Method for producing fluorine-containing ester compound, and composition

Abstract

A method for producing a fluorine-containing ester compound, which comprises fluorinating an ester compound having at least one fluorinated atom in a liquid containing the ester compound, the liquid further containing 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, 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 with respect to 100 parts by mass of the ester compound.

Description

Technical Field

[0001] The present disclosure relates to a method for manufacturing a fluorine-containing ester compound and a composition. Background Art

[0002] Among fluorine-containing ester compounds, there are many industrially useful compounds, and various manufacturing methods have been developed in the past. For example, Patent Document 1 describes a method for manufacturing a fluorine-containing ester compound, in which fluorine gas is supplied to a liquid containing an ester compound obtained by reacting a compound having a hydroxyl group with a carboxylic acid halide, and the ester compound is fluorinated to manufacture a fluorine-containing ester compound

[0003] Prior Art Documents

[0004] Patent Documents

[0005] Patent Document 1: International Publication No. 2000 / 056694 Summary of the Invention

[0006] Problems to be Solved by the Invention

[0007] If a compound having a hydroxyl group is reacted with a carboxylic acid halide to manufacture an ester compound, there is a possibility that the unreacted compound having a hydroxyl group remains, or a compound having a carboxyl group is generated by the reaction of the carboxylic acid halide. That is, a composition containing an ester compound obtained by reacting a compound having a hydroxyl group with a carboxylic acid halide may contain a compound having a hydroxyl group, a compound having a carboxyl group, etc. as impurities. In addition, when sodium fluoride is used as a catalyst in the process of manufacturing an ester compound, there is a possibility that sodium fluoride remains directly as an impurity in the composition containing the obtained ester compound.

[0008] When fluorinating an ester compound in a liquid containing a composition containing these impurities, the presence of these impurities contained in the liquid sometimes affects the yield of the target product in the fluorination reaction.

[0009] An object of one embodiment of the present invention is to provide a method for manufacturing a fluorine-containing ester compound and a composition that can obtain a fluorine-containing ester compound as a target product in a high yield.

[0010] Solutions to the Problems

[0011] The present disclosure includes the following aspects.

[0012] <1>

[0013] A method for manufacturing a fluorine-containing ester compound, which includes fluorinating an ester compound having at least one fluorinable atom in a liquid

[0014] 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. With respect 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 carboxyl group is 2.0 parts by mass or less, and the content of sodium fluoride is 2.0 parts by mass or less.

[0015] <2>

[0016] The method for producing a fluorine-containing ester compound according to <1>, wherein the ester compound includes an ester compound having an ether bond.

[0017] The liquid further contains hydrogen fluoride. With respect to 100 parts by mass of the ester compound, the content of hydrogen fluoride is 3.0 parts by mass or less.

[0018] <3>

[0019] The method for producing a fluorine-containing ester compound according to <1>, wherein with respect to 100 parts by mass of the ester compound, 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 carboxyl group, and the content of sodium fluoride is 0.01 part by mass or more.

[0020] <4>

[0021] The method for producing a fluorine-containing ester compound according to <2>, wherein with respect to 100 parts by mass of the ester compound, 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 carboxyl group, the content of sodium fluoride, and the content of hydrogen fluoride is 0.01 part by mass or more.

[0022] <5>

[0023] The method for producing a fluorine-containing ester compound according to any one of <1> to <4>, 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).

[0024] R A1 -O-(C=O)-R B1 …(1)

[0025] R B2 -(C=O)-O-R A2 -O-(C=O)-R B3 …(2)

[0026] In formulas (1) and (2),

[0027] R A1 、R B1 、RB2 and R B3 each independently represents a monovalent saturated hydrocarbon group, a halogenated monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogenated (heteroatom-containing monovalent saturated hydrocarbon) group,

[0028] R A2 represents 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.

[0029] <6>

[0030] The method for producing a fluorine-containing ester compound according to any one of <1> to <5>, wherein the compound having a hydroxyl group contains at least one selected from the group consisting of the compound represented by the following formula (3) and the compound represented by the following formula (4),

[0031] R A3 -OH…(3)

[0032] HO-R A4 -OH…(4)

[0033] In formulas (3) and (4),

[0034] R A3 represents a monovalent saturated hydrocarbon group, a halogenated monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogenated (heteroatom-containing monovalent saturated hydrocarbon) group,

[0035] R A4 represents 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.

[0036] <7>

[0037] The method for producing a fluorine-containing ester compound according to <6>, wherein R in formula (3) A3 is the same as R in formula (1), and R in formula (4) A1 is the same as R in formula (2). A4 is the same as R in formula (2). A2 is the same.

[0038] <8>

[0039] The method for producing a fluorine-containing ester compound according to any one of <1> to <7>, wherein the compound having a carboxyl group contains the compound represented by the following formula (5),

[0040] R B4 -(C=O)-OH…(5)

[0041] In formula (5),

[0042] RB4 is a monovalent saturated hydrocarbon group, a halogenated monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogenated (heteroatom-containing monovalent saturated hydrocarbon) group.

[0043] <9>

[0044] The method for producing a fluorine-containing ester compound according to <8>, wherein R in the formula (5) B4 is the same as R in the formula (1) B1 or R in the formula (2) B2 is the same.

[0045] <10>

[0046] A composition comprising: an ester compound having at least one fluorinable 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, based on 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 carboxyl group is 2.0 parts by mass or less, and the content of sodium fluoride is 2.0 parts by mass or less.

[0047] <11>

[0048] The composition according to <10>, wherein the ester compound includes an ester compound having an ether bond, and the composition further contains hydrogen fluoride, and based on 100 parts by mass of the ester compound, the content of hydrogen fluoride is 3.0 parts by mass or less.

[0049] <12>

[0050] The composition according to <10>, wherein, based on 100 parts by mass of the ester compound, 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 carboxyl group, and the content of sodium fluoride is 0.01 part by mass or more.

[0051] <13>

[0052] The composition according to <11>, wherein, based on 100 parts by mass of the ester compound, 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 carboxyl group, the content of sodium fluoride, and the content of hydrogen fluoride is 0.01 part by mass or more.

[0053] <14>

[0054] The composition according to any one of <10> to <13>, wherein the ester compound includes at least one selected from the group consisting of the compound represented by the following formula (1) and the compound represented by the following formula (2).

[0055] The compound having a hydroxyl group includes at least one selected from the group consisting of the compound represented by the following formula (3) and the compound represented by the following formula (4).

[0056] The compound having a carboxyl group includes the compound represented by the following formula (5).

[0057] R A1 -O-(C=O)-R B1 …(1)

[0058] R B2 -(C=O)-O-R A2 -O-(C=O)-R B3 …(2)

[0059] R A3 -OH…(3)

[0060] HO-R A4 -OH…(4)

[0061] R B4 -(C=O)-OH…(5)

[0062] In formulas (1) to (5),

[0063] R A1 、R A3 、R B1 、R B2 、R B3 and R B4 are each independently a monovalent saturated hydrocarbon group, a halogenated monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogenated (heteroatom-containing monovalent saturated hydrocarbon) group.

[0064] 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.

[0065] <15>

[0066] The composition according to <14>, wherein R A3 in formula (3) is the same as R A1 in formula (1), R A4 in formula (4) is the same as R A2 in formula (2), and R B4 in formula (5) is the same as R B1 in formula (1) or R B2 in formula (2).

[0067] Effects of the Invention

[0068] According to the present disclosure, a method for producing a fluorinated ester compound and a composition capable of obtaining a fluorinated ester compound as a target product in a high yield can be provided. Detailed Embodiments

[0069] Hereinafter, modes for implementing the 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, unless otherwise specified, components (including element steps, etc.) are not essential. The same applies to numerical values and their ranges, which do not limit the embodiments of the present disclosure.

[0070] In the present disclosure, a numerical range represented by "~" means a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively.

[0071] In the numerical ranges gradually described in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range can be replaced with the upper limit value or the lower limit value of the numerical range described in other stages. In addition, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range can be replaced with the value shown in the examples.

[0072] In the present disclosure, a combination of two or more preferred modes is a more preferred mode.

[0073] In the present disclosure, when there are multiple substances corresponding to each component, unless otherwise specified, the amount of each component refers to the total amount of the multiple substances.

[0074] In the present disclosure, when a compound is represented by a specific formula (X), the compound represented by the formula (X) is sometimes referred to as compound (X).

[0075] [Method for Producing Fluorinated Ester Compound]

[0076] The method for producing a fluorinated ester compound according to an embodiment of the present disclosure includes fluorinating an ester compound having at least one fluorinable atom in a liquid containing the ester compound, the liquid further containing at least one selected from the group consisting of a compound having a hydroxyl group, a compound having a carboxyl group, and sodium fluoride. 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 sodium fluoride is 2.0 parts by mass or less with respect to 100 parts by mass of the ester compound.

[0077] Hereinafter, a compound having a hydroxyl group is also 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 is also referred to as the "amount of OH compound", a compound having a carboxyl group is also referred to as a "carboxylic acid compound", the content of the carboxylic acid compound relative to 100 parts by mass of the ester compound in the liquid is also referred to as the "amount of carboxylic acid", sodium fluoride is also referred to as "NaF", and the content of sodium fluoride relative to 100 parts by mass of the ester compound in the liquid is also referred to as the "amount of NaF".

[0078] As described above, a composition containing an ester compound obtained by the reaction of an OH compound with a carboxylic acid halide sometimes contains unreacted OH compounds, carboxylic acid compounds formed by the reaction of unreacted carboxylic acid halides, etc. as impurities. In addition, when NaF is used as a catalyst in the process of manufacturing an ester compound, NaF sometimes remains directly as an impurity in the composition containing the obtained ester compound.

[0079] Moreover, when fluorinating an ester compound in a liquid containing a composition containing these impurities, the presence of these impurities contained in the liquid sometimes affects the yield of the target product in the fluorination reaction.

[0080] Specifically, when a fluorination reaction is carried out in the presence of an OH compound, the reaction of the OH compound with fluorine is accompanied by a large amount of reaction heat. Due to this reaction heat, sometimes the ester compound as a raw material for the fluorination reaction, the fluorinated ester compound as the target product, etc. are decomposed. Moreover, when the decomposition of the raw material, the decomposition of the target product, etc. occur repeatedly, the yield of the target product decreases.

[0081] Similarly, when a fluorination reaction is carried out in the presence of a carboxylic acid compound, the reaction of the carboxylic acid compound with fluorine is accompanied by a large amount of reaction heat. When the decomposition of the raw material, the decomposition of the target product, etc. occur repeatedly, the yield of the target product sometimes decreases.

[0082] In addition, when a fluorination reaction is carried out in the presence of NaF, due to the action of NaF, sometimes the ester bond of the ester compound as a raw material and the fluorinated ester compound as the target product is decomposed. Moreover, when the decomposition of the raw material and the target product occurs repeatedly, the yield of the target product decreases.

[0083] In contrast, in the method for manufacturing the fluorinated ester compound described above, the amount of OH compound is 0.5 part 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. Therefore, it is presumed that the decomposition of the raw material and the target product accompanying the fluorination reaction of the ester compound is suppressed, and the yield of the target product becomes high.

[0084] In addition, in the method for producing the fluorine-containing ester compound described above, the liquid containing the ester compound further contains at least one selected from the group consisting of an OH compound, a carboxylic acid compound, and sodium fluoride. Therefore, the yield of the target product becomes high. The reason is unknown, but it can be speculated as follows.

[0085] It is considered that by making the liquid contain at least one selected from the group consisting of an OH compound, a carboxylic acid compound, and sodium fluoride, the decomposition reaction of at least one of the raw material and the target product proceeds slightly, generating free radicals. Moreover, it can be speculated that this is because the fluorination reaction of the ester compound becomes easier due to the slightly generated free radicals.

[0086] The method of making the liquid contain at least one selected from the group consisting of an OH compound, a carboxylic acid compound, and sodium fluoride, and making the amounts of the OH compound, the carboxylic acid, and the NaF within the respective ranges is not particularly limited.

[0087] When an ester compound is produced by reacting an OH compound with a carboxylic acid halide, a composition in which the amounts of the OH compound, the carboxylic acid, and the NaF are all greater than the above ranges is often obtained. In this case, the OH compound, the carboxylic acid compound, and sodium fluoride can be removed from the composition in which the amounts of the OH compound, the carboxylic acid, and the NaF are all greater than the above ranges. By the aforementioned removal, a composition containing at least one selected from the group consisting of an OH compound, a carboxylic acid compound, and sodium fluoride, and in which the amounts of the OH compound, the carboxylic acid, and the NaF are within the respective ranges is obtained. Moreover, the fluorination reaction can be carried out in the liquid containing the obtained composition.

[0088] The method for removing the OH compound, the carboxylic acid compound, and sodium fluoride from the composition is not particularly limited, and examples include removal using an adsorbent, removal using filtration, removal using vacuum distillation, removal using centrifugation, removal using extraction, combinations thereof, and the like.

[0089] In the removal using an adsorbent, when the adsorbent is a granular solid, for example, by passing the combined flow through a packed column filled with a dry adsorbent, at least a part of the OH compound, the carboxylic acid compound, and sodium fluoride is removed from the composition.

[0090] Examples of the adsorbent include silica, zeolite, activated carbon, activated alumina, etc. Among them, from the viewpoint of adsorption ability, silica is preferred. Examples of silica include spherical silica gel (product name: M.S.GEL, product number: D75-60A(N), manufacturer: AGC Si-Tech Co., Ltd.).

[0091] The amounts of the OH compound, the carboxylic acid, and the NaF in the above composition can be controlled by adjusting the removal amounts of the OH compound, the carboxylic acid compound, and sodium fluoride, or can be controlled by adding separately after the removal.

[0092] When an OH compound is additionally added to the composition, the additionally added OH compound is optionally the same as or different from the OH compound used in the production of the ester compound. Further, when a carboxylic acid compound is additionally added to the composition, the additionally added carboxylic acid compound is optionally the same as or different from the carboxylic acid compound obtained by reacting a carboxylic acid halide used in the production of the ester compound.

[0093] That is, when the liquid for fluorinating the ester compound contains an OH compound, the structure other than the hydroxyl group in the OH compound is optionally the same as or different from the alcohol residue of the ester compound. Further, when the liquid for fluorinating the ester compound contains a carboxylic acid compound, the structure other than the carboxyl group in the carboxylic acid compound is optionally the same as or different from the carboxylic acid residue of the ester compound.

[0094] 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 the OH compound, the amount of the carboxylic acid, and the amount of NaF is preferably 0.01 part by mass or more.

[0095] Part of the amount of the OH compound, the amount of the carboxylic acid, and the amount of NaF may be 0.01 part by mass or more, or all of the amount of the OH compound, the amount of the carboxylic acid, and the amount of NaF may be 0.01 part by mass or more.

[0096] In one embodiment of the present disclosure, the ester compound as a raw material for the fluorination reaction may include an ester compound having an ether bond.

[0097] 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 is preferably 3.0 parts by mass or less with respect to 100 parts by mass of the ester compound contained in the liquid.

[0098] Hereinafter, hydrogen fluoride is also referred to as "HF", and the content of HF with respect to 100 parts by mass of the ester compound in the liquid is also referred to as the "HF amount".

[0099] 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 sometimes contains HF as an impurity.

[0100] When a fluorination reaction of an ester compound having an ether bond is carried out in the presence of HF, the ether bond of the ester compound having an ether bond as a raw material and the ether bond of the fluorinated ester compound having an ether bond as the target product sometimes decompose due to the action of HF. Moreover, when the decomposition of the ether bond occurs repeatedly, the yield of the target product decreases.

[0101] Therefore, it is speculated that by making the amount of HF within the above range, the decomposition of the ether bond accompanying the fluorination reaction of the ester compound is suppressed, and the yield of the target product becomes high.

[0102] In addition, it is speculated that by making the liquid contain HF, the fluorination reaction of the ester compound becomes easier due to the radicals generated by the decomposition reaction of the ether bond, and the yield of the target product becomes high.

[0103] The method of making the liquid contain HF and making the amount of HF within the above range is not particularly limited.

[0104] When an ester compound is produced by reacting an OH compound with a carboxylic acid halide, a composition with an HF amount greater than the above range is often obtained. In this case, an HF-containing composition with an HF amount within the above range can be obtained by removing HF from the composition with an HF amount greater than the above range, and the fluorination reaction can be carried out in a liquid containing the obtained composition.

[0105] The amount of HF in the above composition can be controlled by adjusting the amount of HF removed, or can also be controlled by adding separately after removal. As a method for removing HF from the composition, removal by vacuum distillation, removal using the above adsorbent, etc. can be cited.

[0106] When the ester compound contains an ester compound having an ether bond, from the viewpoint of obtaining a high yield of the target product, at least one of the OH compound amount, carboxylic acid amount, NaF amount, and HF amount is preferably 0.01 part by mass or more.

[0107] Part of the OH compound amount, carboxylic acid amount, NaF amount, and HF amount can be 0.01 part by mass or more, or all of the OH compound amount, carboxylic acid amount, NaF amount, and HF amount can be 0.01 part by mass or more.

[0108] <Liquid>

[0109] The liquid contains at least: an ester compound having at least one fluorinable atom, and at least one selected from the group consisting of an OH compound, a carboxylic acid compound, and sodium fluoride. Optionally, it can also contain a solvent, other additives, etc.

[0110] (Ester compound)

[0111] The ester compound is an organic compound having at least one fluorinable atom and an ester bond, and is not particularly limited.

[0112] The ester compound may have only one fluorinable atom, or may have two or more. As the number of fluorinable atoms contained in one molecule of the ester compound, for example, 1 to 1000 can be cited, preferably 1 to 500, more preferably 1 to 100.

[0113] The ester compound may have only one ester bond (i.e., -O-(C=O)-), or may have two or more. From the viewpoint of easy availability, the number of ester bonds contained in the ester compound is preferably 1 or 2. That is, the ester compound is preferably a monoester compound or a diester compound.

[0114] Examples of the atom that can be fluorinated include a hydrogen atom, a bromine atom, an iodine atom, etc. Among them, a hydrogen atom is preferred. The ester compound preferably has a hydrogen atom as the atom that can be fluorinated.

[0115] Examples of the ester compound include the compound represented by the following formula (1), the compound represented by the following formula (2), etc.

[0116] R A1 -O-(C=O)-R B1 …(1)

[0117] R B2 -(C=O)-O-R A2 -O-(C=O)-R B3 …(2)

[0118] In formulas (1) and (2),

[0119] R A1 、R B1 、R B2 and R B3 are each independently a monovalent saturated hydrocarbon group, a halogenated monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogenated (heteroatom-containing monovalent saturated hydrocarbon) group,

[0120] R A2 is 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.

[0121] In the present disclosure, the "monovalent saturated hydrocarbon group" can be any of a linear alkyl group, a branched alkyl group, and a cycloalkyl group. The "divalent saturated hydrocarbon group" can be any of a linear alkylene group, a branched alkylene group, and a cycloalkylene group. A linear alkyl group, a branched alkyl group, a linear alkylene group, and a branched alkylene group may contain an alicyclic structure.

[0122] In the present disclosure, "halogenated" means that one or more hydrogen atoms present in the group are replaced by at least one halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Hydrogen atoms may optionally be present or absent in the group.

[0123] In the present disclosure, "halogenated monovalent saturated hydrocarbon group" refers to a group in which one or more hydrogen atoms in a monovalent saturated hydrocarbon group are replaced by halogen atoms. "Halogenated divalent saturated hydrocarbon group" refers to a group in which one or more hydrogen atoms in a divalent saturated hydrocarbon group are replaced by halogen atoms.

[0124] In the present disclosure, "heteroatom" refers to an atom other than a carbon atom and a hydrogen atom, and examples thereof include a nitrogen atom, an oxygen atom, and a sulfur atom.

[0125] In the present disclosure, "heteroatom-containing monovalent saturated hydrocarbon group" refers to a group that contains a divalent heteroatom or a divalent group containing a heteroatom in a monovalent saturated hydrocarbon group. "Heteroatom-containing divalent saturated hydrocarbon group" refers to a group that contains a divalent heteroatom or a divalent group containing a heteroatom in a divalent saturated hydrocarbon group. Examples of the divalent heteroatom include -O- and -S-. In addition, examples of the divalent group containing a heteroatom include -NH-, -C(=O)-, and -SO2-.

[0126] In the present disclosure, "halogenated (heteroatom-containing monovalent saturated hydrocarbon) group" refers to a group in which one or more hydrogen atoms in the above-mentioned heteroatom-containing monovalent saturated hydrocarbon group are replaced by halogen atoms. "Halogenated (heteroatom-containing divalent saturated hydrocarbon) group" refers to a group in which one or more hydrogen atoms in the above-mentioned heteroatom-containing divalent saturated hydrocarbon group are replaced by halogen atoms.

[0127] In formula (1), at least one of R A1 and R B1 preferably contains a hydrogen atom. In addition, in formula (2), at least one of the group consisting of R A2 , R B2 and R B3 preferably contains a hydrogen atom.

[0128] [R A1

[0129] In formula (1), R A1 is a monovalent saturated hydrocarbon group, a halogenated monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogenated (heteroatom-containing monovalent saturated hydrocarbon) group.

[0130] Examples of the monovalent saturated hydrocarbon group represented by R A1 include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, and a cyclohexyl group.

[0131] Examples of the halogenated monovalent saturated hydrocarbon group represented by R A1 are preferably halogenated alkyl groups. The halogen atom contained in the halogenated monovalent saturated hydrocarbon group is preferably a fluorine atom, a chlorine atom, or a bromine atom, and more preferably a fluorine atom.

[0132] R A1 ​The heteroatom-containing monovalent saturated hydrocarbon group shown is preferably a monovalent saturated hydrocarbon group containing an etheric oxygen atom (i.e., -O-), more preferably an alkyl group containing an etheric oxygen atom.

[0133] As R A1 The halogenated (heteroatom-containing monovalent saturated hydrocarbon) group shown is preferably halogenated (heteroatom-containing alkyl). The halogen atom contained in the halogenated (heteroatom-containing monovalent saturated hydrocarbon) group is preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogenated (heteroatom-containing monovalent saturated hydrocarbon) group is preferably a halogenated monovalent saturated hydrocarbon group containing an etheric oxygen atom, more preferably a halogenated alkyl group containing an etheric oxygen atom.

[0134] From the viewpoint of excellent solubility in a solvent described later, the carbon number of R A1 is preferably 1 to 200, more preferably 3 to 100.

[0135] Among them, from the viewpoint of excellent solubility in a liquid, R A1 is preferably represented by the following formula (A1). That is, R A1 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.

[0136] R 11 O-(R 12 O) m1 -R 13 -…(A1)

[0137] In formula (A1), R 11 is an alkyl group optionally having a fluorine atom, and R 12 are each independently an alkylene group having 1 to 6 carbon atoms optionally having a fluorine atom, R 13 is an alkylene group having 1 to 6 carbon atoms optionally having a fluorine atom, and m1 is an integer of 0 to 500.

[0138] In formula (A1), as R 11 , for example, an alkyl group and a fluoroalkyl group can be cited.

[0139] From the viewpoint of excellent solubility in a solvent described later, the carbon number of R 11 is preferably 1 to 100, more preferably 1 to 50, further preferably 1 to 10, and particularly preferably 1 to 6.

[0140] R 11 The alkyl group shown can be a linear alkyl group, a branched alkyl group, or an alkyl group having a ring structure.

[0141] R 11 The fluoroalkyl group shown can be a linear fluoroalkyl group, a branched fluoroalkyl group, or a fluoroalkyl group having a ring structure.

[0142] Among them, R 11 is preferably an alkyl group, more preferably a linear alkyl group, and still more preferably a linear alkyl group having 1 to 6 carbon atoms.

[0143] In formula (A1), -(R 12 O) m1 - is preferably represented by the following formula (A2).

[0144] -[(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)

[0145] Among them,

[0146] R f1 is a fluoroalkylene group having 1 carbon atom,

[0147] R f2 is a fluoroalkylene group having 2 carbon atoms,

[0148] R f3 is a fluoroalkylene group having 3 carbon atoms,

[0149] R f4 is a fluoroalkylene group having 4 carbon atoms,

[0150] R f5 is a fluoroalkylene group having 5 carbon atoms,

[0151] R f6 is a fluoroalkylene group having 6 carbon atoms.

[0152] k1, k2, k3, k4, k5 and k6 each independently represent an integer of 0 or more, and k1 + k2 + k3 + k4 + k5 + k6 is an integer of 0 to 500.

[0153] From the viewpoint of excellent solubility in a 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.

[0154] It should be noted that the bonding order of (R f1 O) to (R f6 O) in formula (A2) is arbitrary. k1 to k6 in formula (A2) respectively represent (R f1 O) to (Rf6 The number of (R f5 O), rather than the configuration. For example, (R k5 represents that the number of (R f5 O) is k5, rather than the block configuration structure of (R f5 O). Similarly, the order of description of (R k5 O) to (R f1 O) does not represent the bonding order of each unit. f6 Among R

[0155] R f3 to R f6 the fluoroalkylene group may be a linear fluoroalkylene group, a branched fluoroalkylene group, or a fluoroalkylene group having a ring structure.

[0156] Specific examples of R f1 include -CF2- and -CHF-.

[0157] Specific examples of R f2 include -CF2CF2-, -CF2CHF-, -CHFCF2-, -CHFCHF-, -CH2CF2- and -CH2CHF-.

[0158] Specific examples of R f3 include -CF2CF2CF2-, -CF2CHFCF2-, -CF2CH2CF2-, -CHFCF2CF2-, -CHFCHFCF2-, -CHFCHFCHF-, -CHFCH2CF2-, -CH2CF2CF2-, -CH2CHFCF2-, -CH2CH2CF2-, -CH2CF2CHF-, -CH2CHFCHF-, -CH2CH2CHF-, -CF(CF3)-CF2-, -CF(CHF2)-CF2-, -CF(CH2F)-CF2-, -CF(CH3)-CF2-, -CF(CF3)-CHF-, -CF(CHF2)-CHF-, -CF(CH2F)-CHF-, -CF(CH3)-CHF-, -CF(CF3)-CH2-, -CF(CHF2)-CH2-, -CF(CH2F)-CH2-, -CF(CH3)-CH2-, -CH(CF3)-CF2-, -CH(CHF2)-CF2-, -CH(CH2F)-CF2-, -CH(CH3)-CF2-, -CH(CF3)-CHF-, -CH(CHF2)-CHF-, -CH(CH2F)-CHF-, -CH(CH3)-CHF-, -CH(CF3)-CH2-, -CH(CHF2)-CH2- and -CH(CH2F)-CH2-.

[0160] As R f4 specific examples, -CF2CF2CF2CF2-, -CF2CF2CF2CHF-, -CF2CF2CF2CH2-, -CF2CHFCF2CF2-, -CHFCHFCF2CF2-, -CH2CHFCF2CF2-, -CF2CH2CF2CF2-, -CHFCH2CF2CF2-, -CH2CH2CF2CF2-, -CHFCF2CHFCF2-, -CH2CF2CHFCF2-, -CF2CHFCHFCF2-, -CHFCHFCHFCF2-, -CH2CHFCHFCF2-, -CF2CH2CHFCF2-, -CHFCH2CHFCF2-, -CH2CH2CHFCF2-, -CF2CH2CH2CF2-, -CHFCH2CH2CF2-, -CH2CH2CH2CF2-, -CHFCH2CH2CHF-, -CH2CH2CH2CHF- and -cycloC4F6- can be cited.

[0161] As R f5 specific examples, -CF2CF2CF2CF2CF2-, -CHFCF2CF2CF2CF2-, -CH2CHFCF2CF2CF2-, -CF2CHFCF2CF2CF2-, -CHFCHFCF2CF2CF2-, -CF2CH2CF2CF2CF2-, -CHFCH2CF2CF2CF2-, -CH2CH2CF2CF2CF2-, -CF2CF2CHFCF2CF2-, -CHFCF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CH2CF2CF2CF2CH2- and -cycloC5F8- can be cited.

[0162] As R f6 specific examples, -CF2CF2CF2CF2CF2CF2-, -CF2CF2CHFCHFCF2CF2-, -CHFCF2CF2CF2CF2CF2-, -CHFCHFCHFCHFCHFCHF-, -CHFCF2CF2CF2CF2CH2-, -CH2CF2CF2CF2CF2CH2- and -cycloC6F 10 -

[0163] Here, -cycloC4F6- means perfluorocyclobutane diyl, and as a specific example thereof, perfluorocyclobutane-1,2-diyl can be cited. -cycloC5F8- means perfluorocyclopentane diyl, and as a specific example thereof, perfluorocyclopentane-1,3-diyl can be cited. -cycloC6F 10 - means perfluorocyclohexane diyl, and as a specific example thereof, perfluorocyclohexane-1,4-diyl can be cited.

[0164] Among them, -(R 12 O) m1 - preferably contains at least one selected from the group consisting of the structures represented by the following formulas (F1) to (F3), and more preferably contains the structure represented by formula (F2).

[0165] -(R f1 O) k1 -(R f2 O) k2 -…(F1)

[0166] -(R f2 O) k2 -(R f4 O) k4 -…(F2)

[0167] -(R f3 O) k3 -…(F3)

[0168] Among them, each symbol of formulas (F1) to (F3) is the same as that of the above formula (A2).

[0169] In formulas (F1) and (F2), the bonding order of (R f1 O) and (R f2 O), (R f2 O) and (R f4 O) is arbitrary respectively. For example, (R f1 O) and (R f2 O) can be alternately arranged, (R f1 O) and (R f2 O) can be block arranged respectively, or can be randomly arranged. The same is true for formula (F2).

[0170] In formula (F1), k1 is preferably 1 to 30, more preferably 1 to 20. In addition, k2 is preferably 1 to 30, more preferably 1 to 20.

[0171] In formula (F2), k2 is preferably 1 to 30, more preferably 1 to 20. In addition, k4 is preferably 1 to 30, more preferably 1 to 20.

[0172] In formula (F3), k3 is preferably 1 to 30, more preferably 1 to 20.

[0173] In formula (A1), as R 13 , substances the same as the above R f1 to R f6 can be cited.

[0174] Among them, R 13 is preferably a fluoroalkylene group having 1 to 4 carbon atoms.

[0175] As a specific example of R A1 , for example, the following structures can be cited. * represents the bonding site with -O-, n1 represents an integer from 0 to 60, and n2 represents an integer from 0 to 500. As n1, for example, 13 can be cited, and as n2, for example, 7 can be cited.

[0176]

[0177] 〔R B1 〕

[0178] In formula (1), R B1 is a monovalent saturated hydrocarbon group, a halogenated monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogenated (heteroatom-containing monovalent saturated hydrocarbon) group.

[0179] As the monovalent saturated hydrocarbon group represented by R B1 , for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, and cyclohexyl can be cited.

[0180] As the halogenated monovalent saturated hydrocarbon group represented by R B1 , it is preferably a halogenated alkyl group. The halogen atom contained in the halogenated monovalent saturated hydrocarbon group is preferably a fluorine atom, a chlorine atom, or a bromine atom.

[0181] R B1 The heteroatom-containing monovalent saturated hydrocarbon group represented is preferably a monovalent saturated hydrocarbon group containing an etheric oxygen atom (i.e., -O-), and more preferably an alkyl group containing an etheric oxygen atom. That is, R B1 preferably further has an ether bond.

[0182] As the halogenated (heteroatom-containing monovalent saturated hydrocarbon) group represented by R B1 , it is preferably a halogenated (heteroatom-containing alkyl). The halogen atom contained in the halogenated (heteroatom-containing monovalent saturated hydrocarbon) group is preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogenated (heteroatom-containing monovalent saturated hydrocarbon) group is preferably a halogenated monovalent saturated hydrocarbon group containing an etheric oxygen atom, and more preferably a halogenated alkyl group containing an etheric oxygen atom.

[0183] From the viewpoint of excellent solubility in a solvent described later, the carbon number of R B1 is preferably 1 to 100, more preferably 2 to 50, and further preferably 3 to 20.

[0184] From the viewpoint of excellent solubility in a solvent described later, R B1 preferably contains at least one fluorine atom and preferably does not contain a hydrogen atom.

[0185] Among them, from the viewpoint of excellent solubility in a solvent described later, R B1 is preferably represented by the following formula (B1).

[0186] R 21 O-(R 22 O) m2 -R 23 -…(B1)

[0187] In formula (B1), R 21 is an alkyl group optionally having a fluorine atom, and each R 22 is independently an alkylene group having 1 to 6 carbon atoms optionally having a fluorine atom, R 23 is an alkylene group having 1 to 6 carbon atoms optionally having a fluorine atom, and m2 is an integer of 0 to 20.

[0188] In formula (B1), as R 21 , for example, an alkyl group and a fluoroalkyl group can be mentioned.

[0189] From the viewpoint of excellent solubility in a solvent described later, the carbon number of R 21 is preferably 1 to 50, more preferably 1 to 10, and still more preferably 1 to 6.

[0190] The alkyl group represented by R 21 can be a linear alkyl group, a branched alkyl group, or an alkyl group having a ring structure.

[0191] The fluoroalkyl group represented by R 21 can be a linear fluoroalkyl group, a branched fluoroalkyl group, or a fluoroalkyl group having a ring structure.

[0192] 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.

[0193] In formula (B1), -(R 22 O) m2 - is preferably represented by the above formula (A2).

[0194] 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.

[0195] In formula (B1), as R 23, substances identical to the above R can be enumerated. f1 ~R f6 Same substances can be enumerated.

[0196] 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.

[0197] As a specific example of R B1 , for example, the following structures can be enumerated. * indicates the bonding site with -O-(C=O)-.

[0198]

[0199] 〔R A2 〕

[0200] In formula (2), R A2 is 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.

[0201] As the divalent saturated hydrocarbon group, halogenated divalent saturated hydrocarbon group, heteroatom-containing divalent saturated hydrocarbon group, or halogenated (heteroatom-containing divalent saturated hydrocarbon) group represented by R A2 , a group obtained by removing one hydrogen atom or halogen atom from the monovalent saturated hydrocarbon group, halogenated monovalent saturated hydrocarbon group, heteroatom-containing monovalent saturated hydrocarbon group, or halogenated (heteroatom-containing monovalent saturated hydrocarbon) group represented by R A1 in formula (1) can be enumerated.

[0202] From the viewpoint of excellent solubility in a solvent described later, the carbon number of R A2 is preferably 1 to 200, more preferably 3 to 100.

[0203] Among them, from the viewpoint of excellent solubility in a solvent described later, R A2 is preferably represented by the following formula (A5). That is, R A2 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.

[0204] -R 31 O-(R 32 O) m5 -R 33 -…(A5)

[0205] In formula (A5), R 31 and R 33 are each independently an alkylene group having 1 to 6 carbon atoms optionally having a fluorine atom, R 32 are each independently an alkylene group having 1 to 6 carbon atoms optionally having a fluorine atom, and m5 is an integer of 0 to 500.

[0206] In formula (A5), as R 31 and R 33 , each independently, substances the same as R 13 in formula (A1) can be exemplified.

[0207] In formula (A5), as -(R 32 O) m5 -, substances the same as -(R 12 O) m1 - in formula (A1) can be exemplified.

[0208] As a specific example of R A2 , for example, the following structures can be exemplified. * represents the bonding site with -O-, and n2 represents an integer of 0 to 500.

[0209]

[0210] 〔R B2 and R B3 〕

[0211] In formula (2), R B2 and R B3 are each independently a monovalent saturated hydrocarbon group, a halogenated monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogenated (heteroatom-containing monovalent saturated hydrocarbon) group.

[0212] As the monovalent saturated hydrocarbon group, halogenated monovalent saturated hydrocarbon group, heteroatom-containing monovalent saturated hydrocarbon group, or halogenated (heteroatom-containing monovalent saturated hydrocarbon) group represented by R B2 or R B3 , groups the same as the monovalent saturated hydrocarbon group, halogenated monovalent saturated hydrocarbon group, heteroatom-containing monovalent saturated hydrocarbon group, or halogenated (heteroatom-containing monovalent saturated hydrocarbon) group represented by R B1 in formula (1) can be exemplified.

[0213] As an example of the ester compound, the following compound (T1) etc. can be exemplified.

[0214]

[0215] The number-average molecular weight of the ester compound is not particularly limited, and for example, it can be 100 to 100,000. From the viewpoint of excellent solubility in a liquid, it is preferably 100 to 20,000, more preferably 300 to 10,000, and further preferably 400 to 6,000.

[0216] The number-average molecular weight of the above ester compound is the number-average value of the molecular weights of each molecule calculated based on the molecular structure determined by 1 H-NMR and 19 F-NMR.

[0217] From the viewpoint of obtaining a high yield of the target product, the content rate of the ester compound contained in the liquid is preferably 1 to 100% by mass, more preferably 3 to 100% by mass, still more preferably 5 to 100% by mass, particularly preferably 8 to 70% by mass, and most preferably 8 to 50% by mass, relative to the total amount of the liquid.

[0218] The method for producing the ester compound is not particularly limited. For example, the ester compound can be obtained by reacting an OH compound with a carboxylic acid halide in an organic solvent. In the production of the ester compound, NaF can be used as a catalyst as needed. In the reaction of the OH compound with the carboxylic acid halide, the reaction time can be, for example, 0.5 to 100 hours, preferably 0.5 to 50 hours. In addition, the reaction temperature can be, for example, 0 to 200 °C, preferably 0 to 100 °C.

[0219] (OH compound)

[0220] The liquid may contain an OH compound.

[0221] When the liquid contains an OH compound, as described above, the amount of the OH compound is 0.5 part by mass or less.

[0222] In addition, from the viewpoint of increasing the yield of the target product, the amount of the OH compound is preferably 0.01 part by mass or more.

[0223] The amount of the OH compound is preferably 0.01 to 0.5 part by mass.

[0224] The OH compound is not 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 easy availability, the number of hydroxyl groups contained in the OH compound is preferably 1 or 2.

[0225] The OH compound may or may not have a fluorinable atom, and preferably has a fluorinable atom. The OH compound may have only one fluorinable atom or may have two or more fluorinable atoms. As the number of fluorinable atoms contained in one molecule of the OH compound, for example, 1 to 1000 can be mentioned, preferably 1 to 500, and more preferably 1 to 100.

[0226] Examples of the OH compound include the compound represented by the following formula (3), the compound represented by the following formula (4), and the like.

[0227] R A3 -OH…(3)

[0228] HO-R A4 -OH…(4)

[0229] In formulas (3) and (4),

[0230] RA3 is a monovalent saturated hydrocarbon group, a halogenated monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogenated (heteroatom-containing monovalent saturated hydrocarbon) group,

[0231] R A4 is 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.

[0232] As the R A3 shown monovalent saturated hydrocarbon group, halogenated monovalent saturated hydrocarbon group, heteroatom-containing monovalent saturated hydrocarbon group, or halogenated (heteroatom-containing monovalent saturated hydrocarbon) group, groups the same as those of R A1 shown in formula (1) can be exemplified.

[0233] As the R A4 shown divalent saturated hydrocarbon group, halogenated divalent saturated hydrocarbon group, heteroatom-containing divalent saturated hydrocarbon group, or halogenated (heteroatom-containing divalent saturated hydrocarbon) group, groups the same as those of R A2 shown in formula (1) can be exemplified.

[0234] When the liquid contains the ester compound shown in formula (1) and the OH compound shown in formula (3), R A3 in the OH compound in formula (3) is optionally the same as or different from R A1 in the ester compound in formula (1), preferably the same.

[0235] When the liquid contains the ester compound shown in formula (2) and the OH compound shown in formula (4), R A4 in the OH compound in formula (4) is optionally the same as or different from R A2 in the ester compound in formula (2), preferably the same.

[0236] As a specific example of the OH compound shown in formula (3), for example, the following structures can be exemplified. n1 represents an integer from 0 to 60, and n2 represents an integer from 0 to 500. As n1, for example, 13 can be cited, and as n2, for example, 7 can be cited.

[0237]

[0238] As a specific example of the OH compound shown in formula (4), for example, the following structures can be exemplified. n2 represents an integer from 0 to 499.

[0239]

[0240] Examples of the OH compound include the following compound (T2) and the like.

[0241]

[0242] The number-average molecular weight of the OH compound is not particularly limited, and examples thereof include 50 to 50,000. From the viewpoint of excellent solubility in a solvent described later, it is preferably 50 to 25,000, and more preferably 50 to 10,000.

[0243] The number-average molecular weight of the above OH compound is the number-average value of the molecular weights of each molecule calculated based on the molecular structure determined by 1 H-NMR and 19 F-NMR.

[0244] (Carboxylic acid compound)

[0245] The liquid may contain a carboxylic acid compound.

[0246] When the liquid contains a carboxylic acid compound, as described above, the amount of the carboxylic acid is 2.0 parts by mass or less. From the viewpoint of increasing the yield of the target product, the amount of the carboxylic acid is preferably 1.7 parts by mass or less, and more preferably 1.5 parts by mass or less.

[0247] In addition, from the viewpoint of increasing the yield of the target product, the amount of the carboxylic acid is preferably 0.01 part by mass or more.

[0248] The amount of the carboxylic acid is preferably 0.01 to 2.0 parts by mass, more preferably 0.01 to 1.7 parts by mass, and further preferably 0.01 to 1.5 parts by mass.

[0249] The carboxylic acid compound is not particularly limited as long as it is a compound having a carboxyl group. The carboxylic acid compound may have only one carboxyl group or two or more carboxyl groups, and preferably has only one carboxyl group.

[0250] The carboxylic acid compound may or may not have a fluorinable atom.

[0251] Examples of the carboxylic acid compound include the compound represented by the following formula (5) and the like.

[0252] R B4 -(C=O)-OH…(5)

[0253] In formula (5),

[0254] R B4 is a monovalent saturated hydrocarbon group, a halogenated monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogenated (heteroatom-containing monovalent saturated hydrocarbon) group.

[0255] As R B4Examples of the monovalent saturated hydrocarbon group, halogenated monovalent saturated hydrocarbon group, heteroatom-containing monovalent saturated hydrocarbon group, or halogenated (heteroatom-containing monovalent saturated hydrocarbon) group shown include the same groups as R in formula (1). B1 Examples of the monovalent saturated hydrocarbon group, halogenated monovalent saturated hydrocarbon group, heteroatom-containing monovalent saturated hydrocarbon group, or halogenated (heteroatom-containing monovalent saturated hydrocarbon) group shown include the same groups as those described above.

[0256] When the liquid contains the ester compound represented by formula (1) and the carboxylic acid compound represented by formula (5), R in formula (5) in the carboxylic acid compound B4 is optionally the same as or different from R in formula (1) in the ester compound, preferably the same. B1 When the liquid contains the ester compound represented by formula (2) and the carboxylic acid compound represented by formula (5), R in formula (5) in the carboxylic acid compound

[0257] is optionally the same as one of R and R in formula (2) in the ester compound, may also be the same as both, or may be different from both, preferably the same as at least one of R and R. B4 is optionally the same as one of R and R in formula (2) in the ester compound, may also be the same as both, or may be different from both, preferably the same as at least one of R and R. B2 and R B3 in the ester compound, may also be the same as both, or may be different from both, preferably the same as at least one of R and R. B2 and R B3 in the ester compound, may also be the same as both, or may be different from both, preferably the same as at least one of R and R.

[0258] Specific examples of the carboxylic acid compound represented by formula (5) include the following structures, for example.

[0259]

[0260] The molecular weight of the carboxylic acid compound is not particularly limited, and examples thereof include 40 to 10,000. From the viewpoint of excellent solubility in a solvent described later, it is preferably 40 to 5,000, more preferably 40 to 1,000.

[0261] The molecular weight of the above-mentioned carboxylic acid compound is a value calculated based on the molecular structure determined by 1 H-NMR and 19 F-NMR.

[0262] (NaF)

[0263] The liquid may contain NaF.

[0264] 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, more preferably 1.2 parts by mass or less.

[0265] In addition, from the viewpoint of increasing the yield of the target product, the amount of NaF is preferably 0.01 part by mass or more.

[0266] 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 still more preferably 0.01 to 1.2 parts by mass.

[0267] (HF)

[0268] The liquid may contain HF.

[0269] 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.

[0270] In addition, from the viewpoint of increasing the yield of the target product, the amount of HF is preferably 0.01 part by mass or more.

[0271] The amount of HF is preferably 0.01 to 3.0 parts by mass, more preferably 0.01 to 2.8 parts by mass.

[0272] (Solvent)

[0273] The liquid may contain a solvent as needed. The solvent is not particularly limited as long as it can dissolve the ester compound.

[0274] From the viewpoint of excellent solubility of the ester compound and the fluorinated ester compound obtained by fluorinating the ester compound, the solvent preferably contains at least one selected from the group consisting of a chlorine-containing solvent and a fluorinated solvent other than the chlorine-containing solvent, and more preferably contains a chlorine-containing solvent. The chlorine-containing solvent is a solvent containing a chlorine atom. The chlorine-containing solvent preferably contains a fluorine atom in addition to the chlorine atom.

[0275] As chlorine-containing solvents, for example, CClF2CClFCF2OCF2CClF2 (CFE-419), CH2ClCHClCH2OCF2CHFCl (HCFE-473), CF2ClCFClCHFOCF2CF2Cl (HCFE-428a, b), CFHClCFClCF2OCF2CF2Cl (HCFE-428c, d), CF2ClCHClCF2OCF2CF2Cl (HCFE-428e), 1,2,3,4-tetrachloroperfluorobutane (R-113), CF2Cl-CFCl-CFCl-O-CF2-CF2Cl (CFE-418), CClHFCClFCHFOCF2CClF2 (HCFE-437a, b), CClF2CClHCHFOCF2CClF2 (HCFE-437c), CClHFCClFCH2OCF2CClF2 (HCFE-446a), CF2ClCCl2CF2OCF2CFHCl (HCFE-427a, b), CF2HCClFCF2OCF2CF2Cl (HCFE-429), etc. can be cited.

[0276] As fluorine-containing solvents other than chlorine-containing solvents, perfluoroalkanes (such as FC-72, etc.), perfluoroethers (such as FC-75, FC-77, etc.), perfluoropolyethers (trade names: Krytox, Fomblin, Galden, Demnum, etc.), inert fluids (trade name: Fluorinert), perfluorocarboxylic acid fluorides, etc. can be cited.

[0277] From the viewpoint of improving the yield of fluorine-containing compounds, the boiling point of the solvent is preferably 10 to 500 °C, more preferably 30 to 250 °C, and further preferably 50 to 150 °C.

[0278] From the viewpoint of improving the yield of fluorine-containing compounds, the number of carbon atoms of the solvent is preferably 4 or more, more preferably 4 to 1000, further preferably 4 to 500, particularly preferably 4 to 100, and most preferably 4 to 50.

[0279] From the viewpoint of improving the yield of fluorine-containing compounds, the molecular weight of the solvent is preferably 200 or more, more preferably 200 to 50000, further preferably 200 to 25000, particularly preferably 200 to 10000, and most preferably 200 to 1000. When the molecular weight has a distribution, the molecular weight represents the weight-average molecular weight (Mw). Mw is measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent and is measured in terms of polystyrene conversion.

[0280] (Other additives)

[0281] The liquid may contain other additives as needed. As other additives, for example, auxiliaries that promote the fluorination of the ester compound can be cited.

[0282] As the auxiliaries, for example, compounds containing C-H bonds and compounds containing carbon-carbon double bonds other than the ester compound can be cited. As the compounds containing C-H bonds, benzene, toluene, etc. can be cited. As the compounds containing carbon-carbon double bonds, hexafluoropropene, hexafluorobutadiene, etc. can be cited. Among them, the auxiliaries are preferably aromatic hydrocarbons such as benzene and toluene.

[0283] <Fluorination reaction>

[0284] As a method for fluorinating the raw material compound in the liquid, for example, the ECF method, the cobalt fluorination method, and the method of reacting with fluorine can be cited. Among them, the method of reacting with fluorine that can advantageously fluorinate the raw material compound is preferred.

[0285] In the method of reacting the raw material compound in the liquid with fluorine, for example, a gas containing fluorine gas is introduced into the liquid containing the raw material compound.

[0286] Hereinafter, as an example of the fluorination reaction, the method of introducing a gas containing fluorine gas into the liquid containing the raw material compound will be described, but it is not limited thereto.

[0287] The gas introduced into the liquid only needs to contain at least fluorine gas. The gas may contain fluorine gas or may contain a gas other than fluorine gas.

[0288] As the gas other than fluorine gas, for example, an inert gas can be cited. As the inert gas, nitrogen, helium, neon, argon, etc. can be cited, preferably nitrogen or helium, and preferably nitrogen from the viewpoint of controlling low cost.

[0289] From the viewpoint of increasing the yield of the target product, the content rate of fluorine gas relative to the total amount of the gas is preferably 10% by volume or more, more preferably 15% by volume or more, further preferably 20% by volume or more, and particularly preferably 25% by volume or more. In addition, from the viewpoint of excellent safety, the content rate of fluorine gas relative to the total amount of the gas is preferably 60% by volume or less, more preferably 50% by volume or less, and further preferably 40% by volume or less. From the foregoing viewpoints, the content rate of fluorine gas relative to the total amount of the gas is preferably 10 to 60% by volume, more preferably 15 to 50% by volume, and further preferably 20 to 40% by volume.

[0290] The temperature of the fluorination of the ester compound can be, for example, in the range of -60°C or higher and below the boiling point of the ester compound, can be in the range of -50 to 100°C, or can be in the range of -20 to 50°C.

[0291] As the pressure in the fluorination of the ester compound, for example, 0 to 2 MPa can be mentioned.

[0292] The fluorination of the ester compound can be carried out in a batch mode or a continuous mode.

[0293] From the viewpoint of increasing the yield of the target product, the residence time of the liquid containing the ester compound and into which fluorine gas is introduced in the reactor for fluorinating the ester compound is preferably 200 hours or less, more preferably 190 hours or less, further preferably 170 hours or less, particularly preferably 150 hours or less, and extremely preferably 100 hours or less. Hereinafter, the residence time of the above liquid in the above reactor is also referred to as "residence time".

[0294] 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 further preferably 1.0 hour or more. The residence time is preferably 0.3 to 200 hours, more preferably 0.3 to 190 hours, further preferably 0.3 to 170 hours, particularly preferably 0.6 to 150 hours, and extremely preferably 1.0 to 100 hours.

[0295] In the case where the fluorination of the ester compound is carried out in a continuous mode, the above residence time is calculated based on the flow rate of the above liquid and the volume of the reactor. In addition, in the case where the fluorination of the ester compound is carried out in a continuous mode, the residence time can be adjusted by the flow rate of the above liquid and the length in the flow direction of the reactor, etc.

[0296] <Fluorinated ester compound>

[0297] The fluorinated ester compound obtained by fluorination of the ester compound is a compound in which at least one fluorinable atom possessed by the ester compound is substituted by a fluorine atom.

[0298] The fluorinated ester compound preferably further has an ether bond, and more preferably contains a perfluoropolyether chain.

[0299] In the case where the ester compound is the compound represented by the formula (1), the fluorinated ester compound is preferably the compound represented by the following formula (6). In addition, in the case where the ester compound is the compound represented by the formula (2), the fluorinated ester compound is preferably the compound represented by the following formula (7).

[0300] R AF1 -O-(C=O)-R BF1 …(6)

[0301] R BF2 -(C=O)-O-R AF2 -O-(C=O)-R BF3 …(7)

[0302] In Formulas (6) and (7),

[0303] R AF1 、R BF1 、R AF2 、R BF2 and R BF3 are groups corresponding to R A1 、R B1 、R A2 、R B2 and R B3 respectively,

[0304] R A1 、R B1 、R A2 、R B2 and R B3 are each independently a group that does not contain a hydrogen atom, R AF1 、R BF1 、R AF2 、R BF2 and R BF3 are the same groups as R A1 、R B1 、R A2 、R B2 and R B3 respectively,

[0305] R A1 、R B1 、R A2 、R B2 and R B3 are each independently a group that contains a hydrogen atom, R AF1 、R BF1 、R AF2 、R BF2 and R BF3 is a group in which all hydrogen atoms present in R A1 、R B1 、R A2 、R B2 and R B3 are replaced by fluorine atoms.

[0306] 〔R AF1 〕

[0307] In Formula (6), R AF1 is the group corresponding to R A1 respectively.

[0308] R A1 contains a hydrogen atom, R AF1 is a group in which all hydrogen atoms present in R A1 are replaced by fluorine atoms. When R A1 does not contain a hydrogen atom, R AF1 is the group corresponding to RA1 Same group.

[0309] From the viewpoint of excellent solubility in a solvent, R AF1 is preferably represented by the following formula (A3).

[0310] R 14 O-(R 15 O) m3 -R 16 -…(A3)

[0311] In formula (A3), R 14 is a perfluoroalkyl group, R 15 are each independently a perfluoroalkylene group having 1 to 6 carbon atoms, R 16 is a perfluoroalkylene group having 1 to 6 carbon atoms, and m3 is an integer of 0 to 500.

[0312] In formula (A3), R 14 corresponds to R 11 in formula (A1). When R 11 contains a hydrogen atom, R 14 is a group in which all hydrogen atoms contained in R 11 are replaced by fluorine atoms. When R 11 does not contain a hydrogen atom, R 14 is the same as R 11 .

[0313] In formula (A3), -(R 15 O) m3 - corresponds to -(R 12 O) m1 - in formula (A1). When R 12 contains a hydrogen atom, R 15 is a group in which all hydrogen atoms contained in R 12 are replaced by fluorine atoms. When R 12 does not contain a hydrogen atom, R 15 is the same as R 12 .

[0314] In formula (A3), -(R 15 O) m3 - is preferably represented by the following formula (A4).

[0315] -[(R ff1 O) k7 (R ff2 O) k8 (R ff3 O) k9 (R ff4 O) k10 (R ff5 O) k11 (R ff6O) k12 -…(A4)

[0316] Among them,

[0317] R ff1 is a perfluoroalkylene group having 1 carbon atom,

[0318] R ff2 is a perfluoroalkylene group having 2 carbon atoms,

[0319] R ff3 is a perfluoroalkylene group having 3 carbon atoms,

[0320] R ff4 is a perfluoroalkylene group having 4 carbon atoms,

[0321] R ff5 is a perfluoroalkylene group having 5 carbon atoms,

[0322] R ff6 is a perfluoroalkylene group having 6 carbon atoms.

[0323] k7, k8, k9, k10, k11 and k12 each independently represent an integer of 0 or more, and k7 + k8 + k9 + k10 + k11 + k12 is an integer of 0 to 500.

[0324] In formula (A4), R ff1 ~R ff6 corresponds to R f1 ~R f6 in formula (A2). For example, when R f1 contains a hydrogen atom, R ff1 is a group in which all hydrogen atoms contained in R f1 are replaced by fluorine atoms. When R f1 does not contain a hydrogen atom, R ff1 is the same as R f1 . Regarding R ff2 ~R ff6 , it is also the same as R ff1 .

[0325] From the viewpoint of excellent solubility in a solvent, 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.

[0326] Among them, -(R 15 O) m3 - preferably contains at least one selected from the group consisting of the structures represented by the following formulas (G1) to (G3), and more preferably contains the structure represented by formula (G2).

[0327] -(R ff1O) k7 -(R ff2 O) k8 -…(G1)

[0328] -(R ff2 O) k8 -(R ff4 O) k10 -…(G2)

[0329] -(R ff3 O) k9 -…(G3)

[0330] Among them, each symbol in formula (G1) to formula (G3) is the same as the above formula (A4).

[0331] In formula (G1) and formula (G2), (R ff1 O) and (R ff2 O), (R ff2 O) and (R ff4 O) can be in any bonding order. For example, (R ff1 O) and (R ff2 O) can be alternately arranged, (R ff1 O) and (R ff2 O) can be block arranged respectively, or can be randomly arranged. The same is true for formula (G2).

[0332] In formula (G1), k7 is preferably 1 to 30, more preferably 1 to 20. In addition, k8 is preferably 1 to 30, more preferably 1 to 20.

[0333] In formula (G2), k8 is preferably 1 to 30, more preferably 1 to 20. In addition, k10 is preferably 1 to 30, more preferably 1 to 20.

[0334] In formula (G3), k9 is preferably 1 to 30, more preferably 1 to 20.

[0335] In formula (A3), R 16 corresponds to R in formula (A1). 13 When R 13 contains a hydrogen atom, R 16 is a group in which all hydrogen atoms contained in R 13 are replaced by fluorine atoms. When R 13 does not contain a hydrogen atom, R 16 is the same as R 13 .

[0336] As R 16 , substances the same as the above R ff1 to R ff6 can be listed.

[0337] Among them, R 16 is preferably a perfluoroalkylene group having 1 to 3 carbon atoms.

[0338] In formula (A3), m3 corresponds to m1 in formula (A1). m3 is the same as m1.

[0339] As R AF1 Specific examples thereof include the following structures. * represents the bonding site to -O-, n1 represents an integer from 0 to 60, and n2 represents an integer from 0 to 500. As n1, for example, 13 can be cited, and as n2, for example, 7 can be cited.

[0340]

[0341] 〔R BF1 〕

[0342] In formula (6), R BF1 is a group corresponding to R B1 .

[0343] When R B1 contains a hydrogen atom, R BF1 is a group in which all hydrogen atoms present in R B1 are replaced by fluorine atoms. When R B1 does not contain a hydrogen atom, R BF1 is the same group as R B1 .

[0344] From the viewpoint of excellent solubility in a solvent, R BF1 is preferably represented by the following formula (B2).

[0345] R 24 O-(R 25 O) m4 -R 26 -…(B2)

[0346] In formula (B2), R 24 is a perfluoroalkyl group, R 25 are each independently a perfluoroalkylene group having 1 to 6 carbon atoms, R 26 is a perfluoroalkylene group having 1 to 6 carbon atoms, and m4 is an integer from 0 to 20.

[0347] In formula (B2), R 24 corresponds to R 21 in formula (B1). When R 21 contains a hydrogen atom, R 24 is a group in which all hydrogen atoms contained in R 21 are replaced by fluorine atoms. When R 21 does not contain a hydrogen atom, R 24 is the same as R 21 .

[0348] In formula (B2), -(R 25 O) m4 - corresponds to -(R 22 O) m2 - in formula (B1). When R 22 contains a hydrogen atom, R 25 is a group in which all hydrogen atoms contained in R 22 are replaced by fluorine atoms. When R 22 does not contain a hydrogen atom, R 25 is the same as R 22 .

[0349] In formula (B2), -(R 25 O) m4 - is preferably represented by the above formula (A4).

[0350] In formula (B2), R 26 corresponds to R 23 in formula (B1). When R 23 contains a hydrogen atom, R 26 is a group in which all hydrogen atoms contained in R 23 are replaced by fluorine atoms. When R 23 does not contain a hydrogen atom, R 26 is the same as R 23 .

[0351] In formula (B2), m4 corresponds to m2 in formula (B1). m4 is the same as m2.

[0352] As a specific example of R BF1 , for example, the following structures can be listed. * indicates the bonding site with -O-(C=O)-.

[0353]

[0354] 〔R AF2 〕

[0355] In formula (7), R AF2 is a group corresponding to R A2 .

[0356] When R A2 contains a hydrogen atom, R AF2 is a group in which all hydrogen atoms present in R A2 are replaced by fluorine atoms. When R A2 does not contain a hydrogen atom, R AF2 is a group the same as R A2 .

[0357] From the viewpoint of excellent solubility in a solvent, R AF2Preferably represented by the following formula (A6). That is, R AF2 Preferably further has an ether bond.

[0358] -R 34 O-(R 35 O) m6 -R 36 -…(A6)

[0359] 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 from 0 to 500.

[0360] In formula (A6), R 34 and R 36 correspond to R 31 and R 33 in formula (A5) respectively. When R 31 contains a hydrogen atom, R 34 is a group in which all hydrogen atoms contained in R 31 are replaced by fluorine atoms. When R 31 does not contain a hydrogen atom, R 34 is the same as R 31 . When R 33 contains a hydrogen atom, R 36 is a group in which all hydrogen atoms contained in R 33 are replaced by fluorine atoms. When R 33 does not contain a hydrogen atom, R 36 is the same as R 34 .

[0361] In formula (A6), -(R 35 O) m6 - corresponds to -(R 32 O) m5 - in formula (A5). When R 32 contains a hydrogen atom, R 35 is a group in which all hydrogen atoms contained in R 32 are replaced by fluorine atoms. When R 32 does not contain a hydrogen atom, R 35 is the same as R 32 .

[0362] In formula (A6), as R 34 and R 36 , substances the same as R 31 and R 33 in formula (A5) can be independently listed respectively.

[0363] In formula (A6), as -(R35 O) m6 -, substances identical to -(R 32 O) m5 - in formula (A5) can be enumerated.

[0364] As specific examples of R AF2 , the following structures can be enumerated, for example. * indicates the bonding site to -O-, and n2 represents an integer from 0 to 500.

[0365]

[0366] 〔R BF2 and R BF3 〕

[0367] In formula (7), R BF2 and R BF3 are groups corresponding to R B2 and R B3 respectively.

[0368] When R B2 contains a hydrogen atom, R BF2 is a group in which all hydrogen atoms present in R B2 are replaced by fluorine atoms. When R B2 does not contain a hydrogen atom, R BF2 is the same group as R B2 .

[0369] When R B3 contains a hydrogen atom, R BF3 is a group in which all hydrogen atoms present in R B3 are replaced by fluorine atoms. When R B3 does not contain a hydrogen atom, R BF3 is the same group as R B3 .

[0370] The groups represented by R BF2 or R BF3 include groups identical to the group represented by R BF1 in formula (6).

[0371] The number-average molecular weight of the fluorine-containing ester compound is not particularly limited. For example, it can be 100 to 101000. From the viewpoint of excellent solubility in a solvent, it is preferably 100 to 21000, more preferably 300 to 11000, and further preferably 400 to 7000.

[0372] The number-average molecular weight of the above-mentioned fluorine-containing ester compound is the number-average value of the molecular weights of each molecule calculated based on the molecular structure determined by 1 H-NMR and 19 F-NMR.

[0373] [Composition]

[0374] One embodiment of the present disclosure relates to a composition comprising: an ester compound having at least one fluorinable 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. With respect 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 carboxyl group is 2.0 parts by mass or less, and the content of sodium fluoride is 2.0 parts by mass or less.

[0375] The above composition is used, for example, in the method for producing the fluorinated ester compound described above. Thereby, the ester compound contained in the composition is fluorinated to obtain a fluorinated ester compound.

[0376] When the above composition is a liquid, it can be directly used as the liquid for fluorination in the method for producing the fluorinated ester compound described above. Additionally, if necessary, a substance obtained by adding a solvent or the like to the above composition can also be used as the liquid for fluorination in the method for producing the fluorinated ester compound described above.

[0377] The above composition contains at least one selected from the group consisting of an OH compound, a carboxylic acid compound, and NaF, and the amount of the OH compound is 0.5 parts by mass or less, the amount of the carboxylic acid is 2.0 parts by mass or less, and the amount of NaF is 2.0 parts by mass or less.

[0378] Therefore, when the above composition is used in the method for producing the fluorinated ester compound described above to perform a fluorination reaction on the ester compound in the composition, the fluorinated ester compound as the target product can be obtained in a high yield.

[0379] In one embodiment of the present disclosure, it is preferred that at least one of the group consisting of the amount of the OH compound, the amount of the carboxylic acid, and the amount of NaF is 0.01 parts by mass or more. Thereby, when the composition is used in the method for producing the fluorinated ester compound described above, the fluorinated ester compound as the target product can be obtained in a high yield.

[0380] It may be that a part of the amount of the OH compound, the amount of the carboxylic acid, and the amount of NaF is 0.01 parts by mass or more, or it may be that the amount of the OH compound, the amount of the carboxylic acid, and the amount of NaF are all 0.01 parts by mass or more.

[0381] In one embodiment of the present disclosure, the ester compound may include an ester compound having an ether bond.

[0382] When the ester compound includes an ester compound having an ether bond, the composition further contains hydrogen fluoride. With respect to 100 parts by mass of the ester compound contained in the liquid, the content of hydrogen fluoride is preferably 3.0 parts by mass or less.

[0383] That is, when the composition contains an ester compound having an ether bond, the composition further contains HF, and the amount of HF is preferably 3.0 parts by mass or less. Thus, when the composition is used in the method for producing the fluorinated ester compound described above, the target fluorinated ester compound can be obtained in a high yield.

[0384] When the composition contains an ester compound having an ether bond, at least one of the group consisting of the amount of the OH compound, the amount of the carboxylic acid, the amount of NaF, and the amount of HF is preferably 0.01 part by mass or more. Thus, when the composition is used in the method for producing the fluorinated ester compound described above, the target fluorinated ester compound can be obtained in a high yield.

[0385] Part of the amount of the OH compound, the amount of the carboxylic acid, the amount of NaF, and the amount of HF may be 0.01 part by mass or more, or all of the amount of the OH compound, the amount of the carboxylic acid, the amount of NaF, and the amount of HF may be 0.01 part by mass or more.

[0386] The amount of the OH compound is preferably 0.01 to 0.5 part by mass.

[0387] The amount of the carboxylic acid is preferably 0.01 to 2.0 parts by mass, more preferably 0.01 to 1.7 parts by mass, and further preferably 0.01 to 1.5 parts by mass.

[0388] 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 further preferably 0.01 to 1.2 parts by mass.

[0389] The amount of HF is preferably 0.01 to 3.0 parts by mass, more preferably 0.01 to 2.8 parts by mass.

[0390] The composition may further contain a solvent, other additives, etc. as needed.

[0391] Details of the above 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 method for producing the fluorinated ester compound described above.

[0392] Preferably, the composition contains an ester compound and at least one selected from the group consisting of an OH compound, a carboxylic acid compound, and sodium fluoride. The ester compound contains at least one selected from the group consisting of the compounds represented by the following formula (1) and the compounds represented by the following formula (2). The OH compound contains at least one selected from the group consisting of the compounds represented by the following formula (3) and the compounds represented by the following formula (4). The carboxylic acid compound contains the compound represented by the following formula (5).

[0393] R A1 -O-(C=O)-RB1 …(1)

[0394] R B2 -(C=O)-O-R A2 -O-(C=O)-R B3 …(2)

[0395] R A3 -OH…(3)

[0396] HO-R A4 -OH…(4)

[0397] R B4 -(C=O)-OH…(5)

[0398] In formulas (1) to (5),

[0399] R A1 、R A3 、R B1 、R B2 、R B3 and R B4 are each independently a monovalent saturated hydrocarbon group, a halogenated monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogenated (heteroatom-containing monovalent saturated hydrocarbon) group,

[0400] 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.

[0401] In addition, preferably, R in formula (3) A3 is the same as R in formula (1) A1 , R in formula (4) A4 is the same as R in formula (2) A2 , and R in formula (5) B4 is the same as R in formula (1) B1 or R in formula (2) B2 .

[0402] Examples

[0403] Hereinafter, the present disclosure will be further specifically described by way of examples. However, the present disclosure is not limited to the following examples as long as it does not deviate from its gist. Examples 1-2, 4, 6 to 11, 12-2, 16 to 20, 22-2, 23-2, 24-2, 25-2, and 26-2 are examples, and Examples 2, 3, 5, 13 to 15, and 21 are comparative examples.

[0404] 19 Perfluorobenzene was used as an internal standard sample in the quantification of 19F-NMR.

[0405] Hereinafter, tetramethylsilane is referred to as TMS, and 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane is referred to as AC-2000. AC-2000 manufactured by AGC Corporation was used.

[0406] Additionally, NMR data are presented as apparent chemical shift ranges.

[0407] <Example 1-1>

[0408] Add 50.1 g of the following alcohol 1 and 1.34 g of NaF to a flask. As NaF, use NaF with an average primary particle size of 5 μm (manufactured by Kanto Chemical, Deer Special Grade 37174-00). Add 25.0 g of AC-2000 and 21.1 g of the following (HFPO)2 and mix. After mixing, seal the mixture and heat and stir at 50°C for 10 hours. After 10 hours of heating and stirring, cool naturally and remove NaF by filtering with silica gel (D75-60A (N), manufactured by AGC Si-Tech). Then, remove (HFPO)2 and AC-2000 by distillation under reduced pressure.

[0409] Alcohol 1: CH3O(CF2CHFO(CF2)3CH2O) 13 CF2CHFO(CF2)3CH2OH(molecular weight: 3924)

[0410] (HFPO)2: 2,3,3,3-tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)-propionyl fluoride (chemical formula: CF3CF2CF2OCF(CF3)COF, manufactured by FUJIFILM Wako Pure Chemical Corporation, product number: QC-2788)

[0411] Highly polar impurities were removed using silica gel chromatography (developing solvent: AC-2000) to obtain 53.9 g (yield 99.9%) of an ester compound.

[0412] 1 H-NMR and 19 As a result of F-NMR analysis, it was confirmed that the obtained compound was the following compound 1-1. 1 H-NMR and 19 F-NMR confirmed that the above-mentioned alcohol 1 and the following carboxylic acid 1 were not detected, and F ion concentration measurement confirmed that HF ​​and NaF were not detected.

[0413] Compound 1-1: CH3O(CF2CHFO(CF2)3CH2O) n CF2CHFO(CF2)3CH2OCOCF(CF3)OCF2CF2CF3

[0414] 1 1H-NMR (300.4 MHz, solvent CDCl3, reference TMS) δ (ppm): 3.7 (3H), 4.7 (32H), 5.2 (2H), 6.7 - 6.9 (8H)

[0415] 19 19F-NMR (282.7 MHz, solvent CDCl3, reference CFCl3) 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 the number of units n: 13

[0416] Carboxylic acid 1: 2,3,3,3 - tetrafluoro - 2 - (1,1,2,2,3,3,3 - heptafluoropropoxy) - propanoic acid (chemical formula: CF3CF2CF2OCF(CF3)COOH)

[0417] <Example 1 - 2>

[0418] Prepare an autoclave (made of nickel, internal volume 500 mL). A cooler maintained at 0 °C, a NaF pellet filling layer, and a cooler maintained at -10 °C are connected in series at the gas outlet of the autoclave. In addition, a liquid reflux line is provided to reflux the flocculated liquid from the cooler maintained at -10 °C back into the autoclave. An aqueous KOH solution is provided on the final outlet gas pipeline.

[0419] Perform the operation as described above to prepare a fluorination reaction apparatus.

[0420] Charge 302 g of CFE - 419 into the autoclave of the fluorination reaction apparatus and stir while maintaining at 20 °C. After blowing nitrogen into the autoclave at 20 °C for 1 hour, blow fluorine gas diluted to 30 vol% with nitrogen into the autoclave at 20 °C at a flow rate of 2.0 L / h for 1 hour. Hereinafter, fluorine gas diluted to 30 vol% with nitrogen is also referred to as "30% fluorine gas".

[0421] Next, while blowing 30% fluorine gas at the same flow rate, inject 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 into the autoclave over 5.3 hours.

[0422] 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. Further, while blowing 30% fluorine gas at the same flow rate, stirring was continued for 1 hour. Then, nitrogen gas was blown for 1 hour.

[0423] After concentrating the contents of the autoclave with an evaporator, high-polarity impurities were removed by silica gel chromatography (developing solvent: AC-2000), and 9.85 g (yield 99.5%) of the following compound 1-2 was recovered.

[0424] Compound 1-2: CF3O(CF2CF2OCF2CF2CF2CF2O) n CF2CF2OCF2CF2CF2CF2OCOCF(CF3)OCF2CF2CF3

[0425] 19 19F-NMR (282.7 MHz, solvent CDCl3, reference CFCl3) δ (ppm): -55.2 (3F), -80.0 (1F), -82.0 to -82.5 (6F), -84.1 (54F), -86.7 to -87.8 (3F), -89.3 (54F), -91.3 (2F), -126.5 (56F), -130.4 (2F), -132.4 (1F). Average value of the number of units n: 13

[0426] <Example 2>

[0427] The fluorination reaction apparatus was prepared in the same manner as in Example 1-2.

[0428] 301 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus, and stirring was carried out while maintaining the temperature at 20°C. After blowing nitrogen gas into the autoclave at 20°C for 1 hour, 30% fluorine gas was blown at a flow rate of 2.0 L / hour at 20°C for 1 hour.

[0429] Next, while blowing 30% fluorine gas at the same flow rate, a solution obtained 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.

[0430] 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. Further, while blowing 30% fluorine gas at the same flow rate, stirring was continued for 1 hour. Then, nitrogen gas was blown for 1 hour.

[0431] After concentrating the contents of the autoclave with an evaporator, high-polarity impurities were removed using silica gel chromatography (developing solvent: AC-2000), and 7.03 g (yield 70.2%) of the compound 1-2 was recovered.

[0432] The structure of the obtained compound 1-2 and 19 the 19F-NMR data were the same as those in Example 1-2.

[0433] <Example 3>

[0434] In the same manner as in Example 1-2, a fluorination reaction apparatus was prepared.

[0435] 300 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus and stirred while maintaining at 20°C. After blowing nitrogen into the autoclave at 20°C for 1 hour, 30% fluorine gas was blown in at a flow rate of 2.0 L / hour at 20°C for 1 hour.

[0436] Next, while blowing 30% fluorine gas at the same flow rate, a solution obtained by dissolving 8.4 g of the 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.

[0437] 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. Further, while blowing 30% fluorine gas at the same flow rate, stirring was continued for 1 hour. Then, nitrogen was blown in for 1 hour.

[0438] After concentrating the contents of the autoclave with an evaporator, high-polarity impurities were removed using silica gel chromatography (developing solvent: AC-2000), and 7.01 g (yield 70.8%) of the compound 1-2 was recovered.

[0439] The structure of the obtained compound 1-2 and 19 the 19F-NMR data were the same as those in Example 1-2.

[0440] <Example 4>

[0441] In the same manner as in Example 1-2, a fluorination reaction apparatus was prepared.

[0442] 300 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus and stirred while maintaining at 20°C. After blowing nitrogen into the autoclave at 20°C for 1 hour, 30% fluorine gas was blown in at a flow rate of 2.0 L / hour at 20°C for 1 hour.

[0443] Next, while blowing in 30% fluorine gas at the same flow rate, a solution obtained 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.

[0444] 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. Further, while blowing in 30% fluorine gas at the same flow rate, stirring was continued for 1 hour. Then, nitrogen gas was blown in for 1 hour.

[0445] After concentrating the contents of the autoclave with an evaporator, high-polarity impurities were removed using silica gel chromatography (developing solvent: AC-2000), and 7.13 g (yield 72.0%) of the said Compound 1-2 was recovered.

[0446] The structure of the obtained Compound 1-2 and 19 the 19F-NMR data were the same as those in Example 1-2.

[0447] <Example 5>

[0448] In the same manner as in Example 1-2, a fluorination reaction apparatus was prepared.

[0449] 301 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus and stirred while maintaining at 20°C. After blowing nitrogen gas into the autoclave at 20°C for 1 hour, 30% fluorine gas was blown in at a flow rate of 2.0 L / hour at 20°C for 1 hour.

[0450] Next, while blowing in 30% fluorine gas at the same flow rate, a solution obtained 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.

[0451] 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. Further, while blowing in 30% fluorine gas at the same flow rate, stirring was continued for 1 hour. Then, nitrogen gas was blown in for 1 hour.

[0452] After concentrating the contents of the autoclave with an evaporator, high-polarity impurities were removed using silica gel chromatography (developing solvent: AC-2000), and 7.12 g (yield 71.1%) of the said Compound 1-2 was recovered.

[0453] The structure of the obtained Compound 1-2 and 19The F-NMR data was the same as that in Example 1-2.

[0454] <Example 6>

[0455] In the same manner as in Example 1-2, a fluorination reaction apparatus was prepared.

[0456] 300 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus and stirred while maintaining at 20°C. After blowing nitrogen into the autoclave at 20°C for 1 hour, 30% fluorine gas was blown in at a flow rate of 2.0 L / hour at 20°C for 1 hour.

[0457] Next, while blowing 30% fluorine gas at the same flow rate, a solution obtained 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.

[0458] 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. Further, while blowing 30% fluorine gas at the same flow rate, stirring was continued for 1 hour. Then, nitrogen was blown in for 1 hour.

[0459] After concentrating the contents of the autoclave with an evaporator, high-polarity impurities were removed by silica gel chromatography (developing solvent: AC-2000), and 9.93 g (yield 99.1%) of the said Compound 1-2 was recovered.

[0460] The structure of the obtained Compound 1-2 and 19 The F-NMR data was the same as that in Example 1-2.

[0461] <Example 7>

[0462] In the same manner as in Example 1-2, a fluorination reaction apparatus was prepared.

[0463] 301 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus and stirred while maintaining at 20°C. After blowing nitrogen into the autoclave at 20°C for 1 hour, 30% fluorine gas was blown in at a flow rate of 2.0 L / hour at 20°C for 1 hour.

[0464] Next, while blowing 30% fluorine gas at the same flow rate, a solution obtained 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.

[0465] 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. Further, while blowing 30% fluorine gas at the same flow rate, stirring was continued for 1 hour. Then, nitrogen gas was blown for 1 hour.

[0466] After concentrating the content of the autoclave with an evaporator, high-polarity 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.

[0467] The structure of the obtained compound 1-2 and 19 the 19F-NMR data were the same as those in Example 1-2.

[0468] <Example 8>

[0469] In the same manner as in Example 1-2, a fluorination reaction apparatus was prepared.

[0470] 300 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus, and stirring was carried out while maintaining the temperature at 20°C. After blowing nitrogen gas into the autoclave at 20°C for 1 hour, 30% fluorine gas was blown at a flow rate of 2.0 L / hour at 20°C for 1 hour.

[0471] Next, while blowing 30% fluorine gas at the same flow rate, a solution obtained by dissolving 8.5 g of the 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.

[0472] 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. Further, while blowing 30% fluorine gas at the same flow rate, stirring was continued for 1 hour. Then, nitrogen gas was blown for 1 hour.

[0473] After concentrating the content of the autoclave with an evaporator, high-polarity 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.

[0474] The structure of the obtained compound 1-2 and 19 the 19F-NMR data were the same as those in Example 1-2.

[0475] <Example 9>

[0476] In the same manner as in Example 1-2, a fluorination reaction apparatus was prepared.

[0477] Charge 300 g of CFE-419 into the autoclave of the fluorination reaction apparatus and stir while maintaining at 20 °C. After blowing nitrogen into the autoclave at 20 °C for 1 hour, blow in 30% fluorine gas at a flow rate of 2.0 L / hour at 20 °C for 1 hour.

[0478] Next, while blowing in 30% fluorine gas at the same flow rate, inject into the autoclave over 5.3 hours a solution obtained 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.

[0479] Next, inject 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 into the autoclave and close the benzene solution inlet of the autoclave. Further, continue stirring for 1 hour while blowing in 30% fluorine gas at the same flow rate. Then, blow in nitrogen for 1 hour.

[0480] After concentrating the contents of the autoclave with an evaporator, remove high-polarity impurities by silica gel chromatography (developing solvent: AC-2000) to recover 9.93 g (yield 99.1%) of the said Compound 1-2.

[0481] The structure of the obtained Compound 1-2 and 19 the 19F-NMR data are the same as those in Example 1-2.

[0482] <Example 10>

[0483] Operate in the same manner as in Example 1-2 to prepare a fluorination reaction apparatus.

[0484] Charge 300 g of CFE-419 into the autoclave of the fluorination reaction apparatus and stir while maintaining at 20 °C. After blowing nitrogen into the autoclave at 20 °C for 1 hour, blow in 30% fluorine gas at a flow rate of 2.0 L / hour at 20 °C for 1 hour.

[0485] Next, while blowing in 30% fluorine gas at the same flow rate, inject into the autoclave over 5.3 hours a solution obtained 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.

[0486] Next, inject 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 into the autoclave and close the benzene solution inlet of the autoclave. Further, continue stirring for 1 hour while blowing in 30% fluorine gas at the same flow rate. Then, blow in nitrogen for 1 hour.

[0487] The contents of the autoclave were concentrated using an evaporator, and then highly polar impurities were removed using a silica gel chromatography (developing solvent: AC-2000), thereby recovering 9.81 g (yield: 99.1%) of the compound 1-2.

[0488] The structure of the obtained compound 1-2 and 19 The F-NMR data were the same as those in Example 1-2.

[0489] <Example 11>

[0490] A fluorination reaction apparatus was prepared in the same manner as in Example 1-2.

[0491] 300 g of CFE-419 was placed in the autoclave of the fluorination reaction apparatus and stirred while maintaining the temperature at 20° C. Nitrogen was blown into the autoclave at 20° C. for 1 hour, and then 30% fluorine gas was blown into the autoclave at 20° C. at a flow rate of 2.0 L / hour for 1 hour.

[0492] Next, while blowing 30% fluorine gas at the same flow rate, a solution prepared by dissolving 8.4 g of the 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.

[0493] 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 injection port of the autoclave was closed. Further, 30% fluorine gas was blown in at the same flow rate while stirring was continued for 1 hour. Then, nitrogen gas was blown in for 1 hour.

[0494] The contents of the autoclave were concentrated using an evaporator, and then highly polar impurities were removed using a silica gel chromatography (developing solvent: AC-2000), thereby recovering 9.79 g (yield: 98.9%) of the compound 1-2.

[0495] The structure of the obtained compound 1-2 and 19 The F-NMR data were the same as those in Example 1-2.

[0496] <Example 12-1>

[0497] Add 50.2 g of the following alcohol 2 and 100.9 g of NaF to a flask. As NaF, use NaF with an average primary particle size of 5 μm (manufactured by Kanto Chemical, Deer Special Grade 37174-00). Add 25.2 g of AC-2000 and 798.1 g of the aforementioned (HFPO)2 thereto and mix. After mixing, seal the mixture and heat and stir at 50°C for 10 hours. After 10 hours of heating and stirring, cool naturally and filter to remove NaF. Then, remove (HFPO)2 and AC-2000 by vacuum distillation.

[0498] Alcohol 2: 1,5-pentanediol (Product code: P0050, Molecular weight: 104)

[0499] By removing highly polar impurities using silica gel chromatography (developing solvent: AC-2000), 349.65 g (yield 99.9%) of the ester compound was obtained.

[0500] 1 H-NMR and 19 As a result of F-NMR analysis, it was confirmed that the obtained compound was Compound 12-1 below. In addition, based on 1 H-NMR and 19 F-NMR, it was confirmed that Alcohol 2 and Carboxylic acid 1 mentioned above were not detected, and it was confirmed by measuring the F ion concentration that HF and NaF were not detected.

[0501] Compound 12-1: CF3CF2CF2OCF(CF3)COOCH2CH2CH2CH2CH2OCOCF(CF3)OCF2CF2CF3

[0502] 1 H-NMR (300.4 MHz, solvent CDCl3, reference TMS) δ (ppm): 1.6 (4H), 1.9 (2H), 4.1 (4H)

[0503] 19 F-NMR (282.7 MHz, solvent CDCl3, reference CFCl3) δ (ppm): -81.7 (6F), -82.0 (6F), -85.6 (4F), -130.0 (4F), -131.8 (2F)

[0504] <Example 12-2>

[0505] The fluorination reaction apparatus was prepared in the same manner as in Example 1-2.

[0506] 300 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus and stirred while maintaining at 20°C. After blowing nitrogen into the autoclave at 20°C for 1 hour, 30% fluorine gas was blown in at a flow rate of 2.0 L / hour at 20°C for 1 hour.

[0507] Next, while blowing 30% fluorine gas at the same flow rate, a solution obtained 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.

[0508] 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. Further, while blowing 30% fluorine gas at the same flow rate, stirring was continued for 1 hour. Then, nitrogen gas was blown for 1 hour.

[0509] After concentrating the contents of the autoclave with an evaporator, high-polarity impurities were removed by silica gel chromatography (developing solvent: AC-2000), and 10.15 g (yield 98.0%) of the following compound 12-2 was recovered.

[0510] Compound 12-2: CF3CF2CF2OCF(CF3)COOCF2CF2CF2CF2CF2OCOCF(CF3)OCF2CF2CF3

[0511] 19 F-NMR (282.7 MHz, solvent CDCl3, reference CFCl3) 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)

[0512] <Example 13>

[0513] In the same manner as in Example 1-2, a fluorination reaction apparatus was prepared.

[0514] 300 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus, and stirring was carried out while maintaining at 20°C. After blowing nitrogen gas into the autoclave at 20°C for 1 hour, 30% fluorine gas was blown at a flow rate of 2.0 L / hour at 20°C for 1 hour.

[0515] Next, while blowing 30% fluorine gas at the same flow rate, a solution obtained 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.

[0516] 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. Further, while blowing 30% fluorine gas at the same flow rate, stirring was continued for 1 hour. Then, nitrogen gas was blown for 1 hour.

[0517] After concentrating the contents of the autoclave with an evaporator, high-polarity impurities were removed by silica gel chromatography (developing solvent: AC-2000), and 7.44 g (yield 71.0%) of the said compound 12-2 was recovered.

[0518] The structure of the obtained compound 12-2 and 19 the F-NMR data are the same as those in Example 12-2.

[0519] <Example 14>

[0520] In the same manner as in Example 1-2, a fluorination reaction apparatus was prepared.

[0521] 300 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus and stirred while maintaining at 20°C. After blowing nitrogen into the autoclave at 20°C for 1 hour, 30% fluorine gas was blown in at a flow rate of 2.0 L / hour at 20°C for 1 hour.

[0522] Next, while blowing 30% fluorine gas at the same flow rate, a solution obtained by dissolving 8.4 g of the 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.

[0523] 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. Further, while blowing 30% fluorine gas at the same flow rate, stirring was continued for 1 hour. Then, nitrogen was blown in for 1 hour.

[0524] The content of the autoclave was concentrated by an evaporator, and high-polarity impurities were removed by silica gel chromatography (developing solvent: AC-2000) to recover 7.42 g (yield 70.8%) of the compound 12-2.

[0525] The structure of the obtained compound 12-2 and 19 the F-NMR data are the same as those in Example 12-2.

[0526] <Example 15>

[0527] In the same manner as in Example 1-2, a fluorination reaction apparatus was prepared.

[0528] 300 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus and stirred while maintaining at 20°C. After blowing nitrogen into the autoclave at 20°C for 1 hour, 30% fluorine gas was blown in at a flow rate of 2.0 L / hour at 20°C for 1 hour.

[0529] Next, while blowing in 30% fluorine gas at the same flow rate, a solution obtained 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.

[0530] 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. Further, while blowing in 30% fluorine gas at the same flow rate, stirring was continued for 1 hour. Then, nitrogen gas was blown in for 1 hour.

[0531] After concentrating the contents of the autoclave with an evaporator, high-polarity impurities were removed by silica gel chromatography (developing solvent: AC-2000), and 7.58 g (yield 71.5%) of the said Compound 12-2 was recovered.

[0532] The structure of the obtained Compound 12-2 and 19 the 19F-NMR data were the same as those of Example 12-2.

[0533] <Example 16>

[0534] In the same manner as in Example 1-2, a fluorination reaction apparatus was prepared.

[0535] 300 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus, and stirring was carried out while maintaining the temperature at 20°C. After blowing nitrogen gas into the autoclave at 20°C for 1 hour, 30% fluorine gas was blown in at a flow rate of 2.0 L / hour at 20°C for 1 hour.

[0536] Next, while blowing in 30% fluorine gas at the same flow rate, a solution obtained 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.

[0537] 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. Further, while blowing in 30% fluorine gas at the same flow rate, stirring was continued for 1 hour. Then, nitrogen gas was blown in for 1 hour.

[0538] After concentrating the contents of the autoclave with an evaporator, high-polarity impurities were removed by silica gel chromatography (developing solvent: AC-2000), and 10.16 g (yield 98.1%) of the said Compound 12-2 was recovered.

[0539] The structure of the obtained Compound 12-2 and19 The F-NMR data was the same as that in Example 12-2.

[0540] <Example 17>

[0541] In the same manner as in Example 1-2, a fluorination reaction apparatus was prepared.

[0542] 300 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus and stirred while maintaining the temperature at 20°C. After blowing nitrogen into the autoclave at 20°C for 1 hour, 30% fluorine gas was blown into the autoclave at a flow rate of 2.0 L / hour at 20°C for 1 hour.

[0543] Next, while blowing 30% fluorine gas at the same flow rate, a solution obtained 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.

[0544] 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. Further, while blowing 30% fluorine gas at the same flow rate, stirring was continued for 1 hour. Then, nitrogen was blown for 1 hour.

[0545] After concentrating the contents of the autoclave with an evaporator, high-polarity impurities were removed by silica gel chromatography (developing solvent: AC-2000), and 10.29 g (yield 98.2%) of the said Compound 12-2 was recovered.

[0546] The structure of the obtained Compound 12-2 and 19 The F-NMR data was the same as that in Example 12-2.

[0547] <Example 18>

[0548] In the same manner as in Example 1-2, a fluorination reaction apparatus was prepared.

[0549] 300 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus and stirred while maintaining the temperature at 20°C. After blowing nitrogen into the autoclave at 20°C for 1 hour, 30% fluorine gas was blown into the autoclave at a flow rate of 2.0 L / hour at 20°C for 1 hour.

[0550] Next, while blowing 30% fluorine gas at the same flow rate, a solution obtained 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.

[0551] 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. Further, while blowing 30% fluorine gas at the same flow rate, stirring was continued for 1 hour. Then, nitrogen gas was blown for 1 hour.

[0552] After concentrating the content of the autoclave with an evaporator, high-polarity 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.

[0553] The structure of the obtained compound 12-2 and 19 the 19F-NMR data were the same as those in Example 12-2.

[0554] <Example 19>

[0555] In the same manner as in Example 1-2, a fluorination reaction apparatus was prepared.

[0556] 300 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus, and stirring was carried out while maintaining the temperature at 20°C. After blowing nitrogen gas into the autoclave at 20°C for 1 hour, 30% fluorine gas was blown at a flow rate of 2.0 L / hour at 20°C for 1 hour.

[0557] Next, while blowing 30% fluorine gas at the same flow rate, a solution obtained by dissolving 8.4 g of the 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.

[0558] 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. Further, while blowing 30% fluorine gas at the same flow rate, stirring was continued for 1 hour. Then, nitrogen gas was blown for 1 hour.

[0559] After concentrating the content of the autoclave with an evaporator, high-polarity 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.

[0560] The structure of the obtained compound 12-2 and 19 the 19F-NMR data were the same as those in Example 12-2.

[0561] <Example 20>

[0562] In the same manner as in Example 1-2, a fluorination reaction apparatus was prepared.

[0563] Charge 300 g of CFE-419 into the autoclave of the fluorination reaction apparatus and stir while maintaining at 20°C. After blowing nitrogen into the autoclave at 20°C for 1 hour, blow in 30% fluorine gas at a flow rate of 2.0 L / hour at 20°C for 1 hour.

[0564] Next, while blowing in 30% fluorine gas at the same flow rate, inject into the autoclave a solution obtained 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 over 3.1 hours.

[0565] Next, inject 9 mL of a benzene solution containing 0.015 g / mL of benzene in CFE-419 into the autoclave and close the benzene solution injection port of the autoclave. Further, while blowing in 30% fluorine gas at the same flow rate, continue stirring for 1 hour. Then, blow in nitrogen for 1 hour.

[0566] After concentrating the content of the autoclave with an evaporator, remove high-polarity impurities by silica gel chromatography (developing solvent: AC-2000) to recover 10.42 g (yield 98.3%) of the said Compound 12-2.

[0567] The structure of the obtained Compound 12-2 and 19 the 19F-NMR data are the same as those of Example 12-2.

[0568] <Example 21>

[0569] Recover the following Compound 21 at a yield of 69.0% according to the method described in Example 2 of the example of International Publication No. 2000-056694.

[0570] Compound 21: CF3(CF3CF2CF2O)CFCOOCF2CF(OCF2CF2CF3)CF3 <Example 22-1>

[0571] Add 50.2 g of the said alcohol 2 and 100.9 g of NaF to a flask. As NaF, use NaF with an average primary particle size of 5 μm (manufactured by Kanto Chemical Co., Ltd., Rokkaku Special Grade 37174-00). Add 25.2 g of AC-2000 and 457 g of (CF3)2CFCOF thereto and mix. After mixing, seal and carry out heating and stirring at 50°C for 10 hours. After 10 hours of heating and stirring, cool naturally and filter to remove NaF. Then, remove (CF3)2CFCOF and AC-2000 by vacuum distillation.

[0572] Remove high-polarity impurities by silica gel chromatography (developing solvent: AC-2000) to obtain 237.59 g (yield 96.9%) of an ester compound.

[0573] 1 1H-NMR and 19 the results of 19F-NMR analysis confirmed that the obtained compound was the following Compound 22-1. In addition, based on 1 1H-NMR and 19 19F-NMR, it was confirmed that the above alcohol 2 and the following carboxylic acid 2 were not detected, and it was confirmed by measuring the F ion concentration that HF and NaF were not detected.

[0574] Compound 22-1: (CF3)2CFCOOCH2CH2CH2CH2CH2OCOCF(CF3)2

[0575] 1 1H-NMR (300.4 MHz, solvent CDCl3, reference TMS) δ (ppm): 1.42 to 1.53 (2H), 1.70 to 1.84 (4H), 4.20 to 5.20 (4H)

[0576] 19 19F-NMR (282.7 MHz, solvent CDCl3, reference CFCl3) δ (ppm): -74.3 (12F), -81.9 (2F)

[0577] Carboxylic acid 2: 2,3,3,3-tetrafluoro-2-(trifluoromethyl)-propanoic acid (chemical formula: (CF3)2CFCOOH)

[0578] <Example 22-2>

[0579] In the same manner as in Example 1-2, a fluorination reaction apparatus was prepared.

[0580] 300 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus and stirred while maintaining at 20°C. After blowing nitrogen into the autoclave at 20°C for 1 hour, 30% fluorine gas was blown in at a flow rate of 2.0 L / hour at 20°C for 1 hour.

[0581] Next, while blowing 30% fluorine gas at the same flow rate, a solution obtained 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.

[0582] 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. Further, while blowing 30% fluorine gas at the same flow rate, stirring was continued for 1 hour. Then, nitrogen was blown in for 1 hour.

[0583] After concentrating the contents of the autoclave with an evaporator, according to1 H-NMR confirmed that the H peak of the raw material disappeared (conversion rate>99.9%), and 11.32 g (yield 98.9%) of the following compound 22-2 was recovered.

[0584] Compound 22-2: (CF3)2CFCOOCF2CF2CF2CF2CF2OCOCF(CF3)2

[0585] 19 F-NMR (282.7 MHz, solvent CDCl3, standard CFCl3) δ (ppm): -74.3 (12F), -86.1 (4F), -122.6 (2F), -125.7 (4F), -181.9 (2F)

[0586] <Example 23-1>

[0587] Add 50.1 g of the following alcohol 3 and 88.9 g of NaF to a flask. As NaF, use NaF with an average primary particle size of 5 μm (manufactured by Kanto Chemical, Deer Special Grade 37174-00). Add 25.2 g of AC-2000 and 1055 g of the following (HFPO) 3 and mix. After mixing, seal the flask and heat and stir at 50°C for 10 hours. After 10 hours of heating and stirring, cool naturally and filter to remove NaF. Then, remove (HFPO) 3 and AC-2000 by vacuum distillation.

[0588] Alcohol 3: 1,6-hexanediol (Product code: H0099, molecular weight: 118)

[0589] (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]-propionyl fluoride (chemical formula: CF3CF2CF2OCF(CF3)CF2OCF(CF3)COF, manufactured by Tokyo Chemical Industry, product number: B1698)

[0590] Highly polar impurities were removed using silica gel chromatography (developing solvent: AC-2000) to obtain 445.98 g (yield 98.0%) of an ester compound.

[0591] 1 H-NMR and 19 The result of F-NMR analysis confirmed that the obtained compound was the following compound 23-1. 1 H-NMR and 19 F-NMR confirmed that the above alcohol 3 and the following carboxylic acid 3 were not detected, and F ion concentration measurement confirmed that HF ​​and NaF were not detected.

[0592] Compound 23-1: CF3CF2CF2OCF(CF3)CF2OCF(CF3)COOCH2CH2CH2CH2CH2CH2OCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3

[0593] 1 1H-NMR (300.4 MHz, solvent CDCl3, reference TMS) δ (ppm): 1.27 (4H), 1.67 (4H), 4.20 (4H)

[0594] 19 19F-NMR (282.7 MHz, solvent CDCl3, reference CFCl3) δ (ppm): -80.8 (6F), -81.7 (14F), -82.0 (6F), -129.7 (4F), -131.8 (2F), -145.2 (2F)

[0595] 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: CF3CF2CF2OCF(CF3)CF2OCF(CF3)COOH)

[0596] <Example 23-2>

[0597] In the same manner as in Example 1-2, a fluorination reaction apparatus was prepared.

[0598] 300 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus and stirred while maintaining at 20 °C. After blowing nitrogen into the autoclave at 20 °C for 1 hour, 30% fluorine gas was blown in at a flow rate of 2.0 L / hour at 20 °C for 1 hour.

[0599] Next, while blowing 30% fluorine gas at the same flow rate, a solution obtained 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.

[0600] 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. Further, while blowing 30% fluorine gas at the same flow rate, stirring was continued for 1 hour. Then, nitrogen was blown in for 1 hour.

[0601] After concentrating the content of the autoclave with an evaporator, according to 1H-NMR confirmed that the H peak of the raw material disappeared (conversion rate>99.9%), and 9.95 g (yield 98.6%) of the following compound 23-2 was recovered.

[0602] Compound 23-2: CF3CF2CF2OCF(CF3)CF2OCF(CF3)COOCF2CF2CF2CF2CF2CF2OCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3

[0603] 19 F-NMR (282.7 MHz, solvent CDCl3, standard CFCl3) 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)

[0604] <Example 24-1>

[0605] Add 50.0 g of the alcohol 4 and 78.4 g of NaF to a flask. As NaF, use NaF with an average primary particle size of 5 μm (produced by Kanto Chemical, Deer Special Grade 37174-00). Add 25.1 g of AC-2000 and 929 g of the (HFPO)3 and mix. After mixing, seal the flask and heat and stir at 50°C for 10 hours. After 10 hours of heating and stirring, cool naturally and filter to remove NaF. Then, remove (HFPO)3 and AC-2000 by vacuum distillation.

[0606] Alcohol 4: Diethylene glycol monoethyl ether (chemical formula: CH3CH2OCH2CH2OCH2CH2OH, product code: E0048, molecular weight: 134)

[0607] Highly polar impurities were removed using silica gel chromatography (developing solvent: AC-2000) to obtain 224.7 g (yield 98.4%) of an ester compound.

[0608] 1 H-NMR and 19 As a result of F-NMR analysis, it was confirmed that the obtained compound was the following compound 24-1. 1 H-NMR and 19 F-NMR confirmed that the alcohol 4 and the carboxylic acid 3 were not detected, and F ion concentration measurement confirmed that HF ​​and NaF were not detected.

[0609] Compound 24-1: CH3CH2OCH2CH2OCH2CH2OCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3

[0610] 1 1H-NMR (300.4 MHz, solvent CDCl3, reference TMS) δ (ppm): 1.20 (3H), 3.53 (2H), 3.62 (4H), 3.71 (2H), 4.55 (2H)

[0611] 19 19F-NMR (282.7 MHz, solvent CDCl3, reference CFCl3) δ (ppm): -80.8 (3F), -81.7 (7F), -82.0 (3F), -129.7 (2F), -131.8 (1F), -145.2 (1F)

[0612] <Example 24-2>

[0613] In the same manner as in Example 1-2, a fluorination reaction apparatus was prepared.

[0614] 300 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus and stirred while maintaining at 20°C. After blowing nitrogen into the autoclave at 20°C for 1 hour, 30% fluorine gas was blown in at a flow rate of 2.0 L / hour at 20°C for 1 hour.

[0615] Next, while blowing 30% fluorine gas at the same flow rate, a solution obtained 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.

[0616] 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. Further, while blowing 30% fluorine gas at the same flow rate, stirring was continued for 1 hour. Then, nitrogen was blown in for 1 hour.

[0617] After concentrating the contents of the autoclave with an evaporator, according to 1 1H-NMR confirmed that the H peak of the raw material disappeared (conversion rate > 99.9%), and 11.48 g (yield 98.9%) of Compound 24-2 was recovered.

[0618] Compound 24-2: CF3CF2OCF2CF2OCF2CF2OCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3

[0619] 19F-NMR (282.7 MHz, solvent CDCl3, reference CFCl3) 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)

[0620] <Example 25-1>

[0621] Add 50.0 g of the following alcohol 5 and 30.9 g of NaF to a flask. As NaF, NaF with an average primary particle size of 5 μm (manufactured by Kanto Chemical Co., Ltd., Lot Special Grade 37174-00) was used. Add 25.2 g of AC-2000 and 244.1 g of the said (HFPO)2 thereto and mix. After mixing, seal and carry out heating and stirring at 50 °C for 10 hours. After 10 hours of heating and stirring, allow to cool naturally and filter to remove NaF. Then, remove (HFPO)2 and AC-2000 by vacuum distillation.

[0622] Alcohol 5: Polyoxyethylene monomethyl ether (chemical formula: CH3-O-(C2H4O) n -H, n = 7, trade name: UNIOX M-400, manufactured by NOF Corporation, molecular weight: 340)

[0623] By removing highly polar impurities with a silica gel chromatograph (developing solvent: AC-2000), 94.94 g (yield 99.0%) of an ester compound was obtained.

[0624] 1 1H-NMR and 19 As a result of 19F-NMR analysis, it was confirmed that the obtained compound was the following compound 25-1. In addition, based on 1 1H-NMR and 19 19F-NMR, it was confirmed that neither the above alcohol 5 nor the carboxylic acid 1 was detected, and it was confirmed by measuring the F ion concentration that neither HF nor NaF was detected.

[0625] Compound 25-1: CH3-O-(C2H4O) n -COCF(CF3)OCF2CF2CF3

[0626] 1 1H-NMR (300.4 MHz, solvent CDCl3, reference TMS) δ (ppm): 3.4 (3H), 3.5 (2H), 3.7 (24H), 4.9 (2H) Average value of the number of units n: 7.0

[0627] 19F-NMR (282.7 MHz, solvent CDCl3, reference CFCl3) δ (ppm): -81.7 (3F), -82.0 (3F), -85.6 (2F), -130.0 (2F), -131.8 (1F)

[0628] <Example 25-2>

[0629] In the same manner as in Example 1-2, a fluorination reaction apparatus was prepared.

[0630] 300 g of CFE-419 was charged into the autoclave of the fluorination reaction apparatus and stirred while maintaining the temperature at 20°C. After blowing nitrogen into the autoclave at 20°C for 1 hour, 30% fluorine gas was blown in at a flow rate of 2.0 L / hour at 20°C for 1 hour.

[0631] Next, while blowing 30% fluorine gas at the same flow rate, a solution obtained 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.

[0632] 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. Further, while blowing 30% fluorine gas at the same flow rate, stirring was continued for 1 hour. Then, nitrogen was blown in for 1 hour.

[0633] After concentrating the contents of the autoclave with an evaporator, according to 1 1H-NMR confirmed that the H peak of the raw material disappeared (conversion rate > 99.9%), and 14.98 g (yield 96.1%) of the following Compound 25-2 was recovered.

[0634] Compound 25-2: CF3-O-(C2F4O) n -COCF(CF3)OCF2CF2CF3

[0635] 19 F-NMR (282.7 MHz, solvent CDCl3, reference CFCl3) 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)

[0636] <Example 26-1>

[0637] Add 50.0 g of the following alcohol 6 and 175 g of NaF to a flask. As NaF, use NaF with an average primary particle size of 5 μm (manufactured by Kanto Chemical Co., Ltd., Rokkaku Special Grade 37174-00). Add 25.2 g of AC-2000 and 2075 g of the said (HFPO)3 thereto, and mix. After mixing, seal and carry out heating and stirring at 50 °C for 10 hours. After 10 hours of heating and stirring, cool naturally and filter to remove NaF. Then, remove (HFPO)3 and AC-2000 by vacuum distillation.

[0638] Alcohol 6: 1-propanol (product code: P0491, molecular weight: 60)

[0639] Remove high-polarity impurities by silica gel chromatography (developing solvent: AC-2000) to obtain 439.4 g (yield 98.0%) of an ester compound.

[0640] 1 H-NMR and 19 As a result of 19F-NMR analysis, it was confirmed that the obtained compound was the following compound 26-1. In addition, based on 1 H-NMR and 19 19F-NMR, it was confirmed that the above alcohol 6 and carboxylic acid 3 were not detected, and it was confirmed by measuring the F ion concentration that HF and NaF were not detected.

[0641] Compound 26-1: CH3CH2CH2OCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3

[0642] 1 H-NMR (300.4 MHz, solvent CDCl3, reference TMS) δ (ppm): 0.95 (3H), 1.73 (2H), 4.26 (2H)

[0643] 19 19F-NMR (282.7 MHz, solvent CDCl3, reference CFCl3) δ (ppm): -80.8 (3F), -81.7 (7F), -82.0 (3F), -129.7 (2F), -131.8 (1F), -145.2 (1F)

[0644] <Example 26-2>

[0645] Operate in the same manner as in Example 1-2 to prepare a fluorination reaction apparatus.

[0646] Charge 300 g of CFE-419 into the autoclave of the fluorination reaction apparatus and stir while maintaining at 20 °C. After blowing nitrogen into the autoclave at 20 °C for 1 hour, blow 30% fluorine gas at a flow rate of 2.0 L / hour at 20 °C for 1 hour.

[0647] Next, while blowing in 30% fluorine gas at the same flow rate, a solution obtained 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.

[0648] 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. Further, while blowing in 30% fluorine gas at the same flow rate, stirring was continued for 1 hour. Then, nitrogen gas was blown in for 1 hour.

[0649] After concentrating the contents of the autoclave with an evaporator, according to 1 1H-NMR, it was confirmed that the H peak of the raw material disappeared (conversion rate > 99.9%), and 10.00 g (yield 96.5%) of the following Compound 26-2 was recovered.

[0650] Compound 26-2: CF3CF2CF2OCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3

[0651] 19 19F-NMR (282.7 MHz, solvent CDCl3, reference CFCl3) 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)

[0652] The amounts of OH compound, carboxylic acid, HF, NaF in Examples 1 to 26 and the yields of the fluorine-containing ester compounds as the target products are shown in the following table. In addition, the presence or absence of an ether bond in the ester compounds as raw materials for the fluorination reaction in Examples 1 to 26 is also shown in the table.

[0653] [Table 1]

[0654]

[0655] [Table 2]

[0656]

[0657] [Table 3]

[0658]

[0659] As shown in Tables 1 to 3, compared with the comparative examples, the fluorine-containing ester compounds as the target products can be obtained in high yields in the examples.

[0660] Industrial applicability

[0661] The method for producing a fluorine-containing ester compound of the present disclosure can produce a fluorine-containing ester compound in a higher yield than in the past. The obtained fluorine-containing ester compound can be derived into fluorine-containing compounds having various functional groups (for example, a hydroxyl group, an ethylenically unsaturated group, an epoxy group, a carboxyl group, etc.). In addition, the obtained fluorine-containing ester compound and fluorine-containing compound can be used as a surface treatment agent, an emulsifier, a rubber, a surfactant, a solvent, a heat medium, a medicine, a pesticide, a lubricating oil, an intermediate thereof, etc.

[0662] The entire 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 in this specification are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually recited.

Claims

1. A method for producing a fluorine-containing ester compound, which comprises fluorinating an ester compound having at least one fluorinable 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. With respect 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 carboxyl group is 2.0 parts by mass or less, and the content of 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 includes an ester compound having an ether bond, the liquid further contains hydrogen fluoride, and with respect to 100 parts by mass of the ester compound, the content of hydrogen fluoride is 3.0 parts by mass or less.

3. The method for producing a fluorine-containing ester compound according to claim 1, wherein, With respect to 100 parts by mass of the ester compound, 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 carboxyl group, and the content of sodium fluoride is 0.01 part by mass or more.

4. The method for producing a fluorine-containing ester compound according to claim 2, wherein, With respect to 100 parts by mass of the ester compound, 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 carboxyl group, the content of sodium fluoride, and the content of hydrogen fluoride is 0.01 part by mass or more.

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

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 the compound represented by the following formula (3) and the compound represented by the following formula (4), R A3 -OH…(3) HO-R A4 -OH…(4) in formulas (3) and (4), R A3 is a monovalent saturated hydrocarbon group, halogenated monovalent saturated hydrocarbon group, heteroatom-containing monovalent saturated hydrocarbon group or halogenated (heteroatom-containing monovalent saturated hydrocarbon) group, R A4 is 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.

7. The method for producing a fluorine-containing ester compound according to claim 6, wherein, R in the formula (3) A3 is the same as R in the formula (1) A1 and R in the formula (4) A4 is the same as R in the formula (2). A2 Same.

8. The method for producing a fluorine-containing ester compound according to claim 5, wherein, the compound having a carboxyl group includes the compound represented by the following formula (5), R B4 -(C=O)-OH…(5) in formula (5), R B4 is a monovalent saturated hydrocarbon group, a halogenated monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogenated (heteroatom-containing monovalent saturated hydrocarbon) group.

9. The method for producing a fluorine-containing ester compound according to claim 8, wherein, R in the formula (5) described above B4 is the same as R in the formula (1) B1 or R in the formula (2) B2 is the same.

10. A composition containing: an ester compound having at least one fluorinable 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. With respect 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 carboxyl group is 2.0 parts by mass or less, and the content of sodium fluoride is 2.0 parts by mass or less.

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

12. The composition according to claim 10, wherein With respect to 100 parts by mass of the ester compound, 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 carboxyl group, and the content of sodium fluoride is 0.01 part by mass or more.

13. The composition according to claim 11, wherein, With respect to 100 parts by mass of the ester compound, 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 carboxyl group, the content of sodium fluoride, and the content of hydrogen fluoride is 0.01 part by mass or more.

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 the compound represented by the following formula (1) and the compound represented by the following formula (2), The compound having a hydroxyl group includes at least one selected from the group consisting of the compounds represented by the following formula (3) and the compounds represented by the following formula (4), The compound having a carboxyl group includes the compound represented by the following formula (5), R A1 -O-(C=O)-R B1 …(1) R B2 -(C=O)-O-R 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 each independently represents a monovalent saturated hydrocarbon group, a halogenated monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogenated (heteroatom-containing monovalent saturated hydrocarbon) group. R A2 and R A4 each independently represents 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.

15. The composition according to claim 14, wherein, R in the formula (3) A3 is the same as R in the formula (1), A1 R in the formula (4) A4 is the same as R in the formula (2), A2 R in the formula (5) B4 is the same as R in the formula (1) B1 or R in the formula (2). B2 The same.

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