Method for producing fluorine-containing carboxylic acid amide

Abstract

To provide a method for producing a fluorine-containing carboxylic acid amide in high purity without separating and removing a fluorine-containing ketone from a raw material containing the fluorine-containing ketone and a fluorine-containing carboxylic acid derivative.SOLUTION: A method for producing a fluorinated carboxylic acid amide represented by the general formula (4), wherein the fluorinated carboxylic acid amide is obtained by reacting a starting material comprising a fluorinated isopropyl ketone represented by the general formula (1) and a fluorinated carboxylic acid derivative represented by the general formula (2) with an amine represented by the general formula (3), and in the general formula (2), when X represents any one of halogen atoms, OR1, OCOR1 and OSO2R1, the amount of the amine used is 1 to 2 times the total amount of the fluorinated isopropyl ketone and the fluorinated carboxylic acid derivative used, when X represents NR2R3 in the general formula (2), the amount of the amine used is 1 to 2 times the amount of the fluorine-containing isopropyl ketone used.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Fluorine-containing compounds having fluorine atoms in the molecule have high thermal and chemical stability and are therefore used in various fields as highly functional compounds. Among them, fluorine-containing carboxylic acid amides, which are compounds having an amide group at the terminal, are used as metal surface modifiers and the like, utilizing the adsorption of the amide group onto metal surfaces. Furthermore, fluorine-containing carboxylic acid amides linked to various functional molecules via amide bonds are attracting attention as even more highly functional compounds.

[0003] For example, Patent Document 1 discloses a release liquid composition containing a fluorine compound having a hydrophilic group with a betaine structure and an amide bond. Patent Document 2 discloses a hair cosmetic containing a perfluoropolyether compound having an amino group and an amide bond. Patent Document 3 discloses a fluorine-containing curable composition containing a fluorine-containing organohydrogensiloxane having an amide bond. Patent Document 4 discloses a lip cosmetic containing a perfluoropolyether compound having an amino group and an amide bond. Patent Document 5 discloses a curable perfluoropolyether rubber composition containing a fluorine-containing amide compound having an allyl group or a phenyl group. Patent Document 6 discloses amides obtained using (-)-α-phenylethylamine or the like as intermediates in the production of fluorine-containing optical analysis reagents. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2021-109917 [Patent Document 2] Japanese Patent Publication No. 2020-152703 [Patent Document 3] Japanese Patent Application Publication No. 2019-35012 [Patent Document 4] Japanese Patent Application Publication No. 2018-52824 [Patent Document 5] Japanese Patent Application Laid-Open No. 2005-330434 [Patent Document 6] Japanese Patent Application Publication No. 60-58538 Summary of the Invention [Problem to be solved by the invention]

[0005] The raw materials for fluorine-containing carboxylic acid amides such as amides of pentafluoropropionic acid and amides of perfluoropolyether carboxylic acids contain fluorine-containing carboxylic acid derivatives such as acyl halides and lower alkyl esters of the corresponding fluorine-containing carboxylic acids, and may further contain impurities that are difficult to separate and remove from the fluorine-containing carboxylic acid derivatives. Specifically, they may contain fluorine-containing ketones in which a perfluoroisopropyl group is substituted on the carbonyl group of the corresponding fluorine-containing carboxylic acid derivative.

[0006] However, since this fluorine-containing ketone has a volatility similar to that of the corresponding fluorine-containing carboxylic acid derivative (for example, an acyl halide or a lower alkyl ester), it is difficult to efficiently remove it by distillation, and further, when the fluorine-containing carboxylic acid derivative has a high boiling point, the distillation operation itself is difficult. Furthermore, although a method has been studied in which an acyl halide or a lower alkyl ester of a fluorine-containing carboxylic acid is once converted into a fluorine-containing carboxylic acid or a long-chain alkyl ester, and then the corresponding fluorine-containing ketone is separated and removed, there is a concern that this will increase the number of production steps and make the operation complicated.

[0007] Furthermore, since fluorine-containing ketones are thought to be produced when hexafluoropropylene is contained in the hexafluoropropylene oxide raw material used in the production of the corresponding fluorine-containing carboxylic acid derivative, attempts have been made to increase the purity of the hexafluoropropylene oxide raw material containing hexafluoropropylene, but there are concerns about a decrease in productivity due to the purification step.

[0008] Therefore, the present inventors have intensively studied a production method by which the target fluorine-containing carboxylic acid amide can be obtained with high purity even when a raw material containing a fluorine-containing ketone in addition to a fluorine-containing carboxylic acid derivative is used, and as a result, have found that a high-purity fluorine-containing carboxylic acid amide can be obtained by reacting such a raw material with a predetermined amine in a fixed molar ratio.

[0009] The present invention provides a method for producing a highly pure fluorinated carboxylic acid amide from raw materials containing a fluorinated ketone and a fluorinated carboxylic acid derivative without separating and removing the fluorinated ketone. [Means for solving the problem]

[0010] An embodiment of the present invention is a method for producing a fluorine-containing carboxylic acid amide represented by the following general formula (4): The fluorine-containing carboxylic acid amide is obtained by reacting a raw material containing a fluorine-containing isopropyl ketone represented by the following general formula (1) and a fluorine-containing carboxylic acid derivative represented by the following general formula (2) with an amine represented by the following general formula (3), [ka] (In the above general formulas (1) to (4), n is an integer of 0 to 5, and m is 0 or 1; l is an integer from 0 to 50, X is a halogen atom, OR 1 ,OCOR 1 , OSO2R 1 and N.R. 2 R 3 represents one of the following: R1 represents an alkyl group or a haloalkyl group having 1 to 10 carbon atoms, R 2 and R 3 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or a heteroaryl group having 2 to 10 carbon atoms, or R 2 and R 3 are bonded to each other to form a ring having 2 to 10 carbon atoms. In the above general formula (2), X is a halogen atom, OR 1 ,OCOR 1 and OSO2R 1 when either of the above is represented, the amount of the amine used is 1 to 2 times the sum of the amounts of the fluorine-containing isopropyl ketone and the fluorine-containing carboxylic acid derivative used on a molar basis, In the above general formula (2), X is NR 2 R 3 wherein the amount of the amine used is 1 to 2 times the amount of the fluorinated isopropyl ketone used on a molar basis. [Effects of the Invention]

[0011] According to the present invention, there is provided a method for producing a highly pure fluorinated carboxylic acid amide from raw materials containing a fluorinated ketone and a fluorinated carboxylic acid derivative without separating and removing the fluorinated ketone. DETAILED DESCRIPTION OF THE INVENTION

[0012] <Method of producing fluorine-containing carboxylic acid amide> In the method for producing a fluorine-containing carboxylic acid amide according to this embodiment, a raw material containing a fluorine-containing isopropyl ketone represented by general formula (1) and a fluorine-containing carboxylic acid derivative represented by general formula (2) is reacted with an amine represented by general formula (3) to obtain a fluorine-containing carboxylic acid amide represented by general formula (4). In this reaction, a raw material containing not only the fluorine-containing carboxylic acid derivative but also fluorine-containing isopropyl ketone as an impurity is reacted with the amine represented by general formula (3) in a certain molar equivalent. As a result, even if a fluorine-containing ketone corresponding to an acyl halide or lower alkyl ester of a fluorine-containing carboxylic acid is contained, the corresponding fluorine-containing carboxylic acid amide can be obtained in high purity without separating and removing the fluorine-containing ketone.

[0013] [ka]

[0014] (Compounds represented by general formulas (1) to (4)) In general formulas (1), (2), and (4), n is 0, 1, 2, 3, 4, or 5, and is preferably an integer of 0 to 3. Furthermore, m is 0 or 1, and when m is 1, n is preferably 1, 2, 3, 4, or 5.

[0015] In general formulas (1), (2), and (4), l is an integer of 0 to 50. The lower limit of l may be 1, 2, or 6, and the upper limit of l may be 40, 30, 20, or 15. Furthermore, each compound represented by general formulas (1), (2), and (4) may contain multiple compounds exhibiting different values ​​of l.

[0016] In the general formula (2), X is a halogen atom, OR 1 ,OCOR 1 , OSO2R 1 (OS(=O)2R 1 ) and NR 2 R 3 The halogen atom is F, Cl, Br or I, and is preferably F.

[0017] R 1 represents an alkyl group or haloalkyl group having 1 to 10 carbon atoms. The upper limit of the number of carbon atoms may be 4, 6, or 8. The alkyl group refers to a saturated chain hydrocarbon group or an alicyclic hydrocarbon group. In addition, in the present disclosure, the haloalkyl group refers to an alkyl group in which at least one hydrogen atom is substituted with a halogen atom, and all hydrogen atoms of the alkyl group may be substituted with halogen atoms. The number of halogen atoms in the haloalkyl group may be 1 to 3. The haloalkyl group may be a perfluoroalkyl group or a trifluoromethyl group.

[0018] In the general formulas (2) to (4), R 2 and R 3 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or a heteroaryl group having 2 to 10 carbon atoms, or R 2 and R 3 are bonded to each other to form a ring having 2 to 10 carbon atoms. Preferably, R 2 represents a hydrogen atom and R 3 represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or a heteroaryl group having 2 to 10 carbon atoms, or R 2 and R 3 are bonded to each other to form a ring having 2 to 10 carbon atoms. The number of carbon atoms in the hydrocarbon group is preferably 1 to 9, more preferably 1 to 8, further preferably 1 to 6, and particularly preferably 2 to 4. The heteroaryl group and R 2 and R 3 The number of carbon atoms in the ring formed by bonding together is preferably 4 to 10, more preferably 6 to 9, and even more preferably 7 or 8, independently.

[0019] The hydrocarbon group is not particularly limited as long as it is a hydrocarbon group having 1 to 10 carbon atoms and consisting of carbon atoms and hydrogen atoms. The hydrocarbon group having 1 to 10 carbon atoms is not particularly limited as long as it is a hydrocarbon group having 1 to 10 carbon atoms and consisting of carbon atoms and hydrogen atoms, and examples thereof include a chain hydrocarbon group, an aromatic hydrocarbon group, and an alicyclic hydrocarbon group. The chain hydrocarbon group is not particularly limited as long as it has a total of 1 to 10 carbon atoms, and may be a linear hydrocarbon group or a branched chain hydrocarbon group. The chain hydrocarbon group may also have a substituent. When the hydrocarbon group having 1 to 10 carbon atoms is an aromatic hydrocarbon group, the aromatic hydrocarbon group is not particularly limited as long as it has a total of 6 to 10 carbon atoms, and may be an aromatic hydrocarbon group having a substituent or an aromatic hydrocarbon group having no substituent. The aromatic hydrocarbon group may also have a fused polycyclic structure. When the hydrocarbon group having 1 to 10 carbon atoms is an alicyclic hydrocarbon group, the alicyclic hydrocarbon group is not particularly limited as long as it has a total of 3 to 10 carbon atoms, and may be an alicyclic hydrocarbon group having a substituent or an alicyclic hydrocarbon group having no substituent. The alicyclic hydrocarbon group may have a bridged ring structure.

[0020] Examples of the chain hydrocarbon group include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group; alkenyl groups such as ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, and decenyl groups; Examples include alkynyl groups such as ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, and decynyl.

[0021] Examples of the aromatic hydrocarbon group include a phenyl group, a benzyl group, a tolyl group, an isopropylphenyl group, a naphthyl group, etc. The substituent of the phenyl group contained in the tolyl group or the isopropylphenyl group may be present at any of the ortho, meta, or para positions, but it is preferable that the substituent be present at the para position.

[0022] Examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, a cyclopentyl group, an adamantyl group, and a norbornyl group.

[0023] When the chain hydrocarbon group has a substituent, one of the hydrogen atoms of the chain hydrocarbon group may be substituted with an alkoxyl group or an aralkyl group. The alkoxyl group is preferably an alkoxyl group having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tet-butoxy group, an n-pentoxy group, or an n-hexyloxy group. The aralkyl group is preferably an alkyl group having 1 to 6 carbon atoms, such as a benzyl group, a phenylethyl group, a phenylpropyl group, or a naphthylmethyl group.

[0024] When the aromatic hydrocarbon group and the alicyclic hydrocarbon group have a substituent, examples of the substituent include the above-mentioned alkyl groups and alkoxyl groups having 1 to 6 carbon atoms.

[0025] A heteroaryl group refers to a group in which at least one of the atoms (ring atoms) constituting the ring of a monocyclic or bicyclic (bicyclo) aromatic hydrocarbon group is replaced with a heteroatom. That is, a heteroaryl group has at least one heteroatom as a ring atom. The number of heteroatoms contained in a heteroaryl group as ring atoms is preferably 1 to 4, more preferably 2 to 3. Examples of heteroatoms include N, S, and O atoms. A heteroaryl group may have one, two, or three types of heteroatoms, but preferably has an N atom and preferably does not have an S atom and / or an O atom. In addition, in a heteroaryl group, it is preferable that the heteroatoms are not adjacent to each other, and it is also preferable that the heteroatom in the heteroaryl group is not adjacent to the N atom shown in general formulas (3) and (4).

[0026] Monocyclic heteroaryl groups include pyrimidinyl, pyridazinyl, pyrazinyl, furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, and the like.

[0027] Bicyclic heteroaryl groups include benzotriazolyl, methylindolyl, indolyl, isoindolyl, quinolyl, isoquinolyl, benzofuryl, indolizinyl, benzothienyl, isobenzofuranyl, indazolyl, purinyl, pteridinyl, quinolidinyl, naphthyridinyl, quinoxalinyl, cinnolinyl, benzothiazolyl, benzisothiazolyl, quinazolinyl, phthalazinyl, benzoxazolyl, benzimidazolyl, pyridopyrimidinyl, indolinyl, isoindolinyl, and the like.

[0028] The bicyclic heteroaryl group preferably has 8 to 10 ring atoms and preferably has a 6-membered ring structure and / or a 5-membered ring structure. In addition, in the bicyclic heteroaryl group, the atoms shared by the two rings preferably do not include heteroatoms and are all carbon atoms.

[0029] The heteroaryl group is preferably a bicyclic heteroaryl group, more preferably having 9 ring atoms, even more preferably a benzimidazolyl group, and especially preferably a 2-benzimidazolyl group.

[0030] R 2 and R 3In the formula (I), the hydrocarbon group having 1 to 10 carbon atoms or the heteroaryl group having 2 to 10 carbon atoms may not have a substituent, but may have an optional substituent (hereinafter also referred to as substituent Y). A hydrocarbon group or heteroaryl group having a substituent Y means that a hydrogen atom of the hydrocarbon group or heteroaryl group is substituted with at least one substituent Y. The number of substituents Y is preferably 1, 2 or 3, more preferably 1 or 2, and even more preferably 1. The substituent Y is preferably bonded to a carbon atom (primary carbon) which is bonded to one carbon atom. The substituent Y is preferably an amino group or OA group which may have a hydrocarbon group having 1 to 10 carbon atoms. 1 and more preferably a dialkylamino group having 2 to 10 carbon atoms or OA 1 and more preferably OA 1 When a plurality of substituents Y are present, the respective substituents Y may be the same as or different from one another.

[0031] Substituent Y is OA 1 If you want to represent 1 preferably represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. When the substituent Y is an amino group which may have a hydrocarbon group having 1 to 10 carbon atoms, the hydrocarbon group preferably has 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. A 1 When is a hydrocarbon group having 1 to 10 carbon atoms, the hydrocarbon group preferably has 1 to 7 carbon atoms, more preferably 1 to 4 carbon atoms, further preferably 1 or 2 carbon atoms, and particularly preferably 1 carbon atom. 1 The hydrocarbon group having 1 to 10 carbon atoms in the formula means the hydrocarbon having 1 to 10 carbon atoms listed above.

[0032] When the substituent Y is a dialkylamino group having 2 to 10 carbon atoms, the dialkylamino group preferably has 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The dialkylamino group having 2 to 10 carbon atoms is not particularly limited as long as the total number of carbon atoms in the two alkyl groups bonded to the amino group is 2 to 10, and examples thereof include a dimethylamino group, a diethylamino group, a dipropylamino group, a diisopropylamino group, a dibutylamino group, a di(tert-butyl)amino group, and a dipentylamino group.

[0033] R 2 and R 3 may be bonded to each other to form a ring having 2 to 10 carbon atoms. Such a ring may be monocyclic or bicyclic, but is preferably a bicyclic ring. The ring may or may not have a substituent, but preferably does not contain any N atoms other than those shown in general formulas (3) and (4), and more preferably, the atoms other than the N atoms shown in general formulas (3) and (4) consist of carbon atoms and hydrogen atoms. The ring preferably has a 6-membered ring structure and / or a 5-membered ring structure. Furthermore, the ring is preferably a bicyclic ring in which an aromatic ring and a non-aromatic ring are fused, and it is preferable that the ring containing the N atom shown in general formulas (3) and (4) is a non-aromatic ring.

[0034] (Amount of amine used) In the method for producing a fluorine-containing carboxylic acid amide according to this embodiment, in the general formula (2), X is a halogen atom, OR 1 ,OCOR 1 and OSO2R 1 When X represents either one of the above, the amount of the amine represented by general formula (3) used is 1 to 2 times, preferably 1 to 1.5 times, more preferably 1 to 1.4 times, even more preferably 1 to 1.3 times, and particularly preferably 1.1 to 1.2 times the sum of the amounts of the fluorine-containing isopropyl ketone represented by general formula (1) and the fluorine-containing carboxylic acid derivative represented by general formula (2) used, on a molar basis. 2 R 3In this case, the amount of the amine represented by general formula (3) used is 1 to 2 times, preferably 1.3 to 1.9 times, more preferably 1.4 to 1.8 times, still more preferably 1.5 to 1.7 times, and particularly preferably 1.6 to 1.7 times, the amount of the fluorinated isopropyl ketone represented by general formula (1) used, on a molar basis.

[0035] By controlling the amount of amine used relative to the amounts of the above-mentioned raw materials used within a specific range, it is possible to produce a highly pure fluorine-containing carboxylic acid amide even when raw materials containing a fluorine-containing carboxylic acid derivative and a fluorine-containing isopropyl ketone are used. Furthermore, the burden of isolating the fluorine-containing carboxylic acid amide from the mixture obtained after the reaction (for example, the burden due to post-treatment such as purification) can be significantly reduced.

[0036] (Other ingredients) In the method for producing a fluorine-containing carboxylic acid amide according to this embodiment, other components (solvents, additives, etc.) may be used in addition to the compounds represented by the general formulae (1) to (3). When other components such as solvents or additives are used, the types and amounts thereof are not particularly limited as long as they do not impair the purpose and effects of the present invention, and the types and amounts can be appropriately selected depending on the purpose.

[0037] Examples of solvents used in the above reaction include fluorine-based organic solvents, chlorine-based organic solvents (dichloroethane, chloroform, carbon tetrachloride, etc.), tetrahydrofuran (THF), dimethylformamide, dimethyl sulfoxide, acetonitrile, diethyl ether, dioxane, chain hydrocarbons having 6 to 8 carbon atoms (isooctane, n-hexane, n-heptane, etc.), toluene, and benzene.

[0038] Examples of additives used in the above reaction include bases (tertiary amines such as triethylamine and diisopropylethylamine). When a base is used, the amount of the amine represented by general formula (3) used is preferably 0.5 to 2 times, more preferably 0.7 to 1.5 times, even more preferably 0.8 to 1.3 times, and particularly preferably 0.9 to 1.2 times the amount of the base used, on a molar basis.

[0039] The molar ratio of the fluorine-containing isopropyl ketone to the fluorine-containing carboxylic acid derivative used in the above reaction is preferably 1:5 to 1:15, more preferably 1:7 to 1:13, further preferably 1:9 to 1:11, and particularly preferably 1:10 to 1:11. If necessary, an operation for increasing the molar ratio of the fluorine-containing carboxylic acid derivative to the fluorine-containing isopropyl ketone, such as distillation or recrystallization, may be carried out before the reaction.

[0040] In the method for producing a fluorine-containing carboxylic acid amide according to one embodiment of the present invention, raw materials containing a fluorine-containing isopropyl ketone represented by general formula (1) and a fluorine-containing carboxylic acid derivative represented by general formula (2) may be added dropwise or in 3 to 10 or 3 to 5 divided portions to an amine represented by general formula (3). A solvent may be optionally added to the amine to be added.

[0041] In the method for producing a fluorine-containing carboxylic acid amide according to one embodiment of the present invention, the amine represented by the general formula (3) may be added dropwise or divided into 3 to 10 times or 3 to 5 times to raw materials containing a fluorine-containing isopropyl ketone and the fluorine-containing carboxylic acid derivative. A solvent may be optionally added to the raw materials to be added.

[0042] The reaction temperature and reaction time are not particularly limited as long as the reaction proceeds to obtain a fluorine-containing carboxylic acid amide. The reaction temperature is, for example, preferably 0 to 100°C, more preferably 5 to 90°C, even more preferably 10 to 70°C, and particularly preferably 15 to 50°C. The reaction time is, for example, preferably 0.5 to 100 hours, more preferably 1 to 90 hours, even more preferably 5 to 75 hours, even more preferably 10 to 50 hours, and particularly preferably 12 to 24 hours.

[0043] The reaction mixture containing the fluorine-containing carboxylic acid amide represented by general formula (4) may be subjected to an extraction operation without, for example, a distillation operation. The extraction operation may be carried out after adding, for example, an organic solvent selected from the group consisting of a fluorine-containing organic solvent and an alkyl alcohol having 1 to 4 carbon atoms, preferably methanol, or water. The extraction operation may be carried out, for example, 1 to 5 times, preferably 2 to 4 times. After the extraction operation, it is preferable to distill off impurities and solvents such as alcohol by, for example, a purification treatment using an evaporator or the like.

[0044] In general formula (2), when X is a halogen atom, particularly F, it is preferable to add a fluorine-based organic solvent to the mixture after the reaction. The reaction mixture or the mixture to which a solvent has been added may be filtered using a membrane filter (e.g., a PTFE (polytetrafluoroethylene) membrane filter). This allows for the removal of insoluble components such as salts of amine and HF (hydrogen fluoride). Furthermore, after the filtration, the above-mentioned extraction procedure may be carried out.

[0045] After the reaction, the fluorine-containing carboxylic acid amide may be isolated without carrying out a distillation operation, or may be isolated after carrying out a distillation operation.Furthermore, after the reaction, the fluorine-containing carboxylic acid amide may be isolated without carrying out chromatography (for example, silica gel column chromatography or ion exchange chromatography).

[0046] In the method for producing a fluorinated carboxylic acid amide according to this embodiment, the yield of the target product, fluorinated carboxylic acid amide represented by general formula (4), is preferably 90% or more based on the total number of moles of the fluorinated isopropyl ketone and the fluorinated carboxylic acid derivative. The obtained fluorinated carboxylic acid amide is useful for various applications such as lubricants, coating agents, surfactants, and antibacterial agents.

[0047] Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, but includes all aspects encompassed by the concept of the present invention and the scope of the claims, and can be modified in various ways within the scope of the present invention.

[0048] Based on the above-described embodiments, the present invention relates to the following [1] to [5]. [1] A method for producing a fluorine-containing carboxylic acid amide represented by the following general formula (4): The fluorine-containing carboxylic acid amide is obtained by reacting a raw material containing a fluorine-containing isopropyl ketone represented by the following general formula (1) and a fluorine-containing carboxylic acid derivative represented by the following general formula (2) with an amine represented by the following general formula (3), [ka] (In the above general formulas (1) to (4), n is an integer of 0 to 5, and m is 0 or 1; l is an integer from 0 to 50, X is a halogen atom, OR 1 ,OCOR 1 , OSO2R 1 and N.R. 2 R 3 represents one of the following: R 1 represents an alkyl group or a haloalkyl group having 1 to 10 carbon atoms, R 2 and R 3each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or a heteroaryl group having 2 to 10 carbon atoms, or R 2 and R 3 are bonded to each other to form a ring having 2 to 10 carbon atoms. In the above general formula (2), X is a halogen atom, OR 1 ,OCOR 1 and OSO 2 R 1 when either of the above is represented, the amount of the amine used is 1 to 2 times the sum of the amounts of the fluorine-containing isopropyl ketone and the fluorine-containing carboxylic acid derivative used on a molar basis, In the above general formula (2), X is NR 2 R 3 wherein the amount of the amine used is 1 to 2 times the amount of the fluorinated isopropyl ketone used, on a molar basis. [2] The method for producing a fluorine-containing carboxylic acid amide according to the above [1], wherein the molar ratio of the fluorine-containing isopropyl ketone to the fluorine-containing carboxylic acid derivative used in the reaction is 1:5 to 1:15. [3] The method for producing a fluorine-containing carboxylic acid amide according to the above [1] or [2], wherein the reaction temperature is 0 to 100°C. [4] The method for producing a fluorine-containing carboxylic acid amide according to any one of the above [1] to [3], wherein the reaction mixture containing the fluorine-containing carboxylic acid amide is subjected to an extraction operation without being subjected to a distillation operation. [5] The method for producing a fluorine-containing carboxylic acid amide according to the above [4], wherein the extraction operation is carried out after adding an organic solvent or water. [Example]

[0049] Examples of the present invention will be described below, but the present invention is not limited to these examples as long as they do not depart from the spirit of the present invention. Unless otherwise specified, all operations are carried out at room temperature, and room temperature is within the range of 20°C ± 5°C.

[0050] Example 1 7,800.0 g of a mixture containing a compound represented by the following structural formula as a raw material was introduced into a flask equipped with a T-shaped connector for nitrogen sealing, a stirring blade, a condenser, a dropping funnel, a thermometer, and a heating mantle heater, and the mixture was stirred. 19 The composition of the mixture calculated by F-NMR was 2.615 mol of perfluoropolyether carboxylic acid fluoride and 0.252 mol of the corresponding fluorine-containing isopropyl ketone.

[0051] [ka]

[0052] Next, a mixture of 400 g (3.0 mol) of 2-aminobenzimidazole and 314 g (3.1 mol) of triethylamine was slowly added dropwise to the flask at room temperature. After the addition was completed, the mixture was heated and stirred for 72 hours in a mantle heater so that the internal temperature reached 92°C. Fourier transform infrared spectroscopy (FT-IR) and 19 After confirming the disappearance of the raw materials by F-NMR, the fluorine-containing organic solvent "Vertrel (registered trademark) XF" (manufactured by Chemours) was added to the reaction mixture and stirred. After sufficient dissolution, insoluble components such as the amine HF salt were removed using a membrane filter (PTFE type, manufactured by Advantec: pore size 3 μm). Next, the fluorine-containing organic solvent "Vertrel (registered trademark) XF" (manufactured by Chemours) and methanol were added to the filtrate, mixed thoroughly, and the lower layer was extracted. This process was repeated three times. Finally, the fluorine-containing organic solvent was distilled off under reduced pressure using an evaporator to obtain a fluorine-containing carboxylic acid amide represented by the following structural formula as a colorless oily substance. The yield of the obtained fluorine-containing carboxylic acid amide was 91% based on the total number of moles of the above compound used as the raw material.

[0053] [ka]

[0054] Example 2 500.0 g of a mixture containing the compound represented by the following structural formula as a raw material was introduced into a flask equipped with a stirring blade, a condenser, a dropping funnel, and a thermometer, and the mixture was stirred. 19 The composition of the mixture calculated by F-NMR was 0.330 mol of perfluoropolyether carboxylic acid methyl ester and 0.032 mol of the corresponding fluorine-containing isopropyl ketone.

[0055] [ka]

[0056] Then, 24.5 g (0.43 mol) of allylamine was slowly added dropwise to the flask at room temperature, and the mixture was stirred for 20 hours. 1 H-NMR and 19 After confirming the disappearance of the raw materials by F-NMR, the reaction mixture was added with methanol, mixed thoroughly, and the lower layer was extracted. This procedure was repeated three times. Methanol was completely distilled off from the lower layer extract, and a fluorine-containing carboxylic acid amide represented by the following structural formula was obtained as a pale yellow oily substance. The yield of the obtained fluorine-containing carboxylic acid amide was 94% based on the total number of moles of the above compound used as the raw material.

[0057] [ka]

[0058] Example 3 Into a flask equipped with a stirring blade, a condenser, a thermometer, and an oil bath, 1000.0 g of a mixture containing a compound represented by the following structural formula as a raw material was introduced and stirred. 19 The composition of the mixture calculated by F-NMR was 0.660 mol of perfluoropolyether carboxylic acid methyl ester and 0.063 mol of the corresponding fluorine-containing isopropyl ketone.

[0059] [ka]

[0060] Next, 88.9 g (0.87 mol) of N,N-dimethyltrimethylenediamine was added to the flask at room temperature in four portions, and the mixture was stirred at 40° C. for 15 hours. 1 After confirming the disappearance of the raw materials by H-NMR, the reaction mixture was added with methanol, mixed thoroughly, and the lower layer was extracted. This procedure was repeated twice. The methanol was completely distilled off from the lower layer extract to obtain a fluorine-containing carboxylic acid amide represented by the following structural formula as a pale yellow oily substance. The yield of the obtained fluorine-containing carboxylic acid amide was 93% based on the total number of moles of the above compound used as the raw material.

[0061] [ka]

[0062] Example 4 685.1 g of a mixture containing the compound represented by the following structural formula as a raw material was introduced into a flask equipped with a stirring blade, a condenser, a dropping funnel, and a thermometer, and the mixture was stirred. 19 The composition of the mixture calculated by F-NMR was 0.452 mol of perfluoropolyether carboxylic acid methyl ester and 0.044 mol of the corresponding fluorine-containing isopropyl ketone.

[0063] [ka]

[0064] Next, 33.6 g (0.55 mol) of 2-aminoethanol was slowly added dropwise to the flask at room temperature, and the mixture was stirred for 17 hours. 1 H-NMR and 19After confirming the disappearance of the raw materials by F-NMR, the reaction mixture was added with methanol, mixed thoroughly, and the lower layer was extracted. This procedure was repeated three times. The methanol was completely removed by distillation from the lower layer extract, yielding a fluorine-containing carboxylic acid amide represented by the following structural formula as a pale yellow oil. The yield of the obtained fluorine-containing carboxylic acid amide was 91% based on the total number of moles of the above compound used as the raw material.

[0065] [ka]

[0066] Example 5 3271 g of a mixture of compounds represented by the following structural formula as raw materials was introduced into a flask equipped with a stirring blade, a condenser, a dropping funnel, and a thermometer, and the mixture was stirred. 19 The composition of the mixture calculated by F-NMR was 1.24 mol of perfluoropolyethercarboxylic acid isobutylamide and 0.12 mol of the corresponding fluorine-containing isopropyl ketone.

[0067] [ka]

[0068] Next, 15 g (0.2 mol) of isobutylamine was slowly added dropwise to the flask at room temperature, and the mixture was stirred for 15 hours. 19 After confirming the disappearance of the fluorine-containing isopropyl ketone by F-NMR, the reaction mixture was added with methanol, mixed thoroughly, and the lower layer was extracted. This procedure was repeated three times in total. The methanol was completely distilled off from the lower layer extract, yielding a fluorine-containing carboxylic acid amide represented by the following structural formula as a pale yellow oily substance. The yield of the obtained fluorine-containing carboxylic acid amide was 98% based on the total number of moles of the above compound used as the raw material.

[0069] [ka]

[0070] Example 6 A flask equipped with a stirring blade, a condenser, a dropping funnel, and a thermometer was charged with 300 g of THF, 78 g (0.6 mol) of n-octylamine, and 50 g (0.5 mol) of triethylamine. Next, 193 g of a raw material mixture containing the compound represented by the following structural formula was slowly added dropwise and stirred. 19 The composition of the mixture calculated by F-NMR was 0.42 mol of the fluorine-containing carboxylic acid pivalic acid mixed acid anhydride and 0.04 mol of the corresponding fluorine-containing isopropyl ketone.

[0071] [ka]

[0072] After stirring for 17 hours, 19 After confirming the disappearance of the raw materials by F-NMR, the reaction mixture was washed with water and purified by distillation to obtain a fluorine-containing carboxylic acid amide represented by the following structural formula as a pale yellow oily substance. The yield of the obtained fluorine-containing carboxylic acid amide was 94% based on the total number of moles of the above compound used as the raw material.

[0073] [ka]

[0074] Example 7 A flask equipped with a stirring blade, a condenser, a dropping funnel, and a thermometer was charged with 2.5 kg of THF, 338 g (2.5 mol) of 4-isopropylaniline, and 271 g (2.1 mol) of diisopropylethylamine. Next, 1,323 g of a raw material mixture containing the compound represented by the following structural formula was slowly added dropwise and stirred. 19 The composition of the mixture calculated by F-NMR was 1.91 mol of perfluoropolyether carboxylic acid trifluoromethanesulfonic acid mixed acid anhydride and 0.19 mol of the corresponding fluorine-containing isopropyl ketone.

[0075] [ka]

[0076] After stirring for 16 hours, 19 After confirming the disappearance of the raw materials by F-NMR, the reaction mixture was washed with water and purified by distillation to obtain a fluorine-containing carboxylic acid amide represented by the following structural formula as a pale yellow oily substance. The yield of the obtained fluorine-containing carboxylic acid amide was 93% based on the total number of moles of the above compound used as the raw material.

[0077] [ka]

[0078] Example 8 80 g of THF and 16 g (0.13 mol) of isoindoline were added to a flask equipped with a stirring blade, a condenser, a dropping funnel, and a thermometer. Then, 21 g of a mixture containing the compound represented by the following structural formula was slowly added dropwise and stirred. 19 The composition of the mixture calculated by F-NMR was 0.1 mol of methyl pentafluoropropanoate and 0.01 mol of the corresponding fluorine-containing isopropyl ketone.

[0079] [ka]

[0080] After stirring for 16 hours, 19 After confirming the disappearance of the raw materials by F-NMR, the reaction mixture was washed with water and purified by distillation to obtain a fluorine-containing carboxylic acid amide represented by the following structural formula as a brown semi-solid substance. The yield of the obtained fluorine-containing carboxylic acid amide was 96% based on the total number of moles of the above compound used as the raw material.

[0081] [ka]

Claims

1. A method for producing a fluorine-containing carboxylic acid amide represented by the following general formula (4): The fluorine-containing carboxylic acid amide is obtained by reacting raw materials containing a fluorine-containing isopropyl ketone represented by the following general formula (1) and a fluorine-containing carboxylic acid derivative represented by the following general formula (2) with an amine represented by the following general formula (3): 【Chemistry 1】 (In the above general formulas (1) to (4), n is an integer from 0 to 5, m is 0 or 1, l is an integer from 0 to 50; X is a halogen atom, OR １ , O.C.O.R. １ , OSO ２ R １ and N.R. ２ R ３ represents one of the following: R １ represents an alkyl group or a haloalkyl group having 1 to 10 carbon atoms, R ２ and R ３ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or a heteroaryl group having 2 to 10 carbon atoms, or R ２ and R ３ are bonded to each other to form a ring having 2 to 10 carbon atoms.) In the above general formula (2), X is a halogen atom, OR １ , O.C.O.R. １ and OSO ２ R １ when either of the above is represented, the amount of the amine used is 1 to 2 times the sum of the amounts of the fluorine-containing isopropyl ketone and the fluorine-containing carboxylic acid derivative used on a molar basis, In the above general formula (2), X is NR ２ R ３ wherein the amount of the amine used is 1 to 2 times the amount of the fluorinated isopropyl ketone used, on a molar basis.

2. 2. The process for producing a fluorine-containing carboxylic acid amide according to claim 1, wherein the molar ratio of said fluorine-containing isopropyl ketone to said fluorine-containing carboxylic acid derivative used in the reaction is from 1:5 to 1:

15.

3. 2. The process for producing a fluorine-containing carboxylic acid amide according to claim 1, wherein the reaction temperature is 0 to 100°C.

4. The process for producing a fluorine-containing carboxylic acid amide according to any one of claims 1 to 3, wherein the reaction mixture containing the fluorine-containing carboxylic acid amide is subjected to an extraction operation without being subjected to a distillation operation.

5. 5. The process for producing a fluorine-containing carboxylic acid amide according to claim 4, wherein the extraction operation is carried out after adding an organic solvent or water.

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