Perfluorodioxolane and method for producing same

Abstract

The present invention provides a composition containing a compound represented by formula (5). The composition further contains 0.00001-1 part by mass of a compound represented by formula (9) and / or 0.00001-1 part by mass of a compound represented by formula (10) per 100 parts by mass of a compound represented by formula (5). In formula (5), R1 represents a fluorine atom or a fluoroalkyl group; in formula (9), two R1 are as defined above; in formula (10), two R1s have the same meanings as described above. # imgabs0 #

Description

[0001] This case is a divisional application with an application date of February 12, 2020, application number 202080014071.0 (PCT / JP2020 / 005417), and invention name "Fluorolactone and method for producing the same". Technical Field

[0002] The present invention relates to perfluorodioxolane and a method for producing the same. Background Art

[0003] 2-(Difluoromethylene)-4,4,5-trifluoro-5-(trifluoromethyl)-1,3-dioxolane is used as a raw material for fluororesins.

[0004] As a method for producing the perfluorodioxolane, a method using 3,5,5,6-tetrafluoro-3,6-bis(trifluoromethyl)-1,4-dioxane-2-one represented by the following formula as a raw material is known (for example, Patent Document 1).

[0005]

[0006] As a method for producing the above-mentioned perfluorodioxane, for example, a two-step method using hexafluoropropylene oxide as a raw material is known (for example, Non-Patent Document 1).

[0007]

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Publication No. 2005-2014

[0011] Non-patent literature

[0012] Non-patent document 1: "Perfluorinated dioxolanes 1.Synthesis of somederivatives of perfluoro-4-oxo-1,3-dioxolane", VSYuminov, SVKartsov, VLMaksimov, and AVFokin, Bulletin of the Academy of Sciences of the USSR, 1988, 37(2), 311-315. Summary of the invention

[0013] Technical problem to be solved by the invention

[0014] The method for producing perfluorodioxane described in Non-Patent Document 1 requires two steps.

[0015] An object of the present invention is to provide a method and the like capable of producing a fluorolactone compound from hexafluoropropylene oxide and the like in one step.

[0016] Technical solutions for solving technical problems

[0017] The present invention includes the following aspects.

[0018] Item 1. A method for producing a compound represented by formula (1), comprising:

[0019] A step A of reacting a compound represented by formula (2) with at least one compound (3) selected from the group consisting of a compound represented by formula (3-1) and a compound represented by formula (3-2) in the presence of a fluorine compound (4) and an organic solvent (the organic solvent does not include the compound represented by formula (3-1) and the compound represented by formula (3-2),

[0020] The fluorine compound (4) is at least one selected from the group consisting of a compound represented by formula (4-1), a compound represented by formula (4-2), and hydrofluoric acid or a salt thereof.

[0021] Formula (1):

[0022]

[0023] [In formula (1), two R 1 is the same as fluorine atom or fluoroalkyl group.]

[0024] Formula (2):

[0025]

[0026] [In formula (2), R 1 Same meaning as above.]

[0027] Formula (3-1):

[0028]

[0029] [In formula (3-1), R 31 , R 32 and R 33 The same or different, hydrogen or C 1－10 An alkyl group may be bonded to each other or two of them may form a ring which may have one or more substituents.]

[0030] Formula (3-2):

[0031]

[0032] [In formula (3-2), R 34 , R35 , R 36 and R 37 The same or different, hydrogen or C 1－10 An alkyl group may be bonded to each other or two of them may form a ring which may have one or more substituents.]

[0033] Formula (4-1):

[0034] MH n F m (4-1)

[0035] [In formula (4-1), M is a metal atom, n is 0 or 1, and the sum of the atomic valence of M and n is m.]

[0036] Formula (4-2):

[0037] LR 41 4F(4-2)

[0038] [In formula (4-2), L is a nitrogen atom or a phosphorus atom, R 41 Same or different, C 1－5 alkyl.]

[0039] Item 2. The method of manufacturing as described in Item 1, wherein two R 1 Same as C 1－10 Fluoroalkyl.

[0040] Item 3. The manufacturing method according to Item 1 or 2, wherein the step A is a step of generating an upper liquid layer and a lower liquid layer, and the manufacturing method further comprises a step B of performing liquid separation.

[0041] Item 4. A method for producing a compound represented by formula (5), comprising:

[0042] A step C of heating the compound represented by formula (1) produced in the above step A or B in the presence of at least one fluorine compound (4) selected from the group consisting of a compound represented by formula (4-1), a compound represented by formula (4-2), and hydrofluoric acid or a salt thereof to produce a compound represented by formula (6);

[0043] Step D of reacting the compound represented by formula (6) with a base to produce a compound represented by formula (8); and

[0044] and step E: heating the compound represented by the formula (8) to generate the compound represented by the above formula (5).

[0045] Formula (5):

[0046]

[0047] [In formula (5), R 1is a fluorine atom or a fluoroalkyl group.]

[0048] Formula (1):

[0049]

[0050] [In formula (1), two R 1 is the same as fluorine atom or fluoroalkyl group.]

[0051] Formula (4-1):

[0052] MH n F m (4-1)

[0053] [In formula (4-1), M is a metal atom, n is 0 or 1, and the sum of the atomic valence of M and n is m.]

[0054] Formula (4-2):

[0055] LR 41 4F(4-2)

[0056] [In formula (4-2), L is a nitrogen atom or a phosphorus atom, R 41 Same or different, C 1－5 alkyl.]

[0057] Formula (6):

[0058]

[0059] [In formula (6), R 1 Same meaning as above.]

[0060] Formula (8):

[0061]

[0062] [In formula (8), R 81 is a group corresponding to the above base, R 1 Same meaning as above.]

[0063] Item 5. The method according to Item 4, wherein the step D is replaced by:

[0064] Step D1 of reacting the compound represented by the above formula (6) with water or an alkyl alcohol to produce a compound represented by the formula (7); and

[0065] Step D2 is to react the compound represented by the formula (7) with a base to produce the compound represented by the above formula (8).

[0066] Formula (7):

[0067]

[0068] [In formula (7), R 71 is a hydrogen atom or an alkyl group, R 1 Same meaning as above.]

[0069] Item 6. The manufacturing method according to Item 5, further comprising:

[0070] A step D1a is to purify the liquid produced in the step D1 to obtain the compound represented by the formula (7).

[0071] Item 7. The method according to Item 4, wherein the above-mentioned step D and step E are replaced by:

[0072] Step F is to heat the compound represented by the above formula (6) in the presence of a base to generate the compound represented by the above formula (5).

[0073] Item 8. A compound represented by formula (7-1).

[0074]

[0075] [Wherein, 2 R 1 are the same, are fluorine atoms or fluoroalkyl groups, R 72 is an alkyl group.]

[0076] Item 9. The compound as described in Item 8, wherein R 72 Straight or branched chain C 1－10 alkyl.

[0077] Item 10. The compound according to Item 8, wherein R 72 It is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.

[0078] Item 11. The method for producing the compound according to Item 8, comprising step D1-1 of reacting the compound represented by formula (6) with an alkyl alcohol to produce the compound represented by formula (7-1).

[0079] Formula (6):

[0080]

[0081] [In formula (6), 2 R 1 is the same as fluorine atom or fluoroalkyl group.]

[0082] Formula (7-1):

[0083]

[0084] [In formula (7-1), R 72 is an alkyl group, R 1Same meaning as above.]

[0085] Item 12. A composition comprising a compound represented by formula (5), further comprising 0.00001 to 1 parts by mass of a compound represented by formula (9) and / or 0.00001 to 1 parts by mass of a compound represented by formula (10) relative to 100 parts by mass of the compound represented by formula (5),

[0086] Formula (5):

[0087]

[0088] [In formula (5), R 1 is a fluorine atom or a fluoroalkyl group.]

[0089] Formula (9):

[0090]

[0091] [In formula (9), two R 1 Same meaning as above.]

[0092] Formula (10):

[0093]

[0094] [In formula (10), two R 1 Same meaning as above.]

[0095] Item 13. The composition according to Item 12, wherein the content of the compound represented by the above formula (9) is 0.00001 to 0.5 parts by mass, and the content of the compound represented by the above formula (10) is 0.00001 to 0.5 parts by mass, relative to 100 parts by mass of the compound represented by the above formula (5).

[0096] Effects of the Invention

[0097] According to the present invention, a method for producing a fluorolactone compound from hexafluoropropylene oxide or the like in one step is provided. According to the present invention, a novel fluorodioxolane compound and a method for producing the same are provided. DETAILED DESCRIPTION

[0098] The above summary of the present invention is not intended to describe each embodiment or all possibilities disclosed herein.

[0099] The following description of the present invention is specifically illustrated by way of example embodiments.

[0100] In several parts of the invention, guidance is provided through illustrations, and the illustrations can be used in various combinations.

[0101] In each combination, the illustrated groups can function as non-exclusive and representative groups.

[0102] All publications, patents and patent applications cited in this specification are directly incorporated into this specification by reference.

[0103] the term

[0104] Unless otherwise specified, the symbols and abbreviations in this specification can be understood as the meanings commonly used in the technical field to which the present invention belongs according to the context of this specification.

[0105] In this specification, the expression "comprising" is used to include the expression "consisting essentially of" and the expression "consisting of".

[0106] Unless otherwise specified, the steps, treatments, or operations described in the present specification can be performed at room temperature.

[0107] In this specification, room temperature can mean a temperature within a range of 10 to 40°C.

[0108] In this specification, the expression "C n－m " (wherein n and m are numbers respectively.) As generally understood by those skilled in the art, it means that the number of carbon atoms is greater than n and less than m.

[0109] In this specification, unless otherwise specified, examples of "substituents" include halogen atoms, alkyl groups, cyano groups, amino groups, alkoxy groups, and alkylthio groups. The number of substituents may be in the range of 1 to the maximum number that can be substituted (e.g., 1, 2, 3, 4, 5, 6), preferably 1 to 4, more preferably 1 to 3, and particularly preferably 1 or 2. Furthermore, two or more substituents may be the same or different from each other.

[0110] In this specification, unless otherwise specified, an "organic group" means a group obtained by removing one hydrogen atom from an organic compound. As can be understood from this, an organic group has one or more carbon atoms.

[0111] In this specification, unless otherwise specified, "organic group" includes: (1) a hydrocarbon group; and (2) a hydrocarbon group having one or more heteroatoms (eg, nitrogen, oxygen, sulfur, phosphorus, halogen).

[0112] In this specification, unless otherwise specified, "hydrocarbon group" means a group consisting only of carbon and hydrogen. A hydrocarbon group may also be referred to as a hydrocarbyl group.

[0113] In this specification, unless otherwise specified, examples of "hydrocarbon groups" include: (1) aliphatic hydrocarbon groups that may be substituted with one or more aromatic hydrocarbon groups (e.g., benzyl); and (2) aromatic hydrocarbon groups that may be substituted with one or more aliphatic hydrocarbon groups. Aromatic hydrocarbon groups may also be referred to as aryl groups.

[0114] In the present specification, unless otherwise specified, the "aliphatic hydrocarbon group" may have a linear, branched, or cyclic structure, or a combination thereof.

[0115] In the present specification, unless otherwise specified, the "aliphatic hydrocarbon group" may be saturated or unsaturated.

[0116] In the present specification, unless otherwise specified, examples of the "aliphatic hydrocarbon group" include an alkyl group, an alkenyl group, an alkynyl group, and a cycloalkyl group.

[0117] In the present specification, unless otherwise specified, examples of “alkyl” include linear or branched alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl (e.g., n-propyl, isopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl), pentyl (e.g., n-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl), hexyl, heptyl, octyl, nonyl and decyl.

[0118] In the present specification, unless otherwise specified, examples of "alkenyl" include linear or branched alkenyl groups having 1 to 10 carbon atoms;

[0119] And, specific examples thereof include ethenyl, 1-propenyl, isopropenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-ethyl-1-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl and 5-hexenyl.

[0120] In the present specification, unless otherwise specified, examples of "alkynyl group" include linear or branched alkynyl groups having 2 to 6 carbon atoms,

[0121] And, specific examples thereof include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl and 5-hexynyl.

[0122] In the present specification, unless otherwise specified, examples of "cycloalkyl" include cycloalkyl groups having 3 to 10 carbon atoms,

[0123] And, specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and an adamantyl group.

[0124] In this specification, unless otherwise specified, examples of the "aromatic hydrocarbon group (aryl group)" include C 6－14 Aromatic hydrocarbon groups (aryl groups),

[0125] And, specific examples thereof include phenyl, naphthyl, phenanthryl, anthracenyl, and pyrenyl.

[0126] In this specification, unless otherwise specified, examples of the "aromatic hydrocarbon ring" include C 6－14 Aromatic hydrocarbon ring,

[0127] And, specific examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring.

[0128] In this specification, unless otherwise specified, "fluoroalkyl" means a group in which one or more hydrogen atoms of an alkyl group are replaced by fluorine atoms, and also includes a perfluoroalkyl group in which all hydrogen atoms of the alkyl group are replaced. Examples of "fluoroalkyl" include linear or branched fluoroalkyl groups having 1 to 10 carbon atoms, such as mono-, di- or trifluoromethyl, mono-, di-, tri-, tetra- or hexafluoroethyl, mono-, di-, tri-, tetra-, hexa- or heptafluorobutyl, and mono-, di-, tri-, tetra-, hexa-, hepta-, octa- or nonafluorobutyl, and mono-, di-, tri-, tetra-, hexa-, hepta-, octa-, nona-, deca- or undecafluoropentyl.

[0129] Method for producing a compound represented by formula (1)

[0130] One embodiment of the present invention is a method for producing a compound represented by formula (1) (sometimes referred to as compound (1) in this specification), comprising: step A of reacting a compound represented by formula (2) (sometimes referred to as compound (2) in this specification) with at least one compound (3) (sometimes referred to as compound (3) selected from a compound represented by formula (3-1) (sometimes referred to as compound (3-1) in this specification) and a compound represented by formula (3-2) (sometimes referred to as compound (3-2) in this specification) in the presence of a fluorine compound (4) (sometimes referred to as compound (4) in this specification) and an organic solvent (the organic solvent does not include the compound represented by formula (3-1) and the compound represented by formula (3-2) above;

[0131] The fluorine compound (4) is at least one selected from the group consisting of a compound represented by formula (4-1) (sometimes referred to as compound (4-1) in this specification), a compound represented by formula (4-2) (sometimes referred to as compound (4-2) in this specification), and hydrofluoric acid or a salt thereof.

[0132] Formula (1):

[0133]

[0134] [In formula (1), two R 1 is the same as fluorine atom or fluoroalkyl group.]

[0135] Formula (2):

[0136]

[0137] [In formula (2), R 1 Same meaning as above.]

[0138] Formula (3-1):

[0139]

[0140] [In formula (3-1), R 31 , R 32 and R 33 The same or different, hydrogen or C 1－10 An alkyl group may be bonded to each other or two of them may form a ring which may have one or more substituents.]

[0141] Formula (3-2):

[0142]

[0143] [In formula (3-2), R 34 , R 35 , R 36 and R 37 The same or different, hydrogen or C 1－10 An alkyl group may be bonded to each other or two of them may form a ring which may have one or more substituents.]

[0144] Formula (4-1):

[0145] MH n F m (4-1)

[0146] [In the formula, M is a metal atom, n is 0 or 1, and the sum of the atomic valence of M and n is m.]

[0147] Formula (4-2):

[0148] LR 41 4F(4-2)

[0149] [wherein, L is a nitrogen atom or a phosphorus atom, R 41 Same or different, C 1－5 alkyl.]

[0150] R 1 Preferably, a fluorine atom or a C 1－10A fluoroalkyl group, more preferably a fluorine atom or a C 1－5 A perfluoroalkyl group, more preferably a fluorine atom or a C 1－3 Perfluoroalkyl, particularly preferably C 1－3 Perfluoroalkyl.

[0151] Suitable specific examples of compound (2) include hexafluoropropylene oxide, 2,2,3-trifluoro-3-(perfluoroethyl)ethylene oxide, and 2,2,3-trifluoro-3-(perfluoropropyl)ethylene oxide.

[0152] Preferred:

[0153] R 31 , R 32 and R 33 The same or different, hydrogen or C 1－5 Alkyl; or

[0154] R 31 A hydrogen atom or C 1－5 Alkyl, R 32 and R 33 bonded to form a pyrrolidine ring or a piperidine ring which may have 1 or 2 substituents on the carbon atoms in the ring, wherein the substituents are methyl or ethyl and when there are plural substituents, they may be the same or different; or

[0155] R 31 and R 32 bonded to form a pyrrolidone ring or piperidone ring which may have one or two substituents on the carbon atoms of the ring, wherein the substituents are methyl or ethyl and may be the same or different when there are multiple substituents, R 33 A hydrogen atom or C 1－5 alkyl.

[0156] More preferably:

[0157] R 31 , R 32 and R 33 The same or different, hydrogen or C 1－3 Alkyl; or

[0158] R 31 A hydrogen atom or C 1－3 Alkyl, R 32 and R 332 bonded to form a pyrrolidine ring or a piperidine ring; or

[0159] R 31 and R 32 bonded to form a pyrrolidone ring or a piperidone ring, R 33 A hydrogen atom or C 1－3 alkyl.

[0160] Further preferred:

[0161] R 31 , R 32 and R 33 The same or different, hydrogen or C 1－3 Alkyl; or

[0162] R 31 A hydrogen atom or C 1－3 Alkyl, R 32 and R 33 bonded to form a pyrrolidine ring; or

[0163] R 31 and R 32 Bonded to form a pyrrolidone ring, R 33 C 1－3 alkyl.

[0164] Particularly preferred:

[0165] R 31 , R 32 and R 33 the same or different, is a hydrogen atom, a methyl group or an ethyl group; or

[0166] R 31 is a hydrogen atom, a methyl group or an ethyl group, R 32 and R 33 bonded to form a pyrrolidine ring; or

[0167] R 31 and R 32 Combined to form a pyrrolidone ring, R 33 It is a hydrogen atom, a methyl group or an ethyl group.

[0168] Suitable specific examples of compound (3-1) include formamide, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone.

[0169] Preferred:

[0170] R 34 , R 35 , R 36 and R 37 The same or different, hydrogen or C 1－5 Alkyl; or

[0171] R 34 and R 35 The same or different, hydrogen or C 1－5 Alkyl, R 36 and R 37 They are bonded to each other to form a tetrahydropyrimidine ring or an imidazoline ring which may have 1 or 2 substituents on the carbon atoms in the ring, and the substituent is a methyl group or an ethyl group.

[0172] More preferably:

[0173] R 34 , R 35 , R 36 and R 37 The same or different, hydrogen or C 1－3 Alkyl; or

[0174] R 34 and R 35 The same or different, hydrogen or C 1－3 Alkyl, R 36 and R 37 They are bonded to each other to form a tetrahydropyrimidine ring or an imidazoline ring.

[0175] Further preferred:

[0176] R 34 , R 35 , R 36 and R 37 are the same or different and are hydrogen, methyl or ethyl; or

[0177] R 34 and R 35 are the same or different and are hydrogen atoms, methyl groups or ethyl groups, R 36 and R 37 They are bonded to each other to form a tetrahydropyrimidine ring or an imidazoline ring.

[0178] Particularly preferred:

[0179] R 34 , R 35 , R 36 and R 37 are both methyl or ethyl, or R 34 and R 35 Both are methyl or ethyl, R 36 and R 37 They are bonded to each other to form a tetrahydropyrimidine ring.

[0180] Suitable specific examples of the compound (3-2) include N,N′-dimethylpropylene urea, N,N′-dimethylethylene urea, and tetramethyl urea.

[0181] In one embodiment of the present invention, a suitable specific example of compound (3) is at least one compound selected from formamide, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N'-dimethylpropylene urea, N,N'-dimethylethylene urea, tetramethyl urea, N,N'-diethylpropylene urea and N,N'-diethylethylene urea.

[0182] M is preferably an alkali metal atom or an alkaline earth metal atom, more preferably an alkali metal atom, a magnesium atom or a calcium atom, further preferably an alkali metal atom or a calcium atom, and particularly preferably a sodium atom, a potassium atom, a cesium atom or a calcium atom.

[0183] Preferably, M is an alkali metal atom and n is 0 or 1, or M is an alkaline earth metal atom and n is 0.

[0184] More preferably, M is a sodium atom, a potassium atom or a cesium atom and n is 0 or 1, or M is a calcium atom and n is 0.

[0185] More preferably, M is a potassium atom or a cesium atom and n is 0 or 1, or M is a calcium atom and n is 0.

[0186] Suitable specific examples of the compound (4-1) include cesium fluoride, potassium hydrofluoride, calcium fluoride, sodium fluoride, potassium fluoride and sodium hydrofluoride.

[0187] Preferably, L is a nitrogen atom or a phosphorus atom, R 41 Same or different C 1－4 alkyl.

[0188] More preferably, L is a nitrogen atom or a phosphorus atom, R 41 Same as C 1－4 alkyl.

[0189] More preferably, L is a nitrogen atom or a phosphorus atom, R 41 The same straight chain C 1－4 alkyl.

[0190] It is particularly preferred that L is a nitrogen atom or a phosphorus atom, R 41 The same is methyl, ethyl or n-butyl.

[0191] Suitable specific examples of the compound (4-2) include tetrabutylammonium fluoride, tetraethylammonium fluoride, tetramethylammonium fluoride, tetrabutylphosphonium fluoride and triethylmethylammonium fluoride.

[0192] Salts of hydrofluoric acid include amine salts, ammonium salts, imidazolium salts, pyridinium salts, phosphonium salts and the like. The salts may contain one or more substituents, and when there are multiple substituents, they may be the same or different.

[0193] The amine salt of hydrofluoric acid is preferably substituted. The number of substituents is, for example, 1 to 3, preferably 2 or 3, and more preferably 3. When there are multiple substituents, they may be the same or different. The substituent is preferably C 1－10 Alkyl, more preferably C 1－5 Alkyl, particularly preferably C 1－4 alkyl.

[0194] Suitable examples of amine salts of hydrofluoric acid include tri-C 1－4 Alkylamine hydrofluoride (HF－ The number of can be any integer from 1 to 7. ).

[0195] Suitable specific examples of amine salts of hydrofluoric acid include trimethylamine hydrofluoride (HF － The number of can be any integer from 1 to 7, preferably 3, 4 or 5. ), triethylamine hydrofluoride (HF － The number of can be any integer from 1 to 7, preferably 3, 4 or 5. ).

[0196] When the ammonium salt of hydrofluoric acid is substituted, the number of substituents is, for example, 1 to 4, preferably 2 to 4, more preferably 3 or 4, and particularly preferably 4. When there are multiple substituents, they may be the same or different. 1－10 Alkyl, more preferably C 1－5 Alkyl, particularly preferably C 1－4 alkyl.

[0197] Suitable examples of ammonium salts of hydrofluoric acid include ammonium fluoride, ammonium hydrofluorate, tetra-C 1－4 Alkyl ammonium fluoride.

[0198] Suitable specific examples of the ammonium salt of hydrofluoric acid include ammonium fluoride, ammonium hydrofluorate, tetramethylammonium fluoride, tetraethylammonium fluoride, and tetrabutylammonium fluoride.

[0199] The imidazolium salt of hydrofluoric acid preferably has a substituent on the nitrogen atom of the imidazolium ring. The number of substituents is, for example, 1 to 3, preferably 2 or 3, and more preferably 2. When there are multiple substituents, they may be the same or different. As a substituent, preferably C 1－10 Alkyl (for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl), cyclohexyl, vinyl or allyl, particularly preferably C 1－3 alkyl.

[0200] Suitable specific examples of the imidazolium salt of hydrofluoric acid include 1-methyl-3-methylimidazolium fluoride and 1-ethyl-3-methylimidazolium fluoride.

[0201] The pyridinium salt of hydrofluoric acid may be substituted, and the number of substituents is, for example, 1 to 3, preferably 1 or 2. When there are multiple substituents, they may be the same or different. 1－10 Alkyl, more preferably C 1－5 Alkyl, particularly preferably C 1－4 alkyl.

[0202] Suitable specific examples of pyridinium salts of hydrofluoric acid include pyridinium poly(hydrofluoric acid) (HF － The number of can be any integer from 1 to 9, preferably 1 or 9. ).

[0203] The phosphonium salt of hydrofluoric acid is preferably substituted, and the number of substituents is, for example, 1 to 4, preferably 3 or 4, and more preferably 4. The substituent is preferably C 1－10 alkyl, phenyl which may have a substituent, or benzyl which may have a substituent, more preferably C 1－5 Alkyl, particularly preferably C 1－4 alkyl.

[0204] Suitable specific examples of the phosphonium salt of hydrofluoric acid include tetramethylphosphonium hydrofluoride, tetraethylphosphonium hydrofluoride, tetrapropylphosphonium hydrofluoride, tetrabutylphosphonium hydrofluoride, tetraoctylphosphonium hydrofluoride, trimethylethylphosphonium hydrofluoride, triethylmethylphosphonium hydrofluoride, hexyltrimethylphosphonium hydrofluoride, trimethyloctylphosphonium hydrofluoride, triethyl(methoxymethyl)phosphonium hydrofluoride, and triethyl(methoxymethyl)phosphonium hydrofluoride.

[0205] In one embodiment of the present invention, a suitable specific example of compound (4) is at least one fluorine compound selected from cesium fluoride, potassium hydrofluoride, calcium fluoride, sodium fluoride, potassium fluoride, sodium hydrofluoride, tetrabutylammonium fluoride, tetraethylammonium fluoride, tetramethylammonium fluoride, tetrabutylphosphonium fluoride, triethylmethylammonium fluoride, triethylamine 3 hydrofluoride, triethylamine 5 hydrofluoride, triethylamine 7 hydrofluoride, pyridinium poly(hydrofluoric acid), pyridine 1 hydrofluoride, pyridinium poly(hydrofluoric acid), pyridine 9 hydrofluoride, ammonium hydrofluorate and ammonium fluoride.

[0206] Examples of organic solvents include aromatic solvents, ester solvents, ketone solvents, saturated hydrocarbon solvents, nitrile solvents, ether solvents, sulfoxide solvents, and halogenated hydrocarbon solvents. The organic solvents may be used alone or in combination of two or more.

[0207] Suitable examples of the organic solvent include ether-based solvents, ester-based solvents, halogenated hydrocarbon-based solvents, and nitrile-based solvents.

[0208] Suitable specific examples of the aromatic solvent include benzene, toluene and xylene.

[0209] Suitable specific examples of the ester solvent include methyl formate, ethyl formate, methyl acetate, ethyl acetate, isopropyl acetate, methyl propionate, ethyl propionate, and n-butyl acetate.

[0210] Suitable specific examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone.

[0211] Suitable specific examples of the saturated hydrocarbon solvent include n-pentane, n-hexane, cyclohexane and n-heptane.

[0212] Suitable specific examples of the nitrile solvent include 1,4-dicyanobutane, acetonitrile and benzonitrile.

[0213] Specific examples of suitable ether solvents include diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, and crown ethers.

[0214] Suitable specific examples of the sulfoxide-based solvent include dimethyl sulfoxide and sulfolane.

[0215] Suitable specific examples of the halogenated hydrocarbon solvent include dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,2-dichlorobenzene, and chlorobenzene.

[0216] Suitable specific examples of the organic solvent include ethyl acetate, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1,4-dicyanobutane, dichloromethane, chloroform, tetrahydrofuran, and acetonitrile.

[0217] In the present invention, it is considered that compounds (3-1) and (3-2) act as reactants in step A. The organic solvent in step A does not include compounds (3-1) and (3-2).

[0218] Process A

[0219] The amount of compound (3) used in step A is preferably in the range of 0.05 to 10 mol, more preferably 0.08 to 5 mol, and even more preferably 0.1 to 2 mol, based on 1 mol of compound (2).

[0220] The amount of compound (4) used in step A is preferably in the range of 0.001 to 0.3 mol, more preferably 0.002 to 0.1 mol, and even more preferably 0.006 to 0.1 mol, based on 1 mol of compound (2).

[0221] The amount of the organic solvent used in step A can be set to an amount that can function as a solvent based on technical common sense, etc. The amount of the organic solvent used in step A is preferably in the range of 0.1 to 50 mol, more preferably in the range of 0.1 to 20 mol, and further preferably in the range of 0.1 to 10 mol, relative to 1 mol of compound (2).

[0222] The reaction temperature of step A is preferably in the range of -30 to 40°C, more preferably in the range of -30 to 30°C, and further preferably in the range of -20 to 30°C. When the reaction temperature of step A is relatively low, the selectivity of compound (1) tends to be relatively improved. When the reaction temperature of step A is relatively high, the reactivity tends to be relatively improved.

[0223] The reaction time of step A is preferably in the range of 0.5 to 48 hours, more preferably in the range of 0.5 to 24 hours, and even more preferably in the range of 0.5 to 12 hours.

[0224] The reaction of step A may be carried out in the presence or absence of an inert gas (eg, nitrogen), and is preferably carried out in the absence of an inert gas.

[0225] Step A can be carried out under reduced pressure, atmospheric pressure or pressurized conditions.

[0226] In step A, compound (2) and compound (3) may be reacted in an organic solvent. Preferably, compound (3), compound (4) and an organic solvent are mixed and cooled (eg, -30°C), and compound (2) is added thereto.

[0227] The compound (1) produced in step A can be isolated or purified by conventional methods such as extraction, dissolution, concentration, precipitation, dehydration, adsorption, distillation, rectification, chromatography, or a combination thereof, as required.

[0228] In the conventional method of producing compound (1) by reacting N,N-dimethylformamide with hexafluoropropylene oxide at 0°C (first reaction), and then heating to 140°C in diethylene glycol dimethyl ether in the presence of cesium fluoride (second reaction), a large amount of difluoroamine is produced as a by-product during the first reaction. Difluoroamine converts the target compound (1) into other compounds, and therefore, difluoroamine needs to be captured and removed using HCl gas that is harmful to the human body before the second reaction. In step A of the present invention, since a solvent is used, difluoroamine moves into the solvent, and the contact between difluoroamine and compound (1) is suppressed, and therefore, it is not necessary to capture difluoroamine using HCl gas.

[0229] In the method disclosed in Patent Document 1, fluorine gas, which is difficult to handle and dangerous, is used when producing 3,5,5,6-tetrafluoro-3,6-bis(trifluoromethyl)-1,4-dioxane-2-one. In addition, in the method disclosed in Patent Document 1, 3,5,5,6-tetrafluoro-3,6-bis(trifluoromethyl)-1,4-dioxane-2-one is produced in the form of a mixture, which is difficult to purify. In contrast, in step A of the present invention, fluorine gas may not be used, and the product liquid obtained in step A can be easily purified, for example, by liquid separation.

[0230] Process B

[0231] The method for producing the compound represented by formula (1) of the present invention may include a step B of liquid separation in addition to step A. The reaction liquid generated in step A may be composed of two layers, an upper liquid layer and a lower liquid layer, and one layer contains compound (1). Therefore, by liquid separation of the reaction liquid, a liquid layer containing the target compound (1) can be easily obtained.

[0232] The method for isolating compound (1) from the liquid layer may be a conventional method such as extraction, dissolution, concentration, precipitation, dehydration, adsorption, distillation, rectification, chromatography, or a combination thereof. The liquid layer containing compound (1) obtained in step B contains few impurity compounds having a boiling point close to that of compound (1), and therefore compound (1) can be easily obtained by distilling the liquid layer.

[0233] Method for producing the compound represented by formula (5)

[0234] One embodiment of the present invention is a method for producing a compound represented by formula (5) (sometimes referred to as compound (5) in this specification).

[0235] Formula (5):

[0236]

[0237] [In formula (5), R 1 is a fluorine atom or a fluoroalkyl group.]

[0238] The method includes:

[0239] Step C of heating the compound represented by the formula (1) produced in the step A or B in the presence of the compound (4) to produce a compound represented by the formula (6) (sometimes referred to as compound (6) in this specification);

[0240] Step D of reacting the compound represented by the formula (6) with a base (sometimes referred to as a base (d) in this specification) to produce a compound represented by the formula (8); and

[0241] Step E: heating the compound represented by the formula (8) (sometimes referred to as compound (8) in this specification) to generate the compound represented by the above formula (5).

[0242] Formula (6):

[0243]

[0244] [In formula (6), R 1 Same meaning as above.]

[0245] Formula (8):

[0246]

[0247] [In formula (8), R 81 is a group corresponding to the above base, R 1 Same meaning as above.]

[0248] Compound (8) is a carboxylate salt of compound (6) corresponding to the above base.

[0249] R 81 Preferred are alkali metal atoms, alkaline earth metal atoms, pyridinium, ammonium, and amino groups which may be substituted with organic groups; more preferred are potassium atoms, sodium atoms, or ammonium; and particularly preferred are sodium atoms or potassium atoms.

[0250] In this specification, step C, step D, step E and step F can be implemented by a known method, for example, according to the method described in Japanese Patent Application Laid-Open No. 2005-002014, U.S. Patent No. 3308107 or U.S. Patent No. 6664431, except that the formula (1) generated in the above step A or B is used as a raw material in step C. The contents of the publications are incorporated into this specification by reference.

[0251] Process C

[0252] In step C, compound (1) produced in step A or B is isomerized by heating in the presence of compound (4) to produce compound (6).

[0253] In step C, the compound (1) produced in step A or B may be isolated and used, or a liquid layer of the reaction solution obtained in step B containing compound (1) may be used.

[0254] The details of the compound (4) in step C apply the same as those described for the compound (4) in step (A) unless otherwise specified.

[0255] The amount of compound (4) used in step C is preferably in the range of 0.001 to 10 mol, more preferably 0.002 to 5.0 mol, and even more preferably 0.006 to 1.0 mol, based on 1 mol of compound (1).

[0256] Step C can be suitably carried out in an organic solvent. Examples and suitable examples of the organic solvent are the same as those described above. Suitable specific examples of the organic solvent include diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1,4-dicyanobutane, acetonitrile, 1,2-dimethyl ether, tetrahydrofuran and dimethyl sulfoxide.

[0257] The amount of the organic solvent used in step C can be an amount that allows the organic solvent to function as a solvent based on common technical knowledge and the like.

[0258] The reaction temperature in step C is preferably in the range of 50 to 300°C, more preferably in the range of 50 to 200°C, and further preferably in the range of 100 to 180°C.

[0259] The reaction time of step C is preferably in the range of 0.5 to 60 hours, more preferably in the range of 1 to 24 hours, and even more preferably in the range of 2 to 24 hours.

[0260] The compound (6) produced in step C can be isolated or purified by conventional methods such as extraction, dissolution, concentration, precipitation, dehydration, adsorption, distillation, rectification, chromatography, or a combination thereof, as required.

[0261] Process D

[0262] In step D, compound (6) is reacted with base (d) to produce compound (8). Compound (8) is a carboxylate of compound (6) corresponding to the base (d).

[0263] The base (d) is, for example, at least one selected from the group consisting of (1) acetates, carbonates, bicarbonates, phosphates, hydrogenphosphates, alkoxides, hydroxides, hydrides, ammonium or amides of alkali or alkaline earth metals, (2) alkali metals, and (3) amines.

[0264] Examples of the alkoxide include sodium methoxide, sodium ethoxide, sodium propoxide, potassium methoxide, potassium ethoxide, potassium propoxide, lithium methoxide, and lithium ethoxide.

[0265] Examples of hydroxide salts include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, and barium hydroxide.

[0266] Examples of hydride salts include sodium hydride, potassium hydride, lithium hydride and calcium hydride.

[0267] Examples of alkali metals include sodium, potassium and lithium.

[0268] Examples of the amine include aliphatic amines, alicyclic amines, aromatic amines and heterocyclic amines. The amine is suitably a tertiary amine.

[0269] The base (d) is preferably at least one selected from the group consisting of sodium methoxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium carbonate and ammonia.

[0270] The base (d) is more preferably at least one selected from the group consisting of potassium hydroxide, potassium hydrogen carbonate, potassium carbonate and sodium carbonate.

[0271] Step D is preferably carried out in an organic solvent. Examples and suitable examples of the organic solvent are the same as those described above. Suitable specific examples of the organic solvent include methanol, ethanol, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1,4-dicyanobutane, 1,2-dimethyl ether, tetrahydrofuran and acetonitrile.

[0272] The amount of the base (d) used in step D is preferably in the range of 0.05 to 10 mol, more preferably 0.1 to 10 mol, and even more preferably 0.1 to 5 mol, based on 1 mol of compound (6).

[0273] The amount of the organic solvent used in step D can be an amount that allows the organic solvent to function as a solvent based on common technical knowledge and the like.

[0274] The reaction temperature in step D is preferably in the range of -50 to 120°C, more preferably in the range of -20 to 100°C, and further preferably in the range of -10 to 70°C.

[0275] The reaction time of step D is preferably in the range of 0.1 to 24 hours, more preferably in the range of 0.1 to 12 hours, and even more preferably in the range of 0.1 to 6 hours.

[0276] The compound (8) produced in step D can be isolated or purified by conventional methods such as extraction, dissolution, concentration, precipitation, dehydration, adsorption, distillation, rectification, chromatography, or a combination thereof, as required.

[0277] Process E

[0278] In step E, compound (8) is heated and thermally decomposed to produce compound (5). Compound (5) is useful as an intermediate for producing a raw material of a resin material.

[0279] Step E can be carried out in an organic solvent or in the absence of a solvent. Examples and suitable examples of the organic solvent are the same as those described above. Suitable specific examples of the organic solvent include ethyl acetate, butyl acetate, propyl acetate, methyl propionate, ethyl propionate, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1,4-dicyanobutane and acetonitrile.

[0280] The amount of the organic solvent used in step E can be an amount that allows the organic solvent to function as a solvent based on common technical knowledge and the like.

[0281] The reaction temperature of step E is preferably in the range of 100 to 400° C., more preferably in the range of 100 to 300° C., and further preferably in the range of 100 to 200° C. when a solvent is included. When no solvent is included, the reaction temperature is preferably in the range of 100 to 400° C., more preferably in the range of 150 to 400° C., and further preferably in the range of 150 to 350° C.

[0282] The reaction time of step E is preferably in the range of 0.1 to 24 hours, more preferably in the range of 0.1 to 12 hours, and even more preferably in the range of 0.1 to 6 hours.

[0283] The reaction in step E may be carried out in the presence or absence of an inert gas (eg, nitrogen), and is preferably carried out in the absence of an inert gas.

[0284] Step E can be carried out under reduced pressure, atmospheric pressure or pressurized conditions.

[0285] The compound (5) produced in step E can be isolated or purified by conventional methods such as extraction, dissolution, concentration, precipitation, dehydration, adsorption, distillation, rectification, chromatography, or a combination thereof, as required.

[0286] One embodiment of the present invention is a method for producing the compound represented by the above formula (5), wherein, instead of the above step D, the method comprises:

[0287] Step D1 of reacting the compound represented by the above formula (6) with water or an alkyl alcohol to produce a compound represented by the formula (7) (sometimes referred to as compound (7) in this specification); and

[0288] Step D2 is to react the compound represented by the formula (7) with a base (sometimes referred to as a base (d2) in this specification) to produce the compound represented by the above formula (8).

[0289] Formula (7):

[0290]

[0291] [In formula (7), R 71 is a hydrogen atom or an alkyl group, R 1 Same meaning as above.]

[0292] R 71 Preferably, a hydrogen atom or a linear or branched C 1－10 Alkyl, more preferably a hydrogen atom or a linear or branched C 1－5 Alkyl, more preferably a linear or branched C 1－4 The alkyl group is particularly preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group or a tert-butyl group, and is further particularly preferably a methyl group or an ethyl group.

[0293] Process D1

[0294] In step D1, compound (6) is reacted with water or an alkyl alcohol to be converted into the corresponding carboxylic acid or alkyl ester to produce compound (7).

[0295] In step D1, compound (6) may be an isolated compound, or the product solution produced in step C containing compound (6) may be used as it is. The use of the product solution is advantageous in that purification of compound (6) is not necessary, and is therefore preferred.

[0296] The alkyl alcohol is preferably a linear or branched C 1－10 Alkyl alcohol, more preferably a linear or branched C 1－5 Alkyl alcohol, more preferably a linear or branched C 1－4 The alkyl alcohol is particularly preferably methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol or tert-butanol, and more particularly preferably methanol or ethanol.

[0297] The amount of water, alkyl alcohol or a mixture of water and the alcohol used in step D1 is preferably in the range of 0.1 to 50 mol, more preferably 0.2 to 20 mol, further preferably 0.5 to 10 mol, based on 1 mol of compound (6).

[0298] In step D1, in addition to water and the above-mentioned alkyl alcohol, other organic solvents may be used. Examples and suitable examples of organic solvents are the same as those described above. Specific examples of the organic solvent include 1,2-dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1,4-dicyanobutane and acetonitrile. The amount of the organic solvent may preferably be in the range of 0.01 to 50 mol, more preferably in the range of 0.1 to 50 mol, relative to 1 mol of compound (6).

[0299] The reaction temperature of step D1 is preferably in the range of -50 to 50°C, more preferably in the range of -20 to 30°C, and further preferably in the range of -20 to 20°C.

[0300] The reaction time of step D1 is preferably in the range of 0.1 to 24 hours, more preferably in the range of 0.1 to 12 hours, and even more preferably in the range of 0.1 to 6 hours.

[0301] The reaction in step D1 may be carried out in the presence or absence of an inert gas (eg, nitrogen), and is preferably carried out in the absence of an inert gas.

[0302] Step D1 can be carried out under reduced pressure, atmospheric pressure, or pressurized conditions.

[0303] The compound (7) produced in step D1 can be isolated or purified by conventional methods such as extraction, dissolution, concentration, precipitation, dehydration, adsorption, distillation, rectification, chromatography, or a combination thereof, as required.

[0304] It is preferred to react the above alkyl alcohol with compound (6) to generate compound (7) in a reaction solution, add water to the reaction solution, recover the generated organic layer, and distill the organic layer, because compound (7) can be purified simply.

[0305] Process D2

[0306] In step D2, compound (7) is reacted with base (d2) to produce compound (8). The details of the base (d2) in step D2 are the same as those described for the base in step D unless otherwise specified.

[0307] The amount of the base (d2) used in step D2 is preferably in the range of 0.1 to 20 mol, more preferably in the range of 0.5 to 15 mol, and even more preferably in the range of 1 to 10 mol, based on 1 mol of compound (7).

[0308] Step D2 is preferably carried out in the presence of an organic solvent. Examples and suitable examples of the organic solvent are the same as those described above.

[0309] The organic solvent is preferably methanol, ethanol, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1,4-dicyanobutane, acetonitrile or tetrahydrofuran, and one of them may be used alone or two or more of them may be mixed and used.

[0310] The reaction temperature in step D2 is preferably in the range of -50 to 120°C, more preferably in the range of -20 to 100°C, and further preferably in the range of -10 to 70°C.

[0311] The reaction time of step D2 is preferably in the range of 0.1 hour to 24 hours, more preferably in the range of 0.1 hour to 12 hours, and even more preferably in the range of 0.1 hour to 6 hours.

[0312] The reaction in step D2 may be carried out in the presence or absence of an inert gas (eg, nitrogen), and is preferably carried out in the absence of an inert gas.

[0313] Step D2 can be carried out under reduced pressure, atmospheric pressure, or pressurized conditions.

[0314] In step D2, compound (8) can be precipitated in a solvent in a solid form. When precipitated, compound (8) can be easily isolated by removing the solvent. The method for removing the solvent may be a known method.

[0315] One embodiment of the present invention is a method for producing the compound represented by the above formula (5), further comprising a step D1a of purifying the liquid generated in the above step D1 to obtain the compound represented by the above formula (7). The purified compound (7) can be provided to the above step D2.

[0316] Process D1a

[0317] In step D1a, the reaction solution generated in step D1 is refined to obtain compound (7). Compound (7) can be isolated or refined by conventional methods such as extraction, dissolution, concentration, precipitation, dehydration, adsorption, distillation, rectification, chromatography, or a combination thereof. Preferably, the organic layer in the reaction solution generated in step D1 is refined, and more preferably, the organic layer is refined by distillation to simply obtain compound (7). When the organic layer is large, it does not contain or contains only a small amount of other substances having a boiling point close to that of compound (7), and is therefore suitable for refining by distillation.

[0318] One embodiment of the present invention is a method for producing a compound represented by the above formula (5), which, instead of the above steps D and E, includes: heating the compound represented by the above formula (6) in the presence of a base (sometimes referred to as a base (f) in this specification) to generate a step F of the compound represented by the above formula (5).

[0319] Process F

[0320] In step F, compound (6) is heated in the presence of a base (f) to generate the compound represented by the above formula (5). Step F can be carried out by a known method, or by a method described in, for example, U.S. Patent No. 3,308,107 or U.S. Patent No. 6,664,431. The contents of the publications are incorporated herein by reference.

[0321] In step F, compound (6) may be an isolated compound, or the product liquid generated in step C containing compound (6) may be used as it is. When the product liquid is used, there is an advantage that purification of compound (6) is unnecessary, which is preferred.

[0322] Regarding the details of the base (f) in step F, the same details as those described for the base in step D apply unless otherwise specified.

[0323] The base (f) is preferably a hydroxide, halide, carbonate or hydrogen carbonate of an alkali metal, or ammonia. The alkali metal halide may be supported on a carrier such as activated carbon or an inorganic oxide.

[0324] The base (f) is more preferably at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonia, potassium fluoride, sodium fluoride, cesium fluoride, sodium chloride and potassium iodide.

[0325] The base (f) is more preferably at least one selected from the group consisting of potassium hydroxide, potassium hydrogen carbonate, potassium carbonate, sodium carbonate, potassium fluoride, sodium fluoride, cesium fluoride, sodium chloride and potassium iodide.

[0326] The support of the base (f) is preferably activated carbon, an alkali metal oxide, an alkaline earth metal oxide, zinc oxide, aluminum oxide, nickel oxide or silicon dioxide.

[0327] The support of the base (f) is more preferably at least one selected from the group consisting of alkaline earth metal oxides, alumina and silica.

[0328] Specific examples of the alkali metal oxide include lithium oxide, sodium oxide, potassium oxide, rubidium oxide, and cesium oxide.

[0329] Specific examples of the alkaline earth metal oxides include magnesium oxide, calcium oxide, and barium oxide.

[0330] Step F can be carried out in an organic solvent or in the absence of a solvent. Examples and suitable examples of the organic solvent are the same as those described above. Suitable specific examples of the organic solvent include ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1,4-dicyanobutane, tetrahydrofuran and acetonitrile.

[0331] The amount of the base (f) used in step F is preferably in the range of 0.1 to 200 mol, more preferably in the range of 0.5 to 100 mol, and even more preferably in the range of 1 to 50 mol, based on 1 mol of compound (6).

[0332] The amount of the inorganic oxide used in step F is preferably in the range of 0.2 to 400 mol, more preferably 1 to 200 mol, and even more preferably 2 to 100 mol, based on 1 mol of compound (6).

[0333] The amount of the organic solvent used in step F can be an amount that allows the organic solvent to function as a solvent based on common technical knowledge and the like.

[0334] The reaction temperature of step F is preferably in the range of 80 to 400° C., more preferably in the range of 100 to 350° C., and further preferably in the range of 100 to 300° C. when a solvent is included. When no solvent is included, the reaction temperature is preferably in the range of 100 to 400° C., more preferably in the range of 150 to 400° C., and further preferably in the range of 150 to 350° C.

[0335] The reaction time of step F is preferably in the range of 0.01 to 24 hours, more preferably in the range of 0.01 to 12 hours, and even more preferably in the range of 0.01 to 6 hours.

[0336] The reaction in step F may be carried out in the presence or absence of an inert gas (eg, nitrogen), and is preferably carried out in the absence of an inert gas.

[0337] Step F can be carried out under reduced pressure, atmospheric pressure or pressurized conditions.

[0338] The compound (5) produced in step F can be isolated or purified by conventional methods such as extraction, dissolution, concentration, precipitation, dehydration, adsorption, distillation, rectification, chromatography, or a combination thereof, as required.

[0339] Compound

[0340] Among the compounds that can be produced by the production method of the present invention, the compound represented by formula (7-1) (sometimes referred to as compound (7-1) in this specification) is a novel compound. The present invention also provides these novel compounds. These novel compounds can be effectively used as raw materials, intermediates, etc. of monomers for polymer production.

[0341] Formula (7-1):

[0342]

[0343] [In formula (7-1), 2 R 1 are the same, are fluorine atoms or fluoroalkyl groups, R 72 is an alkyl group.]

[0344] In compound (7-1), R 1 As mentioned above.

[0345] In compound (7-1), R 72 Preferably, a linear or branched C 1－10 Alkyl, more preferably a hydrogen atom or a linear or branched C 1－5 Alkyl, more preferably a linear or branched C 1－4The alkyl group is particularly preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group or a tert-butyl group, and more particularly preferably a methyl group or an ethyl group.

[0346] Compound (7-1) preferably has R 1 The same is fluorine atom or C 1－10 Fluoroalkyl, R 72 Straight or branched chain C 1－10 alkyl.

[0347] Compound (7-1) is more preferably R 1 The same is fluorine atom or C 1－5 Perfluoroalkyl, R 72 Straight or branched chain C 1－5 alkyl.

[0348] Compound (7-1) is more preferably 1 The same is fluorine atom or C 1－3 Perfluoroalkyl, R 72 Straight or branched chain C 1－4 alkyl.

[0349] Compound (7-1) is particularly preferably 1 Same as C 1－3 Perfluoroalkyl, R 72 It is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.

[0350] Compound (7-1) is particularly preferably 1 Same as C 1－3 Perfluoroalkyl, R 72 It is methyl or ethyl.

[0351] Method for producing the compound represented by formula (7-1)

[0352] The present invention also provides a method for producing the novel compound (7-1). The method comprises a step D1-1 of reacting the compound represented by the above formula (6) with an alkyl alcohol to produce the compound represented by the above formula (7-1).

[0353] The compound (6) used in step D1-1 of the method for producing compound (7-1) may be a compound produced in step C of the method for producing compound (5) or a compound produced by a known technique. Other matters of this step are the same as step D1 in the method for producing compound (5) except that this step does not include a method for reacting compound (6) with water.

[0354] Composition

[0355] One embodiment of the present invention is a composition containing the compound represented by the above formula (5), further containing 0.00001 to 1 parts by mass of a compound represented by formula (9) (sometimes referred to as compound (9) in this specification) and / or 0.00001 to 1 parts by mass of a compound represented by formula (10) (sometimes referred to as compound (10) in this specification) relative to 100 parts by mass of the compound represented by formula (5).

[0356] Formula (9):

[0357]

[0358] [In formula (9), two R 1 Same meaning as above.]

[0359] Formula (10):

[0360]

[0361] [In formula (10), two R 1 Same meaning as above.]

[0362] The method for producing the compound represented by formula (5) of the present invention can also produce the above composition. The above composition may further contain compound (4-1), a polymerization inhibitor, water or a polar solvent.

[0363] The amounts of the various components contained in the composition can be adjusted by setting the reaction conditions (e.g., temperature, time, type and amount of raw materials, type and amount of solvent, type and amount of catalyst). In addition, the amounts of the various components can be adjusted by purifying the generated compound (5).

[0364] Regarding R in the above composition 1 Unless otherwise specified, the details of R in the method for producing the compound represented by the above formula (1) shall apply. 1 Details of the situation.

[0365] Suitable specific examples of compound (9) include 2,2,3,5,6-pentafluoro-3,6-bis(trifluoromethyl)-5-((1,2,2-trifluorovinyl)oxy)-1,4-dioxane.

[0366] The amount of compound (9) in the composition is preferably 0.00001 to 1 part by mass, more preferably 0.00001 to 0.8 part by mass, further preferably 0.00001 to 0.5 part by mass, particularly preferably 0.0001 to 0.1 part by mass, based on 100 parts by mass of compound (5).

[0367] Suitable specific examples of the compound (10) include perfluoro-2,4-dimethyl-1,3-dioxolane.

[0368] The amount of compound (10) in the composition is preferably 0.00001 to 1 part by mass, more preferably 0.00001 to 0.8 part by mass, further preferably 0.00001 to 0.5 part by mass, particularly preferably 0.0001 to 0.1 part by mass, based on 100 parts by mass of compound (5).

[0369] The above composition may contain either or both of compound (9) and compound (10). The composition preferably contains 0.00001 to 0.8 parts by mass of compound (9) and / or 0.00001 to 0.8 parts by mass of compound (10) relative to 100 parts by mass of compound (5), more preferably 0.00001 to 0.5 parts by mass of compound (9) and / or 0.00001 to 0.5 parts by mass of compound (10), and particularly preferably 0.0001 to 0.1 parts by mass of compound (9) and / or 0.0001 to 0.1 parts by mass of compound (10).

[0370] Preferred specific examples of the compound (4-1) and the symbols in the formula (4-1) are the same as those for the compound (4-1) in the above-mentioned method for producing the compound represented by the formula (1).

[0371] Suitable examples of the polar solvent include alcohol solvents, ether solvents, ester solvents and nitrile solvents.

[0372] Suitable specific examples of the alcohol solvent include methanol, ethanol, isopropanol and tert-butanol.

[0373] Suitable specific examples of the ester solvent include methyl formate, ethyl formate, methyl acetate, ethyl acetate, isopropyl acetate, methyl propionate, ethyl propionate, and n-butyl acetate.

[0374] Suitable specific examples of the nitrile solvent include 1,4-dicyanobutane, acetonitrile and benzonitrile.

[0375] Suitable specific examples of the ether solvent include diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, and 1,2-dimethoxyethane.

[0376] Suitable specific examples of the polar solvent include methanol, ethanol, isopropanol, tert-butyl alcohol, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1,4-dicyanobutane, acetonitrile and tetrahydrofuran.

[0377] Suitable examples of the polymerization inhibitor include 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl-tert-butylphenol, 2,6-di-tert-butyl-p-cresol and benzotriazole.

[0378] The amount ratio of the compound (4-1) in the composition is preferably 0.00001 to 0.1 part by mass, more preferably 0.00001 to 0.08 part by mass, further preferably 0.00001 to 0.05 part by mass, particularly preferably 0.00001 to 0.01 part by mass, based on 100 parts by mass of the compound (5).

[0379] The amount ratio of the polar solvent in the composition is preferably 0.00001 to 0.1 part by mass, more preferably 0.00001 to 0.08 part by mass, further preferably 0.00001 to 0.05 part by mass, particularly preferably 0.0001 to 0.01 part by mass, based on 100 parts by mass of compound (5).

[0380] The amount ratio of the polymerization inhibitor in the composition is preferably 0.00001 to 1 part by mass, more preferably 0.00001 to 0.8 part by mass, further preferably 0.00001 to 0.5 part by mass, particularly preferably 0.00001 to 0.1 part by mass, based on 100 parts by mass of the compound (5).

[0381] The amount of water in the composition is preferably 0.00001 to 0.1 parts by mass, more preferably 0.00001 to 0.08 parts by mass, further preferably 0.00001 to 0.05 parts by mass, particularly preferably 0.00001 to 0.01 parts by mass, based on 100 parts by mass of compound (5).

[0382] The composition of the present invention can be preferably used as a raw material for a resin material, for example, when the amount ratio is within the above range, and is advantageous in terms of the production cost of the composition, thereby also being advantageous in terms of the production cost of the final product.

[0383] Although the embodiments have been described above, it should be understood that various changes can be made to the modes and details without departing from the spirit and scope of the scope of the claims.

[0384] Example

[0385] Hereinafter, an embodiment of the present invention will be described in further detail with reference to examples, but the present invention is not limited thereto.

[0386] Symbols and abbreviations in the examples have the following meanings.

[0387] CsF: Cesium Fluoride

[0388] GC: Gas Chromatography

[0389] DMF: N,N-dimethylformamide

[0390] DIGLYME: Diethylene glycol dimethyl ether

[0391] Me:Methyl

[0392] Compound 1a: a compound represented by the following formula (1a)

[0393]

[0394] Compound 6a: A compound represented by the following formula (6a)

[0395]

[0396] Compound 8a: A compound represented by the following formula (8a)

[0397]

[0398] Compound 5a: A compound represented by the following formula (5a)

[0399]

[0400] Compound 9a: A compound represented by the following formula (9a)

[0401]

[0402] Compound 10a: A compound represented by the following formula (10a):

[0403] Compound 11a: A compound represented by the following formula (11a)

[0404] Compound 11b: A compound represented by the following formula (11b):

[0405] Compound 12a: A compound represented by the following formula (12a):

[0406]

[0407] Compound 13a: Compound represented by the following formula (13a): CF2=CFOCF2CF2CF3 (13a)

[0408] Compound 7a: A compound represented by the following formula (7a)

[0409]

[0410] Compound 14a: A compound represented by the following formula (14a)

[0411]

[0412] Compound 14b: A compound represented by the following formula (14b):

[0413]

[0414] Compound 14c: A compound represented by the following formula (14c):

[0415]

[0416] Compound 15a: A compound represented by the following formula (15a)

[0417] CF3CF2CF2OCFCF3COF(15a)

[0418] Compound 15b: A compound represented by the following formula (15b):

[0419] CF3CF2CF2OCFCF3COOMe(15b)

[0420] Compound 15c: A compound represented by the following formula (15c):

[0421] CF3CF2CF2OCFCF3COOK(15c)

[0422] Compound 16a: A compound represented by the following formula (16a):

[0423]

[0424] Example 1: Steps A and B

[0425] 0.83 g of CsF (2.5 mmol), 9.03 g of DMF (0.12 mol) and 16.6 g of DIGLYME (0.12 mol) were added to the reactor and cooled to -20°C. 44 g of 6-fluoropropylene oxide (0.27 mol) was added to the above reactor and stirred for 2 hours. After the 6-fluoropropylene oxide disappeared, the reaction solution was recovered. The reaction solution was separated into two layers, the upper liquid and the lower liquid. The reaction solution was separated and 29 g of the upper liquid and 40 g of the lower liquid were recovered respectively. The upper liquid and the lower liquid were analyzed by GC. Compound 1a was obtained with a yield of 52% and 63 GC%.

[0426] Compound 1a: 63 GC%, hexafluoropropylene: 10 GC%, compound 14a: less than 15 GC%, compound 11a(H): 0.1 GC%, CsF: less than 0.1%, compound 15a: 1.0 GC%, (CH3)2NCF2H: 0.5 GC%, compound 16a: 6.0 GC%, DIGLYME: less than 1.0 GC%.

[0427] It should be noted that "% or less" here means that the content of each component is 0.0000095% or more and is within the range of % or less of the specific numerical value. The same applies to the following examples.

[0428] The CsF content was measured by NMR method.

[0429] The contents of other components were determined by GC method.

[0430] Comparative Example 1: Synthesis of Compound 1a via 2 steps

[0431] 4.27 g of DMF (0.06 mol) was added to the reactor and cooled to -27°C. 12 g of 6-fluoropropylene oxide (0.07 mol) was added to the reactor and stirred for 1 hour. After stirring, the reaction solution was recovered. The reaction solution was analyzed by NMR. 4-Fluoro-5-oxo-2,4-bis(trifluoromethyl)-1,3-dioxolane-2-carbonyl fluoride, which was a precursor of the target product, was obtained at a yield of 5%. Since the yield of the precursor was very low, the second step was not implemented.

[0432] Example 2: Process C

[0433] 20 g of the lower layer liquid (containing 13 g of compound 1a) obtained by the same operation as in Example 1, 3.2 g of CsF (21 mmol), and 7.1 g of DIGLYME (53 mmol) were added to the reactor and heated at 120° C. for 12 hours to obtain a reaction liquid. The upper layer liquid and the lower layer liquid of the reaction liquid were analyzed by GC. 7.2 g of compound 6a was obtained with a purity of 74%.

[0434] Compound 6a: 74 GC%, hexafluoropropylene: 2.0 GC%, compound 1a: 1.1 GC%, compound 14a: 3.0 GC% or less, compound 11a(H): 0.1 GC%, CsF: 0.1% or less, compound 15a: 0.1 GC%, (CH3)2NCF2H: 0.1 GC% or less, DIGLYME: 15 GC% or less.

[0435] The CsF content was measured by NMR method.

[0436] The contents of other components were determined by GC method.

[0437] Example 3: Step D

[0438] The lower layer liquid containing 7.2 g of compound 6a obtained in Example 2 was added with 12.7 g of potassium carbonate (0.09 mol) and 28 g of dimethoxyethane (0.3 mol) and stirred at 60°C for 2 hours to obtain a reaction liquid. The reaction liquid was filtered to obtain a filtrate, and the filtrate was concentrated. As a result of NMR analysis, a concentrate containing 7.0 g of compound 8a was obtained (yield 44%).

[0439] Compound 8a: 80%, Compound 14c: 3.0% or less, Compound 11a(H): 0.1%, CsF: 1.0% or less, KF: 1.0% or less, Compound 15c: 0.1%, Water: 0.1% or less, DIGLYME: 10% or less.

[0440] The water content was determined by Karl Fischer coulometric titration.

[0441] The contents of other components were measured by NMR method.

[0442] Example 4: Step E

[0443] 6.7 g of compound 8a obtained in Example 3 was added to a reactor and heated at 200° C. for 4 hours and 300° C. for 1 hour. The product was collected and recovered at −78° C. and analyzed by NMR and GC to obtain compound 5a with a yield of 60% and a purity of 95%.

[0444] Compound 5a: 95GC%, hexafluoropropylene: 0.01GC%, compound 9a: less than 1.0GC%, compound 11a (H): 0.1GC%, compound 11b (Me): 0.1GC%, compound 12a: 0.1GC%, CsF: less than 0.1%, KF: less than 0.1%, compound 13a: 0.1GC%, compound 10a: less than 0.2GC%, DIGLYME: less than 4.0GC%, water: less than 0.1%.

[0445] The contents of CsF and KF were measured by ion chromatography. In ion chromatography, as a pretreatment, the sample was subjected to liquid-liquid extraction with the same volume of ultrapure water, and the resulting liquid was used for measurement.

[0446] The water content was determined by Karl Fischer coulometric titration.

[0447] The contents of other components were determined by GC method.

[0448] Example 5: Step D1

[0449] 32 g (1 mol) of methanol and 45 g of water were added to 83 g of the upper layer liquid and 79 g of the lower layer liquid obtained in the same manner as in Example 2, and the mixture was stirred for 2 hours. The resulting liquid was separated into two layers, and the lower layer liquid was recovered by separation and distilled (150° C., 5 hours) to obtain compound 7a. The yield was 47%.

[0450] -77ppm(1F,CF2),-81ppm(3F,CF CF3 ),-82ppm(3F,CF3),-83ppm(1F,CF2),-124ppm(1F, CF CF3)

[0451] Compound 7a: 98 GC%, Compound 14b: 0.1 GC% or less, Compound 11a (H): 0.1 GC%, Compound 11b (Me): 0.1 GC%, Compound 15b: 0.1 GC%, Water: 0.1% or less.

[0452] The water content was determined by Karl Fischer coulometric titration.

[0453] The contents of other components were determined by GC method.

[0454] Example 6: Step D2

[0455] 0.13 mol of potassium hydroxide was added to 42 g of methanol. The methanol solution was added to a glass reactor. 0.13 mol of compound 7a was slowly added to the methanol solution and stirred at 20° C. for 1 hour. The solvent was distilled off from the reaction solution using a concentrator, and the solid thus generated was recovered. The individual was dried under reduced pressure to obtain compound 8a in a stoichiometric amount.

Claims

1. A composition containing a compound represented by formula (5), characterized in that: 0.00001 to 1 parts by mass of a compound represented by formula (9) and / or 0.00001 to 1 parts by mass of a compound represented by formula (10) relative to 100 parts by mass of the compound represented by formula (5), Formula (5): In formula (5), R 1 is a fluorine atom or a fluoroalkyl group; Formula (9): In formula (9), the two R 1 Has the same meaning as above; Formula (10): In formula (10), the two R 1 Same meaning as above.

2. The composition according to claim 1, characterized in that: With respect to 100 parts by mass of the compound represented by the formula (5), The content of the compound represented by formula (9) is 0.00001 to 0.5 parts by mass, The content of the compound represented by the formula (10) is 0.00001 to 0.5 parts by mass.

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