing the yield of the target product. Also, the content of fluorine gas in the entire gas is preferably 60% by volume or less, more preferably 50% by volume or less, and even more preferably 40% by volume or less, from the viewpoint of excellent safety. From the above viewpoints, the content of fluorine gas in the entire gas is preferably 10 to 60% by volume, more preferably 15 to 50% by volume, and even more preferably 20 to 40% by volume.

[0132] The temperature for fluorination of the ester compound is, for example, in the range of not less than −60° C. and not more than the boiling point of the ester compound, and may be in the range of −50 to 100° C., or may be in the range of −20 to 50° C. The pressure for fluorination of the ester compound is, for example, 0 to 2 MPa. The fluorination of the ester compound may be carried out by a batch method or a continuous method.

[0133] The residence time of a liquid containing an ester compound and into which fluorine gas has been introduced in a reactor in which the fluorination of an ester compound is carried out is, from the viewpoint of increasing the yield of the target product, preferably 200 hours or less, more preferably 190 hours or less, even more preferably 170 hours or less, particularly preferably 150 hours or less, and extremely preferably 100 hours or less. Hereinafter, the residence time of the liquid in the reactor will also be referred to as the "residence time." From the viewpoint of increasing the yield of the target product, the residence time is preferably 0.3 hours or more, more preferably 0.6 hours or more, and even more preferably 1.0 hour or more. The residence time is preferably 0.3 to 200 hours, more preferably 0.3 to 190 hours, even more preferably 0.3 to 170 hours, particularly preferably 0.6 to 150 hours, and extremely preferably 1.0 to 100 hours. When the fluorination of an ester compound is carried out in a continuous system, the residence time is calculated from the flow rate of the liquid and the volume of the reactor. When the fluorination of the ester compound is carried out in a continuous manner, the residence time may be adjusted by the flow rate of the liquid and the length of the reactor in the flow direction.

[0134] <Fluorine-containing ester compound> A fluorine-containing ester compound obtained by fluorination of an ester compound is a compound in which at least one of the fluorinatable atoms of the ester compound is replaced with a fluorine atom. The fluorine-containing ester compound preferably further has an ether bond, and more preferably contains a perfluoropolyether chain.

[0135] When the ester compound is a compound represented by the formula (1), the fluorine-containing ester compound is preferably a compound represented by the following formula (6). When the ester compound is a compound represented by the formula (2), the fluorine-containing ester compound is preferably a compound represented by the following formula (7). R ＡＦ１ -O-(C=O)-R ＢＦ１ …(6) R ＢＦ２ -(C=O)-OR ＡＦ２ -O-(C=O)-R ＢＦ３ ... (7) In formulas (6) and (7), R ＡＦ１ , R ＢＦ１ , R ＡＦ２ , R ＢＦ２ , and R ＢＦ３are respectively R Ａ１ , R Ｂ１ , R Ａ２ , R Ｂ２ , and R Ｂ３ is a group corresponding to Ａ１ , R Ｂ１ , R Ａ２ , R Ｂ２ , and R Ｂ３ are each independently a group containing no hydrogen atom, R ＡＦ１ , R ＢＦ１ , R ＡＦ２ , R ＢＦ２ , and R ＢＦ３ is R Ａ１ , R Ｂ１ , R Ａ２ , R Ｂ２ , and R Ｂ３ is the same group as Ａ１ , R Ｂ１ , R Ａ２ , R Ｂ２ , and R Ｂ３ are each independently a group containing a hydrogen atom, R ＡＦ１ , R ＢＦ１ , R ＡＦ２ , R ＢＦ２ , and R ＢＦ３ is R Ａ１ , R Ｂ１ , R Ａ２ , R Ｂ２ , and R Ｂ３ is a group in which all hydrogen atoms present in are substituted with fluorine atoms.

[0136] [R ＡＦ１ ] In formula (6), R ＡＦ１ is R Ａ１ is a group corresponding to Ａ１ When contains a hydrogen atom, R ＡＦ１ is R Ａ１ R is a group in which all hydrogen atoms present in R have been substituted with fluorine atoms. Ａ１ When does not contain a hydrogen atom, R ＡＦ１ is R Ａ１ From the viewpoint of excellent solubility in solvents, R ＡＦ１ is preferably represented by the following formula (A3): １４ O-(R １５ O) ｍ３ -R１６ - ... (A3)

[0137] In formula (A3), R １４ is a perfluoroalkyl group, and R １５ are each independently a perfluoroalkylene group having 1 to 6 carbon atoms, and R １６ is a perfluoroalkylene group having 1 to 6 carbon atoms, and m3 is an integer of 0 to 500.

[0138] In formula (A3), R １４ is R in formula (A1). １１ Corresponds to R １１ When R contains a hydrogen atom, １４ is R １１ is a group in which all hydrogen atoms in R have been substituted with fluorine atoms. １１ When does not contain a hydrogen atom, R １４ is R １１ is the same as

[0139] In formula (A3), -(R １５ O) ｍ３ - represents -(R １２ O) ｍ１ Corresponds to -. R １２ When R contains a hydrogen atom, １５ is R １２ is a group in which all hydrogen atoms in R have been substituted with fluorine atoms. １２ When does not contain a hydrogen atom, R １５ is R １２ is the same as

[0140] In formula (A3), -(R １５ O) ｍ３ - is preferably represented by the following formula (A4): -[(R ｆｆ１ O) ｋ７ (R ｆｆ２ O) ｋ８ (R ｆｆ３ O) ｋ９ (R ｆｆ４ O) ｋ１０ (R ｆｆ５ O) ｋ１１ (R ｆｆ６ O) ｋ１２ ]- …(A4) However, R ｆｆ１ is a perfluoroalkylene group having one carbon atom, and Rｆｆ２ is a perfluoroalkylene group having 2 carbon atoms, R ｆｆ３ is a perfluoroalkylene group having 3 carbon atoms, R ｆｆ４ is a perfluoroalkylene group having 4 carbon atoms, R ｆｆ５ is a perfluoroalkylene group having 5 carbon atoms, R ｆｆ６ is a perfluoroalkylene group having 6 carbon atoms. k7, k8, k9, k10, k11, and k12 each independently represent an integer of 0 or 1 or more, and k7 + k8 + k9 + k10 + k11 + k12 is an integer of 0 to 500.

[0141] In formula (A4), R ｆｆ１ ~R ｆｆ６ is R in formula (A2). ｆ１ ~R ｆ６ For example, R ｆ１ When R contains a hydrogen atom, ｆｆ１ is R ｆ１ R is a group in which all hydrogen atoms in R are substituted with fluorine atoms. ｆ１ When does not contain a hydrogen atom, R ｆｆ１ is R ｆ１ It is the same as R ｆｆ２ ~R ｆｆ６ Regarding R ｆｆ１ is the same as:

[0142] From the viewpoint of excellent solubility in solvents, k7 + k8 + k9 + k10 + k11 + k12 is preferably an integer of 1 to 500, more preferably an integer of 1 to 300, still more preferably an integer of 5 to 200, and particularly preferably an integer of 10 to 150.

[0143] Among them, -(R １５ O) ｍ３ - preferably includes at least one selected from the group consisting of structures represented by the following formulas (G1) to (G3), and more preferably includes a structure represented by formula (G2): -(R ｆｆ１ O) ｋ７ - (R ｆｆ２ O) ｋ８ -...(G1) -(R ｆｆ２ O) ｋ８ - (R ｆｆ４ O) ｋ１０-...(G2) -(R ｆｆ３ O) ｋ９ − (G3) where the symbols in formulas (G1) to (G3) are the same as those in formula (A4) above.

[0144] In formula (G1) and formula (G2), (R ｆｆ１ O) and (R ｆｆ２ O), (R ｆｆ２ O) and (R ｆｆ４ O) can be bonded in any order. For example, (R ｆｆ１ O) and (R ｆｆ２ O) may be alternately arranged, and (R ｆｆ１ O) and (R ｆｆ２ O) may be arranged in blocks or randomly. The same applies to formula (G2). In formula (G1), k7 is preferably 1 to 30, more preferably 1 to 20. Also, k8 is preferably 1 to 30, more preferably 1 to 20. In formula (G2), k8 is preferably 1 to 30, more preferably 1 to 20. Also, k10 is preferably 1 to 30, more preferably 1 to 20. In formula (G3), k9 is preferably 1 to 30, more preferably 1 to 20.

[0145] In formula (A3), R １６ is R in formula (A1). １３ Corresponds to R １３ When R contains a hydrogen atom, １６ is R １３ is a group in which all hydrogen atoms in R have been substituted with fluorine atoms. １３ When does not contain a hydrogen atom, R １６ is R １３ is the same as

[0146] R １６ As the above, R ｆｆ１ ~R ｆｆ６ The same can be mentioned.

[0147] Among them, R １６ is preferably a perfluoroalkylene group having 1 to 3 carbon atoms.

[0148] In formula (A3), m3 corresponds to m1 in formula (A1). m3 is the same as m1.

[0149] RＡＦ１ Specific examples of the structure include the following: * represents the bonding site with —O—, n1 represents an integer of 0 to 60, and n2 represents an integer of 0 to 500. n1 is, for example, 13, and n2 is, for example, 7.

[0150]

[0151] [R ＢＦ１ ] In formula (6), R ＢＦ１ is R Ｂ１ is a group corresponding to Ｂ１ When contains a hydrogen atom, R ＢＦ１ is R Ｂ１ R is a group in which all hydrogen atoms present in R have been substituted with fluorine atoms. Ｂ１ When does not contain a hydrogen atom, R ＢＦ１ is R Ｂ１ From the viewpoint of excellent solubility in solvents, R ＢＦ１ is preferably represented by the following formula (B2): ２４ O-(R ２５ O) ｍ４ -R ２６ - ... (B2)

[0152] In formula (B2), R ２４ is a perfluoroalkyl group, and R ２５ are each independently a perfluoroalkylene group having 1 to 6 carbon atoms, and R ２６ is a perfluoroalkylene group having 1 to 6 carbon atoms, and m4 is an integer of 0 to 20.

[0153] In formula (B2), R ２４ is R in formula (B1). ２１ Corresponds to R ２１ When R contains a hydrogen atom, ２４ is R ２１ is a group in which all hydrogen atoms in R have been substituted with fluorine atoms. ２１ When does not contain a hydrogen atom, R ２４ is R ２１ is the same as

[0154] In formula (B2), -(R ２５ O) ｍ４ - represents -(R ２２O) ｍ２ Corresponds to -. R ２２ When R contains a hydrogen atom, ２５ is R ２２ is a group in which all hydrogen atoms in R have been substituted with fluorine atoms. ２２ When does not contain a hydrogen atom, R ２５ is R ２２ is the same as

[0155] In formula (B2), -(R ２５ O) ｍ４ - is preferably represented by the above formula (A4).

[0156] In formula (B2), R ２６ is R in formula (B1). ２３ Corresponds to R ２３ When R contains a hydrogen atom, ２６ is R ２３ is a group in which all hydrogen atoms in R have been substituted with fluorine atoms. ２３ When does not contain a hydrogen atom, R ２６ is R ２３ is the same as

[0157] In formula (B2), m4 corresponds to m2 in formula (B1). m4 is the same as m2.

[0158] R ＢＦ１ Specific examples of the structure include the following: * represents the bonding site with —O—(C═O)—.

[0159]

[0160] [R ＡＦ２ ] In formula (7), R ＡＦ２ is R Ａ２ is a group corresponding to Ａ２ When contains a hydrogen atom, R ＡＦ２ is R Ａ２ R is a group in which all hydrogen atoms present in R have been substituted with fluorine atoms. Ａ２ When does not contain a hydrogen atom, R ＡＦ２ is R Ａ２ is the same group as

[0161] From the viewpoint of excellent solubility in solvents, R ＡＦ２is preferably represented by the following formula (A6): ＡＦ２ Preferably, —R further has an ether bond. ３４ O-(R ３５ O) ｍ６ -R ３６ - ... (A6)

[0162] In formula (A6), R ３４ and R ３６ are each independently a perfluoroalkylene group having 1 to 6 carbon atoms, and R ３５ are each independently a perfluoroalkylene group having 1 to 6 carbon atoms, and m6 is an integer of 0 to 500.

[0163] In formula (A6), R ３４ and R ３６ are R in formula (A5), respectively. ３１ and R ３３ Corresponds to R ３１ When R contains a hydrogen atom, ３４ is R ３１ is a group in which all hydrogen atoms in R have been substituted with fluorine atoms. ３１ When does not contain a hydrogen atom, R ３４ is R ３１ It is the same as R ３３ When R contains a hydrogen atom, ３６ is R ３３ is a group in which all hydrogen atoms in R have been substituted with fluorine atoms. ３３ When does not contain a hydrogen atom, R ３６ is R ３４ is the same as

[0164] In formula (A6), -(R ３５ O) ｍ６ - represents -(R ３２ O) ｍ５ Corresponds to -. R ３２ When R contains a hydrogen atom, ３５ is R ３２ is a group in which all hydrogen atoms in R have been substituted with fluorine atoms. ３２ When does not contain a hydrogen atom, R ３５ is R ３２ is the same as

[0165] In formula (A6), R３４ and R ３６ R in formula (A5) ３１ and R ３３ In formula (A6), -(R ３５ O) ｍ６ - is -(R ３２ O) ｍ５ - and the same as above.

[0166] R ＡＦ２ Specific examples of the structure include the following: * represents the bonding site with —O—, and n2 represents an integer of 0 to 500.

[0167]

[0168] [R ＢＦ２ and R ＢＦ３ ] In formula (7), R ＢＦ２ and R ＢＦ３ are respectively R Ｂ２ and R Ｂ３ is a group corresponding to Ｂ２ When contains a hydrogen atom, R ＢＦ２ is R Ｂ２ R is a group in which all hydrogen atoms present in R have been substituted with fluorine atoms. Ｂ２ When does not contain a hydrogen atom, R ＢＦ２ is R Ｂ２ is the same group as Ｂ３ When contains a hydrogen atom, R ＢＦ３ is R Ｂ３ R is a group in which all hydrogen atoms present in R have been substituted with fluorine atoms. Ｂ３ When does not contain a hydrogen atom, R ＢＦ３ is R Ｂ３ is the same group as

[0169] R ＢＦ２ or R ＢＦ３ is a group represented by R in formula (6) ＢＦ１ Examples of the groups include the same groups as those represented by the following formula:

[0170] The number average molecular weight of the fluorine-containing ester compound is not particularly limited, and may be, for example, 100 to 101,000. From the viewpoint of excellent solubility in solvents, it is preferably 100 to 21,000, more preferably 300 to 11,000, and even more preferably 400 to 7,000. The number average molecular weight of the fluorine-containing ester compound is １ H-NMR and １９ It is the number average molecular weight of each molecule calculated from the molecular structure identified by F-NMR.

[0171] [Composition] A composition according to one embodiment of the present disclosure comprises an ester compound having at least one fluorinatable atom and at least one selected from the group consisting of a compound having a hydroxyl group, a compound having a carboxy group, and sodium fluoride, wherein, relative to 100 parts by mass of the ester compound, the content of the compound having a hydroxyl group is 0.5 parts by mass or less, the content of the compound having a carboxy group is 2.0 parts by mass or less, and the content of the sodium fluoride is 2.0 parts by mass or less. The composition is used, for example, in the method for producing a fluorinated ester compound described above. Thereby, the ester compound contained in the composition is fluorinated to obtain a fluorinated ester compound. When the composition is a liquid, the composition may be used as is as a liquid to be fluorinated in the method for producing a fluorinated ester compound described above. Furthermore, if necessary, a solvent or the like may be added to the composition, and the resulting mixture may be used as a liquid to be fluorinated in the method for producing a fluorinated ester compound described above.

[0172] The composition contains at least one compound selected from the group consisting of an OH compound, a carboxylic acid compound, and NaF, and has an OH compound amount of 0.5 parts by mass or less, a carboxylic acid amount of 2.0 parts by mass or less, and a NaF amount of 2.0 parts by mass or less. Therefore, when the composition is used in the above-mentioned method for producing a fluorinated ester compound and the ester compound in the composition is subjected to a fluorination reaction, the target fluorinated ester compound can be obtained in high yield.

[0173] In one embodiment of the present disclosure, at least one selected from the group consisting of the amount of OH compounds, the amount of carboxylic acid, and the amount of NaF is preferably 0.01 parts by mass or more. Thus, when the composition is used in the method for producing a fluorinated ester compound, the target fluorinated ester compound can be obtained in high yield. A portion of the amount of OH compounds, the amount of carboxylic acid, and the amount of NaF may be 0.01 parts by mass or more, or all of the amount of OH compounds, the amount of carboxylic acid, and the amount of NaF may be 0.01 parts by mass or more.

[0174] In an embodiment of the present disclosure, the ester compound may include an ester compound having an ether bond. When the ester compound includes an ester compound having an ether bond, the composition further contains hydrogen fluoride, and the content of the hydrogen fluoride is preferably 3.0 parts by mass or less per 100 parts by mass of the ester compound contained in the liquid.

[0175] That is, when the composition contains an ester compound having an ether bond, it is preferred that the composition further contains HF in an amount of 3.0 parts by mass or less, whereby when the composition is used in the above-mentioned method for producing a fluorinated ester compound, the target fluorinated ester compound can be obtained in high yield.

[0176] When the composition contains an ester compound having an ether bond, it is preferable that at least one selected from the group consisting of an OH compound amount, a carboxylic acid amount, a NaF amount, and a HF amount is 0.01 parts by mass or more. This allows the target fluorine-containing ester compound to be obtained in high yield when the composition is used in the above-mentioned method for producing a fluorine-containing ester compound. Any of the OH compound amount, the carboxylic acid amount, the NaF amount, and the HF amount may be 0.01 parts by mass or more, or all of the OH compound amount, the carboxylic acid amount, the NaF amount, and the HF amount may be 0.01 parts by mass or more.

[0177] The amount of OH compound is preferably 0.01 to 0.5 parts by mass. The amount of carboxylic acid is preferably 0.01 to 2.0 parts by mass, more preferably 0.01 to 1.7 parts by mass, and even more preferably 0.01 to 1.5 parts by mass. The amount of NaF is preferably 0.01 to 2.0 parts by mass, more preferably 0.01 to 1.5 parts by mass, and even more preferably 0.01 to 1.2 parts by mass. The amount of HF is preferably 0.01 to 3.0 parts by mass, and more preferably 0.01 to 2.8 parts by mass. The composition may further contain a solvent, other additives, etc., as necessary.

[0178] Details of the ester compound, OH compound, carboxylic acid compound, solvent and other additives are the same as those of the ester compound, OH compound, carboxylic acid compound, solvent and other additives in the above-mentioned method for producing a fluorine-containing ester compound.

[0179] The composition preferably contains an ester compound and at least one selected from the group consisting of an OH compound, a carboxylic acid compound, and sodium fluoride, and the ester compound preferably includes at least one selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2), the OH compound preferably includes at least one selected from the group consisting of a compound represented by the following formula (3) and a compound represented by the following formula (4), and the carboxylic acid compound preferably includes a compound represented by the following formula (5). Ａ１ -O-(C=O)-R Ｂ１ …(1) R Ｂ２ -(C=O)-OR Ａ２ -O-(C=O)-R Ｂ３ …(2) R Ａ３ -OH...(3) HO-R Ａ４ -OH ... (4) R Ｂ４ -(C=O)-OH...(5) In formulas (1) to (5), R Ａ１ , R Ａ３ , R Ｂ１ , R Ｂ２ , R Ｂ３ , and R Ｂ４ are each independently a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogeno (heteroatom-containing monovalent saturated hydrocarbon) group; RＡ２ and R Ａ４ are each independently a divalent saturated hydrocarbon group, a halogeno divalent saturated hydrocarbon group, a heteroatom-containing divalent saturated hydrocarbon group, or a halogeno (heteroatom-containing divalent saturated hydrocarbon) group.

[0180] Furthermore, R in formula (3) Ａ３ is R in formula (1) Ａ１ is the same as R in formula (4). Ａ４ is R in formula (2) Ａ２ and R in formula (5) Ｂ４ is R in formula (1) Ｂ１ or R in formula (2) Ｂ２ is preferably the same as

[0181] The present disclosure will be described in more detail below using examples, but the present disclosure is not limited to the following examples as long as it does not deviate from the gist of the disclosure. Examples 1-2, 4, 6 to 11, 12-2, 16 to 20, 22-2, 23-2, 24-2, 25-2, and 26-2 are working examples, and Examples 2, 3, 5, 13 to 15, and 21 are comparative examples.

[0182] １９ For F-NMR quantification, perfluorobenzene was used as an internal standard sample. Hereinafter, tetramethylsilane will be referred to as TMS, and 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane will be referred to as AC-2000. The AC-2000 used was manufactured by AGC. NMR data is shown as the apparent chemical shift range.

[0183] Example 1-1: 50.1 g of the following alcohol 1 and 1.34 g of NaF were added to a flask. NaF with an average primary particle size of 5 μm (manufactured by Kanto Chemical, Kagoshima Special Grade 37174-00) was used. 25.0 g of AC-2000 and the following (HFPO) ２ After mixing, the container was sealed and heated and stirred at 50°C for 10 hours. After 10 hours of heating and stirring, the mixture was allowed to cool and filtered through silica gel (D75-60A(N), manufactured by AGC Si-Tech Co., Ltd.) to remove NaF. Then, (HFPO) ２ and AC-2000 were removed by evaporation under reduced pressure. ​

[0184] Alcohol 1: CH ３ O (CF ２ CHFO (CF ２ ) ３ CH ２ O) １３ CF ２ CHFO (CF ２ ) ３ CH ２ OH (molecular weight: 3,924) (HFPO) ２ : 2,3,3,3-tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)-propanoyl fluoride (chemical formula: CF ３ CF ２ CF ２ OCF (CF ３ ) COF, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product number: QC-2788)

[0185] Highly polar impurities were removed by silica gel chromatography (developing solvent: AC-2000), yielding 53.9 g (yield 99.9%) of an ester compound. １ H-NMR and １９ As a result of F-NMR analysis, the obtained compound was confirmed to be the following compound 1-1. １ H-NMR and １９ It was confirmed by F-NMR that the above alcohol 1 and the following carboxylic acid 1 were not detected, and by F ion concentration measurement, HF and NaF were not detected.

[0186] Compound 1-1: CH ３ O (CF ２ CHFO (CF ２ ) ３ CH ２ O) ｎ CF ２ CHFO (CF ２ ) ３ CH ２ OCOCF (CF ３ ) OCF ２ CF ２ CF ３ １ H-NMR (300.4 MHz, solvent CDCl ３ ​, standard TMS) δ (ppm): 3.7 (3H), 4.7 (32H), 5.2 (2H), 6.7-6.9 (8H) １９ F-NMR (282.7 MHz, solvent CDCl ３ , Reference CFCl ３ ) δ (ppm): -79.0 (1F), -81.1 (3F), -81.9 (3F), -83.7 to -85.0 (28F), -86.0 (1F), -89.0 to -92.0 (28F), -119.8 (2F), -120.2 (26F), -126.6 (28F), -129.3 (2F), -131.5 (1F), -145.0 (14F) Average value of number of units n: 13 Carboxylic acid 1: 2,3,3,3-tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)-propionic acid (chemical formula: CF ３ CF ２ CF ２ OCF (CF ３ ) COOH)

[0187] Example 1-2 An autoclave (made of nickel, internal volume 500 mL) was prepared, and a cooler maintained at 0°C, a NaF pellet packed layer, and another cooler maintained at -10°C were installed in series at the gas outlet of the autoclave. In addition, a liquid return line was installed to return the condensed liquid from the cooler maintained at -10°C to the autoclave. An aqueous KOH solution was installed in the final outlet gas line. In this manner, a fluorination reaction apparatus was prepared.

[0188] 302 g of CFE-419 was charged into the autoclave of a fluorination reaction apparatus and stirred while maintaining the temperature at 20°C. Nitrogen gas was blown into the autoclave at 20°C for 1 hour, and then fluorine gas diluted to 30% by volume with nitrogen gas was blown in at 20°C and a flow rate of 2.0 L / hour for 1 hour. Hereinafter, fluorine gas diluted to 30% by volume with nitrogen gas will also be referred to as "30% fluorine gas". Next, while blowing 30% fluorine gas at the same flow rate, a solution prepared by dissolving 8.4 g of Compound 1-1 obtained in Example 1-1, 0.04 g of Alcohol 1, 0.12 g of Carboxylic Acid 1, 0.22 g of HF, and 0.09 g of NaF in 84.0 g of CFE-419 was injected into the autoclave over 5.3 hours.

[0189] Next, 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 was injected into the autoclave, and the benzene solution inlet of the autoclave was closed. Furthermore, stirring was continued for 1 hour while blowing in 30% fluorine gas at the same flow rate. Next, nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated using an evaporator, and then highly polar impurities were removed using silica gel chromatography (developing solvent: AC-2000), and 9.85 g (yield 99.5%) of the following compound 1-2 was recovered.

[0190] Compound 1-2: CF ３ O (CF ２ CF ２ OCF ２ CF ２ CF ２ CF ２ O) ｎ CF ２ CF ２ OCF ２ CF ２ CF ２ CF ２ OCOCF (CF ３ ) OCF ２ CF ２ CF ３ １９ F-NMR (282.7 MHz, solvent CDCl ３ , Reference CFCl ３ ) δ (ppm): -55.2 (3F), -80.0 (1F), -82.0 to -82.5 (6F), -84.1 (54F), -86.7 to -87.8 (3F), -89.3 (54F), -91.3 (2F), -126.5 (56F), -130.4 (2F), -132.4 (1F) Average value of number of units n: 13

[0191] ​Example 2 A fluorination reactor was prepared in the same manner as in Example 1-2. 301 g of CFE-419 was charged into the autoclave of the fluorination reactor and stirred while maintaining the temperature at 20°C. Nitrogen gas was blown into the autoclave at 20°C for 1 hour, and then 30% fluorine gas was blown into the autoclave at 20°C and a flow rate of 2.0 L / hour for 1 hour. Next, while blowing 30% fluorine gas at the same flow rate, a solution prepared by dissolving 8.5 g of Compound 1-1 obtained in Example 1-1, 0.09 g of Alcohol 1, 0.13 g of Carboxylic Acid 1, 0.22 g of HF, and 0.09 g of NaF in 84.0 g of CFE-419 was injected into the autoclave over 5.3 hours.

[0192] Next, 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 was injected into the autoclave, and the benzene solution inlet of the autoclave was closed. Furthermore, stirring was continued for 1 hour while blowing in 30% fluorine gas at the same flow rate. Then, nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated using an evaporator, and then highly polar impurities were removed by silica gel chromatography (developing solvent: AC-2000), and 7.03 g (yield 70.2%) of the compound 1-2 was recovered. The structure and １９ The F-NMR data was the same as in Example 1-2.

[0193] Example 3 A fluorination reactor was prepared in the same manner as in Example 1-2. 300 g of CFE-419 was charged into the autoclave of the fluorination reactor and stirred while maintaining the temperature at 20°C. Nitrogen gas was blown into the autoclave at 20°C for 1 hour, and then 30% fluorine gas was blown into the autoclave at 20°C and a flow rate of 2.0 L / hour for 1 hour. Next, while blowing 30% fluorine gas at the same flow rate, a solution prepared by dissolving 8.4 g of Compound 1-1 obtained in Example 1-1, 0.04 g of Alcohol 1, 0.18 g of Carboxylic Acid 1, 0.22 g of HF, and 0.09 g of NaF in 84.0 g of CFE-419 was injected into the autoclave over 5.3 hours.

[0194] Next, 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 was injected into the autoclave, and the benzene solution inlet of the autoclave was closed. Furthermore, stirring was continued for 1 hour while blowing in 30% fluorine gas at the same flow rate. Then, nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated using an evaporator, and highly polar impurities were removed by silica gel chromatography (developing solvent: AC-2000), and 7.01 g (yield 70.8%) of the compound 1-2 was recovered. The structure and １９ The F-NMR data was the same as in Example 1-2.

[0195] Example 4 A fluorination reactor was prepared in the same manner as in Example 1-2. 300 g of CFE-419 was charged into the autoclave of the fluorination reactor and stirred while maintaining the temperature at 20°C. Nitrogen gas was blown into the autoclave at 20°C for 1 hour, and then 30% fluorine gas was blown into the autoclave at 20°C and a flow rate of 2.0 L / hour for 1 hour. Next, while blowing 30% fluorine gas at the same flow rate, a solution prepared by dissolving 8.4 g of Compound 1-1 obtained in Example 1-1, 0.04 g of Alcohol 1, 0.12 g of Carboxylic Acid 1, 0.27 g of HF, and 0.09 g of NaF in 84.0 g of CFE-419 was injected into the autoclave over 5.3 hours.

[0196] Next, 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 was injected into the autoclave, and the benzene solution inlet of the autoclave was closed. Furthermore, stirring was continued for 1 hour while blowing in 30% fluorine gas at the same flow rate. Then, nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated using an evaporator, and highly polar impurities were removed by silica gel chromatography (developing solvent: AC-2000), and 7.13 g (yield 72.0%) of the compound 1-2 was recovered. The structure and １９ The F-NMR data was the same as in Example 1-2.

[0197] Example 5 A fluorination reactor was prepared in the same manner as in Example 1-2. 301 g of CFE-419 was charged into the autoclave of the fluorination reactor and stirred while maintaining the temperature at 20°C. Nitrogen gas was blown into the autoclave at 20°C for 1 hour, and then 30% fluorine gas was blown into the autoclave at 20°C and a flow rate of 2.0 L / hour for 1 hour. Next, while blowing 30% fluorine gas at the same flow rate, a solution prepared by dissolving 8.5 g of Compound 1-1 obtained in Example 1-1, 0.05 g of Alcohol 1, 0.13 g of Carboxylic Acid 1, 0.22 g of HF, and 0.18 g of NaF in 84.0 g of CFE-419 was injected into the autoclave over 5.3 hours.

[0198] Next, 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 was injected into the autoclave, and the benzene solution inlet of the autoclave was closed. Furthermore, stirring was continued for 1 hour while blowing in 30% fluorine gas at the same flow rate. Then, nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated using an evaporator, and highly polar impurities were removed by silica gel chromatography (developing solvent: AC-2000), and 7.12 g (yield 71.1%) of the compound 1-2 was recovered. The structure and １９ The F-NMR data was the same as in Example 1-2.

[0199] Example 6 A fluorination reactor was prepared in the same manner as in Example 1-2. 300 g of CFE-419 was charged into the autoclave of the fluorination reactor and stirred while maintaining the temperature at 20°C. Nitrogen gas was blown into the autoclave at 20°C for 1 hour, and then 30% fluorine gas was blown into the autoclave at 20°C and a flow rate of 2.0 L / hour for 1 hour. Next, while blowing 30% fluorine gas at the same flow rate, a solution prepared by dissolving 8.5 g of Compound 1-1 obtained in Example 1-1, 0.001 g of Alcohol 1, 0.13 g of Carboxylic Acid 1, 0.22 g of HF, and 0.09 g of NaF in 84.0 g of CFE-419 was injected into the autoclave over 5.3 hours.

[0200] Next, 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 was injected into the autoclave, and the benzene solution inlet of the autoclave was closed. Furthermore, stirring was continued for 1 hour while blowing in 30% fluorine gas at the same flow rate. Then, nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated using an evaporator, and then highly polar impurities were removed by silica gel chromatography (developing solvent: AC-2000), and 9.93 g (yield 99.1%) of the compound 1-2 was recovered. The structure and １９ The F-NMR data was the same as in Example 1-2.

[0201] Example 7 A fluorination reaction apparatus was prepared in the same manner as in Example 1-2. 301 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus and stirred while maintaining the temperature at 20°C. Nitrogen gas was blown into the autoclave at 20°C for 1 hour, and then 30% fluorine gas was blown into the autoclave at 20°C and a flow rate of 2.0 L / hour for 1 hour. Next, while blowing 30% fluorine gas at the same flow rate, a solution prepared by dissolving 8.4 g of Compound 1-1 obtained in Example 1-1 and 0.001 g of Alcohol 1 in 84.0 g of CFE-419 was injected into the autoclave over 5.3 hours.

[0202] Next, 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 was injected into the autoclave, and the benzene solution inlet of the autoclave was closed. Furthermore, stirring was continued for 1 hour while blowing in 30% fluorine gas at the same flow rate. Then, nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated using an evaporator, and highly polar impurities were removed by silica gel chromatography (developing solvent: AC-2000), and 9.80 g (yield 99.0%) of the compound 1-2 was recovered. The structure and １９ The F-NMR data was the same as in Example 1-2.

[0203] Example 8 A fluorination reactor was prepared in the same manner as in Example 1-2. 300 g of CFE-419 was charged into the autoclave of the fluorination reactor and stirred while maintaining the temperature at 20°C. Nitrogen gas was blown into the autoclave at 20°C for 1 hour, and then 30% fluorine gas was blown into the autoclave at 20°C and a flow rate of 2.0 L / hour for 1 hour. Next, while blowing 30% fluorine gas at the same flow rate, a solution prepared by dissolving 8.5 g of Compound 1-1 obtained in Example 1-1, 0.04 g of Alcohol 1, 0.001 g of Carboxylic Acid 1, 0.22 g of HF, and 0.09 g of NaF in 84.0 g of CFE-419 was injected into the autoclave over 5.3 hours.

[0204] Next, 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 was injected into the autoclave, and the benzene solution inlet of the autoclave was closed. Furthermore, stirring was continued for 1 hour while blowing in 30% fluorine gas at the same flow rate. Then, nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated using an evaporator, and then highly polar impurities were removed by silica gel chromatography (developing solvent: AC-2000), and 9.91 g (yield 98.9%) of the compound 1-2 was recovered. The structure and １９ The F-NMR data was the same as in Example 1-2.

[0205] Example 9 A fluorination reactor was prepared in the same manner as in Example 1-2. 300 g of CFE-419 was charged into the autoclave of the fluorination reactor and stirred while maintaining the temperature at 20°C. Nitrogen gas was blown into the autoclave at 20°C for 1 hour, and then 30% fluorine gas was blown into the autoclave at 20°C and a flow rate of 2.0 L / hour for 1 hour. Next, while blowing 30% fluorine gas at the same flow rate, a solution prepared by dissolving 8.5 g of Compound 1-1 obtained in Example 1-1, 0.04 g of Alcohol 1, 0.13 g of Carboxylic Acid 1, 0.001 g of HF, and 0.09 g of NaF in 84.0 g of CFE-419 was injected into the autoclave over 5.3 hours.

[0206] Next, 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 was injected into the autoclave, and the benzene solution inlet of the autoclave was closed. Furthermore, stirring was continued for 1 hour while blowing in 30% fluorine gas at the same flow rate. Then, nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated using an evaporator, and then highly polar impurities were removed by silica gel chromatography (developing solvent: AC-2000), and 9.93 g (yield 99.1%) of the compound 1-2 was recovered. The structure and １９ The F-NMR data was the same as in Example 1-2.

[0207] Example 10 A fluorination reactor was prepared in the same manner as in Example 1-2. 300 g of CFE-419 was charged into the autoclave of the fluorination reactor and stirred while maintaining the temperature at 20°C. Nitrogen gas was blown into the autoclave at 20°C for 1 hour, and then 30% fluorine gas was blown into the autoclave at 20°C and a flow rate of 2.0 L / hour for 1 hour. Next, while blowing 30% fluorine gas at the same flow rate, a solution prepared by dissolving 8.4 g of Compound 1-1 obtained in Example 1-1, 0.04 g of Alcohol 1, 0.12 g of Carboxylic Acid 1, and 0.22 g of HF in 84.0 g of CFE-419 was injected into the autoclave over 5.3 hours.

[0208] Next, 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 was injected into the autoclave, and the benzene solution inlet of the autoclave was closed. Furthermore, stirring was continued for 1 hour while blowing in 30% fluorine gas at the same flow rate. Then, nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated using an evaporator, and then highly polar impurities were removed by silica gel chromatography (developing solvent: AC-2000), and 9.81 g (yield 99.1%) of the compound 1-2 was recovered. The structure and １９ The F-NMR data was the same as in Example 1-2.

[0209] Example 11 A fluorination reaction apparatus was prepared in the same manner as in Example 1-2. 300 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus and stirred while maintaining the temperature at 20°C. Nitrogen gas was blown into the autoclave at 20°C for 1 hour, and then 30% fluorine gas was blown into the autoclave at 20°C and a flow rate of 2.0 L / hour for 1 hour. Next, while blowing 30% fluorine gas at the same flow rate, a solution prepared by dissolving 8.4 g of Compound 1-1 obtained in Example 1-1 and 0.09 g of NaF in 84.0 g of CFE-419 was injected into the autoclave over 5.3 hours.

[0210] Next, 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 was injected into the autoclave, and the benzene solution inlet of the autoclave was closed. Furthermore, stirring was continued for 1 hour while blowing in 30% fluorine gas at the same flow rate. Then, nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated using an evaporator, and then highly polar impurities were removed by silica gel chromatography (developing solvent: AC-2000), and 9.79 g (yield 98.9%) of the compound 1-2 was recovered. The structure and １９ The F-NMR data was the same as in Example 1-2.

[0211] Example 12-1: 50.2 g of the following alcohol 2 and 100.9 g of NaF were added to a flask. NaF with an average primary particle size of 5 μm (manufactured by Kanto Chemical, Kagoshima special grade 37174-00) was used. 25.2 g of AC-2000 and the above (HFPO) ２ After mixing, the container was sealed and heated and stirred at 50°C for 10 hours. After heating and stirring for 10 hours, the container was allowed to cool and filtered to remove NaF. Then, (HFPO) ２ and AC-2000 were removed by distillation under reduced pressure. Alcohol 2: 1,5-pentanediol (product code: P0050, molecular weight: 104)

[0212] Highly polar impurities were removed by silica gel chromatography (developing solvent: AC-2000), and 349.65 g (yield 99.9%) of an ester compound was obtained. １ H-NMR and １９As a result of F-NMR analysis, the obtained compound was confirmed to be the following compound 12-1. １ H-NMR and １９ It was confirmed by F-NMR that the alcohol 2 and the carboxylic acid 1 were not detected, and by F ion concentration measurement, HF and NaF were not detected.

[0213] Compound 12-1: CF ３ CF ２ CF ２ OCF (CF ３ ) COOCH ２ CH ２ CH ２ CH ２ CH ２ OCOCF (CF ３ ) OCF ２ CF ２ CF ３ １ H-NMR (300.4 MHz, solvent CDCl ３ , standard TMS) δ (ppm): 1.6 (4H), 1.9 (2H), 4.1 (4H) １９ F-NMR (282.7 MHz, solvent CDCl ３ , Reference CFCl ３ ) δ (ppm): -81.7 (6F), -82.0 (6F), -85.6 (4F), -130.0 (4F), -131.8 (2F)

[0214] Example 12-2 A fluorination reaction apparatus was prepared in the same manner as in Example 1-2. 300 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus and stirred while maintaining the temperature at 20°C. Nitrogen gas was blown into the autoclave at 20°C for 1 hour, and then 30% fluorine gas was blown into the autoclave at 20°C and a flow rate of 2.0 L / hour for 1 hour. Next, while blowing 30% fluorine gas at the same flow rate, a solution prepared by dissolving 8.3 g of compound 12-1 obtained in Example 12-1, 0.04 g of alcohol 2, 0.12 g of carboxylic acid 1, 0.22 g of HF, and 0.09 g of NaF in 84.1 g of CFE-419 was injected into the autoclave over 3.1 hours.

[0215] ​Next, 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 was injected into the autoclave, and the benzene solution inlet of the autoclave was closed. Furthermore, stirring was continued for 1 hour while blowing in 30% fluorine gas at the same flow rate. Next, nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated using an evaporator, and then highly polar impurities were removed using silica gel chromatography (developing solvent: AC-2000), and 10.15 g (yield 98.0%) of the following compound 12-2 was recovered.

[0216] Compound 12-2: CF ３ CF ２ CF ２ OCF (CF ３ ) COOCF ２ CF ２ CF ２ CF ２ CF ２ OCOCF (CF ３ ) OCF ２ CF ２ CF ３ １９ F-NMR (282.7 MHz, solvent CDCl ３ , Reference CFCl ３ ) δ (ppm): -81.7 (6F), -82.0 (6F), -85.6 (4F), -92.8 (4F), -122.0 (4F), -122.6 (2F), -130.0 (4F), -131.8 (2F)

[0217] Example 13 A fluorination reactor was prepared in the same manner as in Example 1-2. 300 g of CFE-419 was charged into the autoclave of the fluorination reactor and stirred while maintaining the temperature at 20°C. Nitrogen gas was blown into the autoclave at 20°C for 1 hour, and then 30% fluorine gas was blown into the autoclave at 20°C and a flow rate of 2.0 L / hour for 1 hour. Next, while blowing 30% fluorine gas at the same flow rate, a solution prepared by dissolving 8.4 g of compound 12-1 obtained in Example 12-1, 0.09 g of alcohol 2, 0.13 g of carboxylic acid 1, 0.22 g of HF, and 0.09 g of NaF in 84.1 g of CFE-419 was injected into the autoclave over 3.1 hours.

[0218] ​Next, 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 was injected into the autoclave, and the benzene solution inlet of the autoclave was closed. Furthermore, stirring was continued for 1 hour while blowing in 30% fluorine gas at the same flow rate. Then, nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated using an evaporator, and highly polar impurities were removed by silica gel chromatography (developing solvent: AC-2000), and 7.44 g (yield 71.0%) of the compound 12-2 was recovered. The structure and １９ The F-NMR data was the same as in Example 12-2.

[0219] Example 14 A fluorination reactor was prepared in the same manner as in Example 1-2. 300 g of CFE-419 was charged into the autoclave of the fluorination reactor and stirred while maintaining the temperature at 20°C. Nitrogen gas was blown into the autoclave at 20°C for 1 hour, and then 30% fluorine gas was blown into the autoclave at 20°C and a flow rate of 2.0 L / hour for 1 hour. Next, while blowing 30% fluorine gas at the same flow rate, a solution prepared by dissolving 8.4 g of compound 12-1 obtained in Example 12-1, 0.05 g of alcohol 2, 0.18 g of carboxylic acid 1, 0.22 g of HF, and 0.09 g of NaF in 84.1 g of CFE-419 was injected into the autoclave over 3.1 hours.

[0220] Next, 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 was injected into the autoclave, and the benzene solution inlet of the autoclave was closed. Furthermore, stirring was continued for 1 hour while blowing in 30% fluorine gas at the same flow rate. Then, nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated using an evaporator, and highly polar impurities were removed by silica gel chromatography (developing solvent: AC-2000), and 7.42 g (yield 70.8%) of the compound 12-2 was recovered. The structure and １９ The F-NMR data was the same as in Example 12-2.

[0221] Example 15 A fluorination reactor was prepared in the same manner as in Example 1-2. 300 g of CFE-419 was charged into the autoclave of the fluorination reactor and stirred while maintaining the temperature at 20°C. Nitrogen gas was blown into the autoclave at 20°C for 1 hour, and then 30% fluorine gas was blown into the autoclave at 20°C and a flow rate of 2.0 L / hour for 1 hour. Next, while blowing 30% fluorine gas at the same flow rate, a solution prepared by dissolving 8.5 g of compound 12-1 obtained in Example 12-1, 0.05 g of alcohol 2, 0.13 g of carboxylic acid 1, 0.22 g of HF, and 0.18 g of NaF in 84.1 g of CFE-419 was injected into the autoclave over 3.1 hours.

[0222] Next, 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 was injected into the autoclave, and the benzene solution inlet of the autoclave was closed. Furthermore, stirring was continued for 1 hour while blowing in 30% fluorine gas at the same flow rate. Then, nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated using an evaporator, and highly polar impurities were removed by silica gel chromatography (developing solvent: AC-2000), and 7.58 g (yield 71.5%) of the compound 12-2 was recovered. The structure and １９ The F-NMR data was the same as in Example 12-2.

[0223] Example 16 A fluorination reactor was prepared in the same manner as in Example 1-2. 300 g of CFE-419 was charged into the autoclave of the fluorination reactor and stirred while maintaining the temperature at 20°C. Nitrogen gas was blown into the autoclave at 20°C for 1 hour, and then 30% fluorine gas was blown into the autoclave at 20°C and a flow rate of 2.0 L / hour for 1 hour. Next, while blowing 30% fluorine gas at the same flow rate, a solution prepared by dissolving 8.3 g of compound 12-1 obtained in Example 12-1, 0.001 g of alcohol 2, 0.12 g of carboxylic acid 1, 0.22 g of HF, and 0.09 g of NaF in 84.1 g of CFE-419 was injected into the autoclave over 3.1 hours.

[0224] Next, 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 was injected into the autoclave, and the benzene solution inlet of the autoclave was closed. Furthermore, stirring was continued for 1 hour while blowing in 30% fluorine gas at the same flow rate. Then, nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated using an evaporator, and then highly polar impurities were removed by silica gel chromatography (developing solvent: AC-2000), and 10.16 g (yield 98.1%) of the compound 12-2 was recovered. The structure and １９ The F-NMR data was the same as in Example 12-2.

[0225] Example 17 A fluorination reaction apparatus was prepared in the same manner as in Example 1-2. 300 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus and stirred while maintaining the temperature at 20°C. Nitrogen gas was blown into the autoclave at 20°C for 1 hour, and then 30% fluorine gas was blown into the autoclave at 20°C and a flow rate of 2.0 L / hour for 1 hour. Next, while blowing 30% fluorine gas at the same flow rate, a solution prepared by dissolving 8.4 g of compound 12-1 obtained in Example 12-1 and 0.001 g of alcohol 2 in 84.1 g of CFE-419 was injected into the autoclave over 3.1 hours.

[0226] Next, 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 was injected into the autoclave, and the benzene solution inlet of the autoclave was closed. Furthermore, stirring was continued for 1 hour while blowing in 30% fluorine gas at the same flow rate. Then, nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated using an evaporator, and then highly polar impurities were removed by silica gel chromatography (developing solvent: AC-2000), and 10.29 g (yield 98.2%) of the compound 12-2 was recovered. The structure and １９ The F-NMR data was the same as in Example 12-2.

[0227] Example 18 A fluorination reactor was prepared in the same manner as in Example 1-2. 300 g of CFE-419 was charged into the autoclave of the fluorination reactor and stirred while maintaining the temperature at 20°C. Nitrogen gas was blown into the autoclave at 20°C for 1 hour, and then 30% fluorine gas was blown into the autoclave at 20°C and a flow rate of 2.0 L / hour for 1 hour. Next, while blowing 30% fluorine gas at the same flow rate, a solution prepared by dissolving 8.4 g of compound 12-1 obtained in Example 12-1, 0.04 g of alcohol 2, 0.001 g of carboxylic acid 1, 0.22 g of HF, and 0.09 g of NaF in 84.1 g of CFE-419 was injected into the autoclave over 3.1 hours.

[0228] Next, 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 was injected into the autoclave, and the benzene solution inlet of the autoclave was closed. Furthermore, stirring was continued for 1 hour while blowing in 30% fluorine gas at the same flow rate. Then, nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated using an evaporator, and highly polar impurities were removed by silica gel chromatography (developing solvent: AC-2000), and 10.28 g (yield 98.1%) of the compound 12-2 was recovered. The structure and １９ The F-NMR data was the same as in Example 12-2.

[0229] Example 19 A fluorination reactor was prepared in the same manner as in Example 1-2. 300 g of CFE-419 was charged into the autoclave of the fluorination reactor and stirred while maintaining the temperature at 20°C. Nitrogen gas was blown into the autoclave at 20°C for 1 hour, and then 30% fluorine gas was blown into the autoclave at 20°C and a flow rate of 2.0 L / hour for 1 hour. Next, while blowing 30% fluorine gas at the same flow rate, a solution prepared by dissolving 8.4 g of compound 12-1 obtained in Example 12-1, 0.04 g of alcohol 2, 0.12 g of carboxylic acid 1, and 0.22 g of HF in 84.1 g of CFE-419 was injected into the autoclave over 3.1 hours.

[0230] Next, 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 was injected into the autoclave, and the benzene solution inlet of the autoclave was closed. Furthermore, stirring was continued for 1 hour while blowing in 30% fluorine gas at the same flow rate. Then, nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated using an evaporator, and then highly polar impurities were removed by silica gel chromatography (developing solvent: AC-2000), and 10.31 g (yield 98.4%) of the compound 12-2 was recovered. The structure and １９ The F-NMR data was the same as in Example 12-2.

[0231] Example 20 A fluorination reaction apparatus was prepared in the same manner as in Example 1-2. 300 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus and stirred while maintaining the temperature at 20°C. Nitrogen gas was blown into the autoclave at 20°C for 1 hour, and then 30% fluorine gas was blown into the autoclave at 20°C and a flow rate of 2.0 L / hour for 1 hour. Next, while blowing 30% fluorine gas at the same flow rate, a solution prepared by dissolving 8.5 g of compound 12-1 obtained in Example 12-1 and 0.09 g of NaF in 84.1 g of CFE-419 was injected into the autoclave over 3.1 hours.

[0232] Next, 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 was injected into the autoclave, and the benzene solution inlet of the autoclave was closed. Furthermore, stirring was continued for 1 hour while blowing in 30% fluorine gas at the same flow rate. Then, nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated using an evaporator, and then highly polar impurities were removed by silica gel chromatography (developing solvent: AC-2000), and 10.42 g (yield 98.3%) of the compound 12-2 was recovered. The structure and １９ The F-NMR data was the same as in Example 12-2.

[0233] Example 21 According to the method described in Example 2 of International Publication No. 2000-056694, the following compound 21 was recovered in a yield of 69.0%. Compound 21: CF ３ (CF ３ CF２ CF ２ O) CFCOOCF ２ CF (OCF ２ CF ２ CF ３ )CF ３

[0234] Example 22-1: 50.2 g of the alcohol 2 and 100.9 g of NaF were added to a flask. NaF with an average primary particle diameter of 5 μm (Kanto Chemical Co., Ltd., Kaga Special Grade 37174-00) was used. 25.2 g of AC-2000 and 100.9 g of NaF were added to the flask. ３ ) ２ 457 g of CFCOF was added and mixed. After mixing, the container was sealed and heated and stirred at 50°C for 10 hours. After 10 hours of heating and stirring, the container was allowed to cool and filtered to remove NaF. ３ ) ２ CFCOF and AC-2000 were removed by evaporation under reduced pressure.

[0235] Highly polar impurities were removed by silica gel chromatography (developing solvent: AC-2000), yielding 237.59 g (yield 96.9%) of an ester compound. １ H-NMR and １９ As a result of F-NMR analysis, the obtained compound was confirmed to be the following compound 22-1. １ H-NMR and １９ It was confirmed by F-NMR that the above alcohol 2 and the following carboxylic acid 2 were not detected, and by F ion concentration measurement, HF and NaF were not detected.

[0236] Compound 22-1: (CF ３ ) ２ CFCOOCH ２ CH ２ CH ２ CH ２ CH ２ OCOCF (CF ３ ) ２ １ H-NMR (300.4 MHz, solvent CDCl ３ , standard TMS) δ (ppm): 1.42 to 1.53 (2H), 1.70 to 1.84 (4H), 4.20 to 5.20 (4H) １９ ​F-NMR (282.7 MHz, solvent CDCl ３ , Reference CFCl ３ ) δ (ppm): -74.3 (12F), -81.9 (2F) Carboxylic acid 2: 2,3,3,3-tetrafluoro-2-(trifluoromethyl)-propionic acid (chemical formula: (CF ３ ) ２ CFCOOH)

[0237] Example 22-2 A fluorination reaction apparatus was prepared in the same manner as in Example 1-2. 300 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus and stirred while maintaining the temperature at 20°C. Nitrogen gas was blown into the autoclave at 20°C for 1 hour, and then 30% fluorine gas was blown into the autoclave at 20°C and a flow rate of 2.0 L / hour for 1 hour. Next, while blowing 30% fluorine gas at the same flow rate, a solution prepared by dissolving 8.3 g of compound 22-1 obtained in Example 22-1, 0.04 g of alcohol 2, 0.12 g of carboxylic acid 2, 0.22 g of HF, and 0.09 g of NaF in 84.1 g of CFE-419 was injected into the autoclave over 3.1 hours.

[0238] Next, 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 was injected into the autoclave, and the benzene solution inlet of the autoclave was closed. Furthermore, stirring was continued for 1 hour while blowing in 30% fluorine gas at the same flow rate. Then, nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated with an evaporator, and then １ It was confirmed by H-NMR that the H peak of the raw material had disappeared (conversion rate >99.9%), and 11.32 g (yield 98.9%) of the following compound 22-2 was recovered.

[0239] Compound 22-2: (CF ３ ) ２ CFCOOCF ２ CF ２ CF ２ CF ２ CF ２ OCOCF (CF ３ ) ２ １９ F-NMR (282.7 MHz, solvent CDCl ３ , Reference CFCl ３ ​) δ (ppm): -74.3 (12F), -86.1 (4F), -122.6 (2F), -125.7 (4F), -181.9 (2F)

[0240] Example 23-1: 50.1 g of the following alcohol 3 and 88.9 g of NaF were added to a flask. NaF with an average primary particle size of 5 μm (manufactured by Kanto Chemical, Kagoshima Special Grade 37174-00) was used. 25.2 g of AC-2000 and the following (HFPO) ３ After mixing, the container was sealed and heated and stirred at 50°C for 10 hours. After heating and stirring for 10 hours, the container was allowed to cool and filtered to remove NaF. Then, (HFPO) ３ and AC-2000 were removed by evaporation under reduced pressure.

[0241] Alcohol 3: 1,6-hexanediol (product code: H0099, molecular weight: 118) (HFPO) ３ 2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propoxy]-propanoyl fluoride (chemical formula: CF ３ CF ２ CF ２ OCF (CF ３ )CF ２ OCF (CF ３ ) COF, manufactured by Tokyo Chemical Industry Co., Ltd., product number: B1698)

[0242] Highly polar impurities were removed by silica gel chromatography (developing solvent: AC-2000), yielding 445.98 g (yield 98.0%) of an ester compound. １ H-NMR and １９ As a result of F-NMR analysis, the obtained compound was confirmed to be the following compound 23-1. １ H-NMR and １９ It was confirmed by F-NMR that the above alcohol 3 and the following carboxylic acid 3 were not detected, and by F ion concentration measurement, HF and NaF were not detected.

[0243] Compound 23-1: CF ３ CF ２ CF ２ OCF (CF３ )CF ２ OCF (CF ３ ) COOCH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OCOCF (CF ３ ) OCF ２ CF (CF ３ ) OCF ２ CF ２ CF ３ １ H-NMR (300.4 MHz, solvent CDCl ３ , standard TMS) δ (ppm): 1.27 (4H), 1.67 (4H), 4.20 (4H) １９ F-NMR (282.7 MHz, solvent CDCl ３ , Reference CFCl ３ ) δ (ppm): -80.8 (6F), -81.7 (14F), -82.0 (6F), -129.7 (4F), -131.8 (2F), -145.2 (2F) Carboxylic acid 3: 2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propoxy]-propionic acid (chemical formula: CF ３ CF ２ CF ２ OCF (CF ３ )CF ２ OCF (CF ３ ) COOH)

[0244] Example 23-2 A fluorination reaction apparatus was prepared in the same manner as in Example 1-2. 300 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus and stirred while maintaining the temperature at 20°C. Nitrogen gas was blown into the autoclave at 20°C for 1 hour, and then 30% fluorine gas was blown into the autoclave at 20°C and a flow rate of 2.0 L / hour for 1 hour. Next, while blowing 30% fluorine gas at the same flow rate, a solution prepared by dissolving 8.4 g of compound 23-1 obtained in Example 23-1, 0.04 g of the alcohol 3, 0.12 g of the carboxylic acid 3, 0.22 g of HF, and 0.09 g of NaF in 84.0 g of CFE-419 was injected into the autoclave over 3.1 hours. ​

[0245] Next, 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 was injected into the autoclave, and the benzene solution inlet of the autoclave was closed. Furthermore, stirring was continued for 1 hour while blowing in 30% fluorine gas at the same flow rate. Then, nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated with an evaporator, and then １ It was confirmed by H-NMR that the H peak of the raw material had disappeared (conversion rate >99.9%), and 9.95 g (yield 98.6%) of the following compound 23-2 was recovered.

[0246] Compound 23-2: CF ３ CF ２ CF ２ OCF (CF ３ )CF ２ OCF (CF ３ ) COOCF ２ CF ２ CF ２ CF ２ CF ２ CF ２ OCOCF (CF ３ ) OCF ２ CF (CF ３ ) OCF ２ CF ２ CF ３ １９ F-NMR (282.7 MHz, solvent CDCl ３ , Reference CFCl ３ ) δ (ppm): -80.8 (6F), -81.7 (14F), -82.0 (6F), -122.0 (4F), -125.3 (4F), -129.7 (4F), -131.8 (2F), -145.2 (2F)

[0247] Example 24-1: 50.0 g of the following alcohol 4 and 78.4 g of NaF were added to a flask. NaF with an average primary particle size of 5 μm (manufactured by Kanto Chemical, Kagoshima special grade 37174-00) was used. 25.1 g of AC-2000 and the above (HFPO) ３ After mixing, the container was sealed and heated and stirred at 50°C for 10 hours. After heating and stirring for 10 hours, the container was allowed to cool and filtered to remove NaF. Then, (HFPO) ３ ​and AC-2000 were removed by distillation under reduced pressure. Alcohol 4: Diethylene glycol monoethyl ether (chemical formula: CH ３ CH ２ OCH ２ CH ２ OCH ２ CH ２ OH, product code: E0048, molecular weight: 134)

[0248] Highly polar impurities were removed by silica gel chromatography (developing solvent: AC-2000), yielding 224.7 g (yield 98.4%) of an ester compound. １ H-NMR and １９ As a result of F-NMR analysis, the obtained compound was confirmed to be the following compound 24-1. １ H-NMR and １９ It was confirmed by F-NMR that the alcohol 4 and the carboxylic acid 3 were not detected, and by F ion concentration measurement, HF and NaF were not detected.

[0249] Compound 24-1: CH ３ CH ２ OCH ２ CH ２ OCH ２ CH ２ OCOCF (CF ３ ) OCF ２ CF (CF ３ ) OCF ２ CF ２ CF ３ １ H-NMR (300.4 MHz, solvent CDCl ３ , standard TMS) δ (ppm): 1.20 (3H), 3.53 (2H), 3.62 (4H), 3.71 (2H), 4.55 (2H) １９ F-NMR (282.7 MHz, solvent CDCl ３ , Reference CFCl ３ ) δ (ppm): -80.8 (3F), -81.7 (7F), -82.0 (3F), -129.7 (2F), -131.8 (1F), -145.2 (1F)

[0250] ​Example 24-2 A fluorination reaction apparatus was prepared in the same manner as in Example 1-2. 300 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus and stirred while maintaining the temperature at 20°C. Nitrogen gas was blown into the autoclave at 20°C for 1 hour, and then 30% fluorine gas was blown into the autoclave at 20°C and a flow rate of 2.0 L / hour for 1 hour. Next, while blowing 30% fluorine gas at the same flow rate, a solution prepared by dissolving 8.4 g of compound 24-1 obtained in Example 24-1, 0.04 g of alcohol 4, 0.12 g of carboxylic acid 3, 0.22 g of HF, and 0.09 g of NaF in 84.0 g of CFE-419 was injected into the autoclave over 3.1 hours.

[0251] Next, 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 was injected into the autoclave, and the benzene solution inlet of the autoclave was closed. Furthermore, stirring was continued for 1 hour while blowing in 30% fluorine gas at the same flow rate. Then, nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated with an evaporator, and then １ It was confirmed by H-NMR that the H peak of the raw material had disappeared (conversion rate >99.9%), and 11.48 g (yield 98.9%) of compound 24-2 was recovered.

[0252] Compound 24-2: CF ３ CF ２ OCF ２ CF ２ OCF ２ CF ２ OCOCF (CF ３ ) OCF ２ CF (CF ３ ) OCF ２ CF ２ CF ３ １９ F-NMR (282.7 MHz, solvent CDCl ３ , Reference CFCl ３ ) δ (ppm): -80.8 (3F), -81.7 (7F), -82.0 (3F), -86.3 (2F), -89.6 (3F), -91.6 (6F), -92.2 (2F), -129.7 (2F), -131.8 (1F), -145.2 (1F)

[0253] ​Example 25-1: 50.0 g of the following alcohol 5 and 30.9 g of NaF were added to a flask. NaF with an average primary particle size of 5 μm (manufactured by Kanto Chemical, Kagoshima Special Grade 37174-00) was used. 25.2 g of AC-2000 and the above (HFPO) ２ After mixing, the container was sealed and heated and stirred at 50°C for 10 hours. After heating and stirring for 10 hours, the container was allowed to cool and filtered to remove NaF. Then, (HFPO) ２ and AC-2000 were removed by distillation under reduced pressure. Alcohol 5: Polyoxyethylene-monomethyl ether (chemical formula: CH ３ -O-(C ２ H ４ O) ｎ -H, n=7, trade name: Uniox M-400, manufactured by NOF Corporation, molecular weight: 340)

[0254] Highly polar impurities were removed by silica gel chromatography (developing solvent: AC-2000), yielding 94.94 g (yield 99.0%) of an ester compound. １ H-NMR and １９ As a result of F-NMR analysis, the obtained compound was confirmed to be the following compound 25-1. １ H-NMR and １９ It was confirmed by F-NMR that the alcohol 5 and the carboxylic acid 1 were not detected, and by F ion concentration measurement, HF and NaF were not detected.

[0255] Compound 25-1: CH ３ -O-(C ２ H ４ O) ｎ -COCF (CF ３ ) OCF ２ CF ２ CF ３ １ H-NMR (300.4 MHz, solvent CDCl ３ , standard TMS) δ (ppm): 3.4 (3H), 3.5 (2H), 3.7 (24H), 4.9 (2H) Average value of number of units n: 7.0 １９ F-NMR (282.7 MHz, solvent CDCl ３ , Reference CFCl ３ ​) δ (ppm): -81.7 (3F), -82.0 (3F), -85.6 (2F), -130.0 (2F), -131.8 (1F)

[0256] Example 25-2 A fluorination reaction apparatus was prepared in the same manner as in Example 1-2. 300 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus and stirred while maintaining the temperature at 20°C. Nitrogen gas was blown into the autoclave at 20°C for 1 hour, and then 30% fluorine gas was blown into the autoclave at 20°C and a flow rate of 2.0 L / hour for 1 hour. Next, while blowing 30% fluorine gas at the same flow rate, a solution prepared by dissolving 8.4 g of compound 25-1 obtained in Example 25-1, 0.04 g of alcohol 5, 0.12 g of carboxylic acid 1, 0.22 g of HF, and 0.09 g of NaF in 84.0 g of CFE-419 was injected into the autoclave over 3.1 hours.

[0257] Next, 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 was injected into the autoclave, and the benzene solution inlet of the autoclave was closed. Furthermore, stirring was continued for 1 hour while blowing in 30% fluorine gas at the same flow rate. Then, nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated with an evaporator, and then １ It was confirmed by H-NMR that the H peak of the raw material had disappeared (conversion rate >99.9%), and 14.98 g (yield 96.1%) of the following compound 25-2 was recovered.

[0258] Compound 25-2: CF ３ -O-(C ２ F ４ O) ｎ -COCF (CF ３ ) OCF ２ CF ２ CF ３ １９ F-NMR (282.7 MHz, solvent CDCl ３ , Reference CFCl ３ ) δ (ppm): -59.1 (3F), -81.7 (3F), -82.0 (3F), -85.6 (2F), -86.3 (2F), -89.8 to -91.6 (22F), -92.2 (2F), -93.7 (2F), -130.0 (2F), -131.8 (1F) ​

[0259] Example 26-1: 50.0 g of the following alcohol 6 and 175 g of NaF were added to a flask. NaF with an average primary particle size of 5 μm (manufactured by Kanto Chemical, Kagoshima special grade 37174-00) was used. 25.2 g of AC-2000 and the above (HFPO) ３ After mixing, the container was sealed and heated and stirred at 50°C for 10 hours. After heating and stirring for 10 hours, the container was allowed to cool and filtered to remove NaF. Then, (HFPO) ３ and AC-2000 were removed by distillation under reduced pressure. Alcohol 6:1-propanol (product code: P0491, molecular weight: 60)

[0260] Highly polar impurities were removed by silica gel chromatography (developing solvent: AC-2000), yielding 439.4 g (yield 98.0%) of an ester compound. １ H-NMR and １９ As a result of F-NMR analysis, the obtained compound was confirmed to be the following compound 26-1. １ H-NMR and １９ It was confirmed by F-NMR that the alcohol 6 and the carboxylic acid 3 were not detected, and by F ion concentration measurement, it was confirmed that HF ​​and NaF were not detected.

[0261] Compound 26-1: CH ３ CH ２ CH ２ OCOCF (CF ３ ) OCF ２ CF (CF ３ ) OCF ２ CF ２ CF ３ １ H-NMR (300.4 MHz, solvent CDCl ３ , standard TMS) δ (ppm): 0.95 (3H), 1.73 (2H), 4.26 (2H) １９ F-NMR (282.7 MHz, solvent CDCl ３ , Reference CFCl ３ ) δ (ppm): -80.8 (3F), -81.7 (7F), -82.0 (3F), -129.7 (2F), -131.8 (1F), -145.2 (1F) ​

[0262] Example 26-2 A fluorination reaction apparatus was prepared in the same manner as in Example 1-2. 300 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus and stirred while maintaining the temperature at 20°C. Nitrogen gas was blown into the autoclave at 20°C for 1 hour, and then 30% fluorine gas was blown into the autoclave at 20°C and a flow rate of 2.0 L / hour for 1 hour. Next, while blowing 30% fluorine gas at the same flow rate, a solution prepared by dissolving 8.4 g of compound 26-1 obtained in Example 26-1, 0.04 g of alcohol 6, 0.12 g of carboxylic acid 3, 0.22 g of HF, and 0.09 g of NaF in 84.0 g of CFE-419 was injected into the autoclave over 3.1 hours.

[0263] Next, 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 was injected into the autoclave, and the benzene solution inlet of the autoclave was closed. Furthermore, stirring was continued for 1 hour while blowing in 30% fluorine gas at the same flow rate. Then, nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated with an evaporator, and then １ It was confirmed by H-NMR that the H peak of the raw material had disappeared (conversion rate >99.9%), and 10.00 g (yield 96.5%) of the following compound 26-2 was recovered.

[0264] Compound 26-2: CF ３ CF ２ CF ２ OCOCF (CF ３ ) OCF ２ CF (CF ３ ) OCF ２ CF ２ CF ３ １９ F-NMR (282.7 MHz, solvent CDCl ３ , Reference CFCl ３ ) δ (ppm): -80.8 (3F), -81.7 (7F), -82.0 (6F), -92.8 (2F), -129.7 (2F), -130.0 (2F), -131.8 (1F), -145.2 (1F)

[0265] ​The following table shows the amounts of OH compounds, carboxylic acids, HF, and NaF, as well as the yields of the target fluorine-containing ester compounds in Examples 1 to 26. The table also shows whether or not the ester compounds, which are raw materials for the fluorination reactions in Examples 1 to 26, contain an ether bond.

[0266]

[0267]

[0268]

[0269] As shown in Tables 1 to 3, the target fluorine-containing ester compound was obtained in higher yields in the Examples than in the Comparative Examples.

[0270] The method for producing a fluorine-containing ester compound according to the present disclosure can produce a fluorine-containing ester compound in a higher yield than conventional methods. The obtained fluorine-containing ester compound can be derived into a fluorine-containing compound having various functional groups (e.g., a hydroxyl group, an ethylenically unsaturated group, an epoxy group, a carboxyl group, etc.). Furthermore, the obtained fluorine-containing ester compound and fluorine-containing compound can be used as a surface treatment agent, an emulsifier, rubber, a surfactant, a solvent, a heat transfer medium, a pharmaceutical, an agricultural chemical, a lubricating oil, an intermediate thereof, etc.

[0271] The disclosure of Japanese Patent Application No. 2022-185980, filed on November 21, 2022, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A method for producing a fluorinated ester compound, comprising fluorinating an ester compound having at least one fluorinatable atom in a liquid containing the ester compound, wherein the liquid further contains at least one compound selected from the group consisting of a compound having a hydroxyl group, a compound having a carboxyl group, and sodium fluoride, and wherein, per 100 parts by mass of the ester compound, the content of the compound having a hydroxyl group is 0.5 parts by mass or less, the content of the compound having a carboxyl group is 2.0 parts by mass or less, and the content of the sodium fluoride is 2.0 parts by mass or less.

2. The method for producing a fluorine-containing ester compound according to claim 1, wherein the ester compound comprises an ester compound having an ether bond, and the liquid further contains hydrogen fluoride, the content of the hydrogen fluoride being 3.0 parts by mass or less per 100 parts by mass of the ester compound.

3. The method for producing a fluorine-containing ester compound according to claim 1, wherein at least one selected from the group consisting of the content of the compound having a hydroxyl group, the content of the compound having a carboxy group, and the content of sodium fluoride is 0.01 parts by mass or more per 100 parts by mass of the ester compound.

4. The method for producing a fluorine-containing ester compound according to claim 2, wherein at least one selected from the group consisting of the content of the compound having a hydroxyl group, the content of the compound having a carboxy group, the content of the sodium fluoride, and the content of the hydrogen fluoride is 0.01 parts by mass or more per 100 parts by mass of the ester compound.

5. The method for producing a fluorine-containing ester compound according to any one of claims 1 to 4, wherein the ester compound comprises at least one selected from the group consisting of compounds represented by the following formula (1) and compounds represented by the following formula (2): Ａ１ -O-(C=O)-R Ｂ１ …(1) R Ｂ２ -(C=O)-OR Ａ２ -O-(C=O)-R Ｂ３ ... (2) In formulas (1) and (2), R Ａ１ , R Ｂ１ , R Ｂ２ , and R Ｂ３ are each independently a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogeno (heteroatom-containing monovalent saturated hydrocarbon) group; R Ａ２ is a divalent saturated hydrocarbon group, a halogeno divalent saturated hydrocarbon group, a heteroatom-containing divalent saturated hydrocarbon group, or a halogeno (heteroatom-containing divalent saturated hydrocarbon) group.

6. The method for producing a fluorine-containing ester compound according to claim 5, wherein the compound having a hydroxyl group includes at least one selected from the group consisting of compounds represented by the following formula (3) and compounds represented by the following formula (4): Ａ３ -OH...(3) HO-R Ａ４ —OH (4) In formulas (3) and (4), R Ａ３ is a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogeno (heteroatom-containing monovalent saturated hydrocarbon) group; R Ａ４ is a divalent saturated hydrocarbon group, a halogeno divalent saturated hydrocarbon group, a heteroatom-containing divalent saturated hydrocarbon group, or a halogeno (heteroatom-containing divalent saturated hydrocarbon) group.

7. R in the formula (3) Ａ３ is R in the formula (1). Ａ１ and R in the formula (4) Ａ４ is R in the formula (2). Ａ２ The method for producing a fluorine-containing ester compound according to claim 6, wherein the above formula (I) is the same as 8. The method for producing a fluorine-containing ester compound according to claim 5, wherein the compound having a carboxy group includes a compound represented by the following formula (5): Ｂ４ -(C=O)-OH...(5) In formula (5), R Ｂ４ is a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogeno(heteroatom-containing monovalent saturated hydrocarbon) group.

9. R in the formula (5) Ｂ４ is R in the formula (1). Ｂ１ Or R in the formula (2) Ｂ２ The method for producing a fluorine-containing ester compound according to claim 8, wherein the above formula (I) is the same as 10. A composition comprising an ester compound having at least one fluorinatable atom and at least one member selected from the group consisting of a compound having a hydroxyl group, a compound having a carboxyl group, and sodium fluoride, wherein the content of the compound having a hydroxyl group is 0.5 parts by mass or less, the content of the compound having a carboxyl group is 2.0 parts by mass or less, and the content of the sodium fluoride is 2.0 parts by mass or less, per 100 parts by mass of the ester compound.

11. The composition according to claim 10, wherein the ester compound comprises an ester compound having an ether bond, the composition further contains hydrogen fluoride, and the content of the hydrogen fluoride is 3.0 parts by mass or less per 100 parts by mass of the ester compound.

12. The composition according to claim 10, wherein the content of at least one selected from the group consisting of the compound having a hydroxyl group, the compound having a carboxyl group, and the sodium fluoride is 0.01 parts by mass or more per 100 parts by mass of the ester compound.

13. The composition according to claim 11, wherein the content of at least one selected from the group consisting of the compound having a hydroxyl group, the compound having a carboxyl group, the sodium fluoride, and the hydrogen fluoride is 0.01 parts by mass or more per 100 parts by mass of the ester compound.

14. The composition according to any one of claims 10 to 13, wherein the ester compound includes at least one selected from the group consisting of compounds represented by the following formula (1) and compounds represented by the following formula (2), the compound having a hydroxyl group includes at least one selected from the group consisting of compounds represented by the following formula (3) and compounds represented by the following formula (4), and the compound having a carboxy group includes a compound represented by the following formula (5). R Ａ１ -O-(C=O)-R Ｂ１ …(1) R Ｂ２ -(C=O)-OR Ａ２ -O-(C=O)-R Ｂ３ …(2) R Ａ３ -OH...(3) HO-R Ａ４ -OH ... (4) R Ｂ４ -(C=O)-OH...(5) In formulas (1) to (5), R Ａ１ , R Ａ３ , R Ｂ１ , R Ｂ２ , R Ｂ３ , and R Ｂ４ are each independently a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogeno (heteroatom-containing monovalent saturated hydrocarbon) group; R Ａ２ and R Ａ４ are each independently a divalent saturated hydrocarbon group, a halogeno divalent saturated hydrocarbon group, a heteroatom-containing divalent saturated hydrocarbon group, or a halogeno (heteroatom-containing divalent saturated hydrocarbon) group.

15. R in the formula (3) Ａ３ is R in the formula (1). Ａ１ and R in the formula (4) Ａ４ is R in the formula (2). Ａ２ and R in the formula (5) Ｂ４ is R in the formula (1). Ｂ１ Or R in the formula (2) Ｂ２ The composition of claim 14, wherein