Fluorolactone and method for producing the same

Abstract

The present invention provides a method for producing a fluorolactone compound from hexafluoropropylene oxide or the like in one step. The present invention relates to a method for producing a compound represented by formula (1) [wherein, two R 1 The same is a fluorine atom or a fluoroalkyl group. ], including making the compound represented by formula (2) [wherein, 2 R 1 The meaning is the same as above. ], the compound represented by formula (3) [wherein, R 31 , R 32 and R 33 are the same or different and are hydrogen atoms or alkyl groups, or R 31 , R 32 and R 33 Two of them may be bonded to each other to form a ring which may have one or more substituents. ] and compounds represented by formula (4-1) etc. [wherein, R 41 , R 42 , R 43 and R 44 are the same or different and are hydrogen atoms or alkyl groups, or R 41 , R 42 , R 43 and R 44 Two of them may be bonded to each other to form a ring which may have one or more substituents. ] Step A of the reaction.

Description

Technical Field

[0001] The present invention relates to fluorolactone and a method for producing the same. Background Art

[0002] 2-(Difluoromethylene)-4,4,5-trifluoro-5-(trifluoromethyl)-1,3-dioxirane is used as a raw material for fluororesins.

[0003] As a method for producing perfluorobis(oxirane), a method represented by the following formula using 3,5,5,6-tetrafluoro-3,6-bis(trifluoromethyl)-1,4-dioxan-2-one as a raw material is known (for example, Patent Document 1).

[0004]

[0005] As a method for producing the above-mentioned perfluorodioxane, for example, a two-step method represented by the following formula using hexafluoropropylene oxide as a raw material is known (for example, Non-Patent Document 1).

[0006]

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Publication No. 2005-2014

[0010] Non-patent literature

[0011] 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

[0012] Technical problem to be solved by the invention

[0013] In the method for producing perfluorodioxane described in Non-Patent Document 1, two steps are necessary.

[0014] The main object of the present invention is to provide a method for producing a fluorolactone compound from hexafluoropropylene oxide or the like in one step.

[0015] Solutions for solving technical problems

[0016] The present invention includes the following aspects.

[0017] Item 1.

[0018] A method for producing a compound represented by formula (1), comprising step A of reacting a compound represented by formula (2), a compound represented by formula (3), and at least one compound (4) selected from the group consisting of a compound represented by formula (4-1) and a compound represented by formula (4-2),

[0019]

[0020] In formula (1), the two R 1 is the same as fluorine atom or fluorinated alkyl group,

[0021]

[0022] In formula (2), R 1 The meaning is the same as above,

[0023]

[0024] In formula (3),

[0025] R 31 , R 32 and R 33 are the same or different and are hydrogen atoms or alkyl groups, or R 31 , R 32 and R 33 Two of them may be bonded to each other to form a ring which may have one or more substituents,

[0026]

[0027] In formula (4-1), R 41 , R 42 , R 43 and R 44 are the same or different and are hydrogen atoms or alkyl groups, or R 41 , R 42 , R 43 and R 44 Two of them may be bonded to each other to form a ring which may have one or more substituents,

[0028]

[0029] In formula (4-2),

[0030] R 46 is a hydrogen atom, an organic group or an amino group which may have one or more substituents,

[0031] R 47 , R 48 , R 49 and R 50 are the same or different and are hydrogen atoms or alkyl groups, or R 47 and R 48 may be combined with each other to form a ring which may have one or more substituents, R 48 and R 50 may be combined with each other to form a ring which may have one or more substituents, R 49 and R 50 They may be bonded to each other to form a ring which may have one or more substituents.

[0032] Item 2.

[0033] The production method according to item 1, wherein step A is carried out in the presence of an organic solvent (the organic solvent does not contain the compound represented by the above formula (3) and the compound (4)).

[0034] Item 3.

[0035] The manufacturing method as described in item 1 or 2, wherein the above-mentioned step A is a step of generating an upper liquid layer and a lower liquid layer, and the above-mentioned manufacturing method further includes a step B of separating the upper liquid layer and the lower liquid layer.

[0036] Item 4.

[0037] The production method according to any one of items 1 to 3, wherein the compound (4) is a compound represented by the formula (4-1).

[0038] Item 5.

[0039] The production method according to any one of items 1 to 4, wherein R 41 , R 42 , R 43 and R 44 The same or different, hydrogen or C 1－10 Alkyl, or R 41 , R 42 , R 43 and R 44 Two of them may be bonded to each other to form a ring which may have one or more substituents.

[0040] Item 6.

[0041] The production method according to any one of items 1 to 5, wherein R 41 and R 42 Same or different, C 1－5 alkyl,

[0042] R 43 and R44 Same or different, C 1－5 or they are combined with each other to form a ring which may have one or more substituents.

[0043] Item 7.

[0044] The production method according to any one of items 1 to 6, wherein the compound represented by the formula (4-1) is at least one compound selected from the group consisting of N,N'-dimethylpropyleneurea, N,N'-dimethylethyleneurea and tetramethylurea.

[0045] Item 8.

[0046] A manufacturing method as described in any one of items 4 to 7, wherein in step A, the compound represented by formula (2) is supplied in the form of a gas, the amount of the compound represented by formula (2) is 70 mass % to 99.8 mass % relative to the weight of the gas, and the amount of the compound represented by formula (4-1) is 0.001 to 0.3 mol relative to 1 mol of the compound represented by formula (2).

[0047] Item 9.

[0048] The production method according to any one of items 4 to 8, wherein the step A does not contain CsF.

[0049] Item 10.

[0050] The production method according to any one of items 1 to 3, wherein the compound (4) is a compound represented by the formula (4-2).

[0051] Item 11.

[0052] The production method according to item 1 to 3 or 10, wherein R 46 C 1－4 Alkyl, 1-pyrrolidinyl, 1-piperidinyl, may be replaced by 1, 2 or 3 C 1－4 Alkyl-substituted phenyl or 2 C 1－4 Alkyl-substituted amino groups,

[0053] R 47 , R 48 , R 49 and R 50 The same or different, hydrogen or C 1－4 Alkyl, or R 47 and R 48 can combine with each other to form a pyrrolidine ring or a piperidine ring, R 48 and R 50 can combine with each other to form a pyrrolidine ring or a piperidine ring, R 49 and R 50 They may combine with each other to form a pyrrolidine ring or a piperidine ring.

[0054] Item 12.

[0055] The production method according to any one of items 1 to 3, 10 or 11, wherein the compound represented by the formula (4-2) is hexamethylphosphoric acid triamide and / or tripyrrolidinephosphine oxide.

[0056] Item 13.

[0057] A manufacturing method as described in any one of items 10 to 12, wherein in step A, the compound represented by formula (2) is supplied in the form of a gas, the amount of the compound represented by formula (2) is 90 mass % to 99.8 mass % relative to the weight of the gas, and the amount of the compound represented by formula (4-2) is 0.005 to 0.05 mol relative to 1 mol of the compound represented by formula (2).

[0058] Item 14.

[0059] A method for producing a compound represented by formula (5), comprising:

[0060] A step C of heating the compound represented by formula (1) produced in the step A or B in the presence of at least one fluorine compound (9) selected from the group consisting of a compound represented by formula (9-1), a compound represented by formula (9-2), and hydrofluoric acid or a salt thereof to produce a compound represented by formula (6);

[0061] Step D of reacting the compound represented by formula (6) with a base to produce a compound represented by formula (8); and

[0062] Step E: heating the compound represented by the formula (8) to generate the compound represented by the formula (5);

[0063]

[0064] In formula (5), R 1 is a fluorine atom or a fluorinated alkyl group,

[0065]

[0066] In formula (1), the two R 1 is the same as fluorine atom or fluorinated alkyl group,

[0067] MH n F m (9-1)

[0068] In formula (9-1), M is a metal atom, n is 0 or 1, and the sum of the atomic valence of M and n is m.

[0069] LR 91 4 F(9-2)

[0070] In formula (9-2), L is a nitrogen atom or a phosphorus atom, and R 91 Same or different, C 1－5 alkyl,

[0071]

[0072] In formula (6), R 1 The meaning is the same as above,

[0073]

[0074] In formula (8), R 81 is a group corresponding to the base, R 1 The meaning is the same as above.

[0075] Item 15.

[0076] The manufacturing method as described in item 14, wherein

[0077] Instead of the above step D, it comprises:

[0078] Step D1 of reacting the compound represented by the above formula (6) with water or an alkanol to produce a compound represented by the formula (7); and

[0079] Step D2 of reacting the compound represented by the formula (7) with a base to produce the compound represented by the above formula (8),

[0080]

[0081] In formula (7), R 71 is a hydrogen atom or an alkyl group, R 1 The meaning is the same as above.

[0082] Item 16.

[0083] The production method according to item 15, further comprising a step D1a of purifying the product of the step D1 to obtain the compound represented by the formula (7).

[0084] Item 17.

[0085] The manufacturing method as described in item 14, wherein

[0086] Instead of the above steps D and E, the method comprises:

[0087] Step F is to heat the compound represented by the above formula (6) in the presence of a base to produce the compound represented by the above formula (5).

[0088] Item 18.

[0089] A composition containing a compound represented by formula (1), wherein:

[0090] 0.00001 to 1 part by mass of a compound represented by formula (10) and / or 0.00001 to 1 part by mass of a compound represented by formula (11) relative to 100 parts by mass of the compound represented by formula (1),

[0091]

[0092] In formula (1), the two R 1 is the same as fluorine atom or fluorinated alkyl group,

[0093]

[0094] In formula (10), R 41 , R 42 , R 43 and R 44 are the same or different and are hydrogen atoms or alkyl groups, or R 41 , R 42 , R 43 and R 44 Two of them may be bonded to each other to form a ring which may have one or more substituents,

[0095]

[0096] In formula (11),

[0097] R 46 is a hydrogen atom, an organic group or an amino group which may have one or more substituents,

[0098] R 47 , R 48 , R 49 and R 50 are the same or different and are hydrogen atoms or alkyl groups, or R 47 and R 48 may be combined with each other to form a ring which may have one or more substituents, R 48 and R 50 may be combined with each other to form a ring which may have one or more substituents, R 49 and R 50 They may be bonded to each other to form a ring which may have one or more substituents.

[0099] Item 19.

[0100] The composition as described in item 18, wherein

[0101] With respect to 100 parts by mass of the compound represented by the above formula (1),

[0102] The content of the compound represented by the above formula (10) is 0.00001 to 0.5 parts by mass,

[0103] The content of the compound represented by the above formula (11) is 0.00001 to 0.5 parts by mass.

[0104] Effects of the Invention

[0105] According to the present invention, a method for producing a fluorolactone compound from hexafluoropropylene oxide or the like in one step can be provided. According to the present invention, a novel fluorobis(oxirane) compound and a method for producing the same can be provided. According to the present invention, the production rate of the fluorolactone compound in step A is high, thereby simplifying the purification of the fluorolactone, or the reaction solution obtained in step A can be directly used in other reactions (e.g., synthesis of fluorobis(oxirane) compounds) using the fluorolactone compound as a raw material or as an intermediate. DETAILED DESCRIPTION

[0106] The above summary of the present invention is not intended to describe each disclosed embodiment or every implementation of the present invention.

[0107] The following description of the present invention more specifically illustrates exemplary embodiments.

[0108] Several sections of the disclosure provide guidance through examples, which examples can be used in various combinations.

[0109] In each case, the illustrated groups can function as non-exclusive and representative groups.

[0110] All literature, patents and patent applications cited in this specification can be cited in the specification by direct reference.

[0111] the term

[0112] Unless otherwise specified, symbols and abbreviations in the present specification can be understood as having the meanings generally used in the technical field to which the present invention relates, according to the context of the present specification.

[0113] In this specification, the phrase "comprising..." is used to include "consisting essentially of..." and the phrase "consisting of...".

[0114] Unless otherwise specified, the steps, treatments or operations described in this specification can be performed at room temperature. In this specification, room temperature can refer to a temperature within the range of 10 to 40°C.

[0115] In this specification, the expression "C n－m"(Here, 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.

[0116] In the present specification, unless otherwise specified, examples of the "halogen atom" can include fluorine, chlorine, bromine and iodine.

[0117] In the present specification, unless otherwise specified, the "ring which may have one or more substituents" in formula (3) may include a pyrrolidine ring, a piperidine ring, a pyrrolidone ring, and a piperidone ring. Specific examples thereof may include a 1-pyrrolidine ring, a 1-piperidine ring, a 2-pyrrolidone ring, and a 2-piperidone ring.

[0118] In the present specification, unless otherwise specified, the "ring which may have one or more substituents" in formula (4-1) may include a tetrahydropyrimidinone ring, an imidazolidinone ring, a pyrrolidine ring, and a piperidine ring. Specific examples thereof may include a tetrahydropyrimidin-2-one ring, a 2-imidazolidinone ring, a 1-pyrrolidine ring, and a 1-piperidine ring.

[0119] In the present specification, unless otherwise specified, the "ring which may have one or more substituents" in formula (4-2) may include a diazaphosphotinyl oxide ring, a pyrrolidine ring, and a piperidine ring. Specific examples thereof may include a diazaphosphotinyl-2-oxide ring, a 1-pyrrolidine ring, and a 1-piperidine ring.

[0120] 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 can 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. In addition, two or more substituents may be the same or different from each other.

[0121] In this specification, unless otherwise specified, an "organic group" refers to a group formed by removing one hydrogen atom from an organic compound. As can be understood from this, an organic group has one or more carbon atoms.

[0122] In this specification, unless otherwise specified, "organic group" includes

[0123] (1) hydrocarbon groups, and

[0124] (2) A hydrocarbon group having one or more heteroatoms (e.g., nitrogen, oxygen, sulfur, phosphorus, or halogen).

[0125] In this specification, unless otherwise specified, the term "hydrocarbon group" refers to a group consisting only of carbon and hydrogen. A hydrocarbon group may also be referred to as a hydrocarbyl group.

[0126] In this specification, unless otherwise specified, examples of the "hydrocarbon group" include:

[0127] (1) an aliphatic hydrocarbon group which may be substituted with one or more aromatic hydrocarbon groups (e.g., benzyl) and

[0128] (2) An aromatic hydrocarbon group which may be substituted with one or more aliphatic hydrocarbon groups.

[0129] An aromatic hydrocarbon group may also be referred to as an aryl group.

[0130] In the present specification, unless otherwise specified, the "aliphatic hydrocarbon group" may have a linear, branched, or cyclic structure, or a combination thereof.

[0131] In the present specification, unless otherwise specified, the "aliphatic hydrocarbon group" may be saturated or unsaturated.

[0132] 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.

[0133] In the present specification, unless otherwise specified, examples of the "alkyl group" include 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, and other linear or branched alkyl groups having 1 to 10 carbon atoms.

[0134] In the present specification, unless otherwise specified, examples of the “alkenyl group” include linear or branched alkenyl groups having 1 to 10 carbon atoms, 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.

[0135] In the present specification, unless otherwise specified, examples of the “alkynyl group” include linear or branched alkynyl groups having 2 to 6 carbon atoms, 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.

[0136] In the present specification, unless otherwise specified, examples of the "cycloalkyl group" include cycloalkyl groups having 3 to 10 carbon atoms, and specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and adamantyl.

[0137] In the present specification, unless otherwise specified, examples of the "aromatic hydrocarbon group" (aryl group) include aromatic hydrocarbon groups having 6 to 14 carbon atoms (aryl groups having 6 to 14 carbon atoms), and specific examples thereof include phenyl, naphthyl, phenanthrenyl, anthracenyl, and pyrenyl.

[0138] In this specification, unless otherwise specified, examples of "aromatic hydrocarbon ring" include C 6－14 An aromatic hydrocarbon ring, and specific examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring.

[0139] In this specification, unless otherwise specified, "alkoxy" can be RO-[wherein R is an alkyl group (e.g., C 1－11 alkyl).] represented by the group [e.g. C 1－11 alkoxy (e.g., methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, pentyloxy and hexyloxy)].

[0140] In this specification, unless otherwise specified, "fluoroalkyl" refers to a group obtained by replacing one or more hydrogen atoms on an alkyl group with fluorine atoms, and also includes a perfluoroalkyl group obtained by replacing all hydrogen atoms of an alkyl group. 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.

[0141] In the present specification, unless otherwise specified, the "amino group which may have one or more substituents" may be an amino group, a mono-C 1－10 Alkylamino, di-C 1－10 Alkylamino (two alkyl groups may be the same or different, or may be combined to form a ring). Specific examples thereof, unless otherwise specified, include amino, methylamino, ethylamino, propylamino, isopropylamino, dimethylamino, diethylamino, dipropylamino, diisopropylamino, ethylmethylamino, methylpropylamino, methylisopropylamino, ethylpropylamino, pyrrolidinyl, piperidinyl, and ethylisopropylamino.

[0142] Method for producing a compound represented by formula (1)

[0143] One embodiment of the present invention is a method for producing a compound represented by formula (1) (hereinafter sometimes referred to as compound (1)).

[0144]

[0145] [Wherein, 2 R 1 is the same as fluorine atom or fluorinated alkyl group.]

[0146] The method includes a step A of reacting a compound represented by formula (2) (sometimes referred to as compound (2) in the present specification), a compound represented by formula (3) (sometimes referred to as compound (3) in the present specification), and at least one compound (4) selected from the group consisting of a compound represented by formula (4-1) (sometimes referred to as compound (4-1) in the present specification, and a compound represented by formula (4-2) (sometimes referred to as compound (4-2) in the present specification).

[0147]

[0148] [Where R 1 has the same meaning as above.]

[0149]

[0150] [Wherein,

[0151] R 31 , R 32 and R 33 are the same or different and are hydrogen atoms or alkyl groups, or R 31 , R 32 and R 33 Two of them are bonded to each other to form a ring which may have one or more substituents.]

[0152]

[0153] [Where R 41 , R 42 , R 43 and R 44 are the same or different and are hydrogen atoms or alkyl groups, or R 41 , R 42 , R 43 and R 44 Two of them may be bonded to each other to form a ring which may have one or more substituents.]

[0154]

[0155] [Wherein,

[0156] R 46is a hydrogen atom, an organic group or an amino group which may have one or more substituents,

[0157] R 47 , R 48 , R 49 and R 50 are the same or different and are hydrogen atoms or alkyl groups, or R 47 and R 48 may be combined with each other to form a ring which may have one or more substituents, R 48 and R 50 may be combined with each other to form a ring which may have one or more substituents, R 49 and R 50 They may combine with each other to form a ring which may have one or more substituents.]

[0158] R 1 Preferably, a fluorine atom or a C 1－10 A fluorinated alkyl 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.

[0159] Preferred specific examples of the compound (2) include hexafluoropropylene oxide, 2,2,3-trifluoro-3-(perfluoroethyl)ethylene oxide, and 2,2,3-trifluoro-3-(perfluoropropyl)ethylene oxide.

[0160] Preferably:

[0161] R 31 , R 32 and R 33 The same or different, hydrogen or C 1－5 Alkyl, or

[0162] R 31 A hydrogen atom or C 1－5 Alkyl, R 32 and R 33 The carbon atoms on the ring may have one or two substituents, and the substituents may be the same or different when they are methyl or ethyl.

[0163] R 31 and R 32 The carbon atoms on the ring may have one or two substituents, and the substituents may be the same or different when they are methyl or ethyl. 33 A hydrogen atom or C 1－5 alkyl.

[0164] More preferably:

[0165] R 31 , R 32 and R 33 The same or different, hydrogen or C 1－3 Alkyl, or

[0166] R 31 A hydrogen atom or C 1－3 Alkyl, R 32 and R 33 Combined to form a pyrrolidine ring or a piperidine ring, or

[0167] R 31 and R 32 Combined to form a pyrrolidone ring or a piperidone ring, R 33 A hydrogen atom or C 1－3 alkyl.

[0168] More preferably:

[0169] R 31 , R 32 and R 33 The same or different, hydrogen or C 1－3 Alkyl, or

[0170] R 31 A hydrogen atom or C 1－3 Alkyl, R 32 and R 33 Combine to form a pyrrolidine ring, or

[0171] R 31 and R 32 Combined to form a pyrrolidone ring, R 33 C 1－3 alkyl.

[0172] Particularly preferred are:

[0173] R 31 , R 32 and R 33 are the same or different and are hydrogen atoms, methyl groups or ethyl groups, or

[0174] R 31 is a hydrogen atom, a methyl group or an ethyl group, R 32 and R 33 Combine to form a pyrrolidine ring, or

[0175] 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.

[0176] Preferred specific examples of compound (3) include formamide, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone.

[0177] For example,

[0178] R 41 , R 42 , R 43 and R 44 The same or different, hydrogen or C 1－10 Alkyl, or R 41 , R 42 , R 43 and R 44 In addition, as will be appreciated by those skilled in the art, when two groups are combined to form a ring (e.g., a pyrrolidine ring), the remaining group is as defined above, i.e., a hydrogen atom or a C 1－10 In the present specification, the same also applies to the description of the ring formed by two groups in the formulae (3), (4-1) and (4-2).

[0179] In addition, for example,

[0180] R 41 and R 42 Same or different, C 1－5 alkyl,

[0181] R 43 and R 44 Same or different, C 1－5 or they are combined with each other to form a ring which may have one or more substituents.

[0182] Preferably:

[0183] R 41 , R 42 , R 43 and R 44 The same or different, hydrogen or C 1－5 Alkyl, or

[0184] R 41 and R 42 The same or different, hydrogen or C 1－5 Alkyl, R 43 and R 44 The tetrahydropyrimidinone ring or the imidazolidinone ring may have one or two substituents on the carbon atoms on the ring, and the substituents are methyl or ethyl.

[0185] More preferably:

[0186] R41 , R 42 , R 43 and R 44 The same or different, hydrogen or C 1－3 Alkyl, or

[0187] R 41 and R 42 The same or different, hydrogen or C 1－3 Alkyl, R 43 and R 44 Combined with each other to form a tetrahydropyrimidinone ring or an imidazolinone ring.

[0188] More preferably:

[0189] R 41 , R 42 , R 43 and R 44 are the same or different and are hydrogen atoms, methyl groups or ethyl groups, or

[0190] R 41 and R 42 are the same or different and are hydrogen atoms, methyl groups or ethyl groups, R 43 and R 44 Combined with each other to form a tetrahydropyrimidinone ring or an imidazolinone ring.

[0191] Particularly preferred are:

[0192] R 41 , R 42 , R 43 and R 44 is methyl or ethyl, or R 41 and R 42 The same is methyl or ethyl, R 43 and R 44 Combined with each other to form a tetrahydropyrimidinone ring.

[0193] Preferred specific examples of the compound (4-1) include N,N′-dimethylpropylene urea, N,N′-dimethylethylene urea, tetraethyl urea, and tetramethyl urea.

[0194] For example,

[0195] R 46 is a hydrogen atom, an organic group or an amino group which may have one or more substituents,

[0196] R 47 , R 48 , R 49 and R 50 are the same or different and are hydrogen atoms or alkyl groups, or R 47 and R 48may be combined with each other to form a ring which may have one or more substituents, R 48 and R 50 may be combined with each other to form a ring which may have one or more substituents, R 49 and R 50 They may be bonded to each other to form a ring which may have one or more substituents.

[0197] Preferably:

[0198] R 46 C 1－5 Alkyl, 1-pyrrolidinyl, 1-piperidinyl, may be replaced by 1, 2 or 3 C 1－5 Alkyl-substituted phenyl may be substituted with 2 C 1－5 Alkyl-substituted amino groups,

[0199] R 47 , R 48 , R 49 and R 50 The same or different, hydrogen or C 1－4 Alkyl, or R 47 and R 48 can combine with each other to form a pyrrolidine ring or a piperidine ring, R 47 and R 49 can combine with each other to form a pyrrolidine ring or a piperidine ring, R 49 and R 50 They can be combined to form a pyrrolidine ring or a piperidine ring. In addition, in this case, the phenyl group is 2 or 3 C 1－4 When substituted with an alkyl group, the alkyl groups may be the same or different. The two C 1－4 The alkyl groups may be the same or different.

[0200] Any one of the following (1) to (3) is more preferable.

[0201] (1)R 46 C 1－4 Alkyl, can be 1, 2 or 3 C 1－4 Alkyl-substituted phenyl, 2 C 1－4 Alkyl-substituted amino, or 1-pyrrolidinyl, R 47 and R 48 Combined with each other to form a pyrrolidine ring, R 49 and R 50 Combined with each other to form a pyrrolidine ring,

[0202] (2)R 46 C 1－4 Alkyl, can be 1, 2 or 3 C 1－4 Alkyl-substituted phenyl, 2 C 1－4Alkyl-substituted amino, or 1-piperidinyl, R 47 and R 48 Combined with each other to form a piperidine ring, R 49 and R 50 Combined with each other to form a piperidine ring,

[0203] (3)R 46 C 1－4 Alkyl, may be 1, 2 or 3 C 1－4 Alkyl-substituted phenyl, 2 C 1－4 Alkyl substituted amino group, R 47 , R 48 , R 49 and R 50 The same or different, hydrogen or C 1－4 Alkyl, or R 48 and R 50 Combined with each other to form a pyrrolidine ring or a piperidine ring.

[0204] More preferably, it is any one of the following (1) to (5).

[0205] (1)R 46 Can be 1, 2 or 3 C 1－4 Alkyl-substituted phenyl, 2 C 1－4 Alkyl-substituted amino, or 1-pyrrolidinyl, R 47 and R 48 Combined with each other to form a pyrrolidine ring, R 49 and R 50 Combined with each other to form a pyrrolidine ring,

[0206] (2)R 46 Can be 1, 2 or 3 C 1－4 Alkyl-substituted phenyl, 2 C 1－4 Alkyl-substituted amino, or 1-piperidinyl, R 47 and R 48 Combined with each other to form a piperidine ring, R 49 and R 50 Combined with each other to form a piperidine ring,

[0207] (3)R 46 For the same 2 C 1－4 Alkyl substituted amino, -NR 47 R 48 and -NR 49 R 50 is the same group as the amino group,

[0208] (4)R 46 is phenyl, R 47 , R 48 , R49 and R 50 Same or different, C 1－4 alkyl,

[0209] (5)R 46 C 1－4 Alkyl, R 47 , R 48 , R 49 and R 50 Same or different, C 1－4 Alkyl, or R 48 and R 50 Combined with each other to form a pyrrolidine ring.

[0210] In particular, any one of the following (1) to (6) is preferred.

[0211] (1)R 46 is 1-pyrrolidinyl, R 47 and R 48 Combined with each other to form a pyrrolidine ring, R 49 and R 50 Combined with each other to form a pyrrolidine ring,

[0212] (2)R 46 is 1-piperidinyl, R 47 and R 48 Combined with each other to form a piperidine ring, R 49 and R 50 Combined with each other to form a piperidine ring,

[0213] (3)R 46 is dimethylamino, diethylamino, dipropylamino or diisopropylamino, -NR 47 R 48 and -NR 49 R 50 is the same group as the amino group,

[0214] (4)R 46 is phenyl, R 47 , R 48 , R 49 and R 50 is identically methyl, ethyl, propyl or isopropyl,

[0215] (5)R 46 is methyl or ethyl, R 47 and R 49 is methyl, ethyl, propyl or isopropyl, R 48 and R 50 Combined with each other to form a pyrrolidine ring,

[0216] (6)R 46 is methyl or ethyl, R47 and R 48 , R 49 and R 50 Equivalently methyl, ethyl, propyl or isopropyl.

[0217] Preferred specific examples of compound (4-2) include hexamethylphosphoric acid triamide (sometimes referred to as HMPA in this specification), 1,2,3-trimethyl-1,3,2-diazaphosphaidine 2-oxide, methylbis(dimethylamino)phosphine oxide, phenylbis(dimethylamino)phosphine oxide, tripyrrolidinylphosphine oxide, and methylbis(diethylamino)phosphine oxide.

[0218] In one embodiment of the present invention, a preferred specific example of compound (4) is at least one compound selected from N,N'-dimethylpropylene urea, N,N'-dimethylethylene urea, tetramethyl urea, tetraethyl urea, 1,2,3-trimethyl-1,3,2-diazaphosphidine 2-oxide, methylbis(dimethylamino)phosphine oxide, phenylbis(dimethylamino)phosphine oxide, tripyrrolidinophosphine oxide and methylbis(diethylamino)phosphine oxide.

[0219] Process A

[0220] In step A, the compound (2) is preferably supplied to the reaction system in the form of a gas. The amount of the compound (2) in the gas may be, for example, in the range of 70% to 99.8% by mass, preferably in the range of 90% to 99.8% by mass, more preferably in the range of 92% to 99.8% by mass, and particularly preferably in the range of 95% to 99.8% by mass, relative to the weight of the gas.

[0221] The amount of compound (3) used in step A is preferably in the range of 0.05 to 10 mol, more preferably in the range of 0.08 to 5 mol, and even more preferably in the range of 0.1 to 2 mol, relative to 1 mol of compound (2).

[0222] The amount of compound (4) used in step A is preferably in the range of 0.001 to 0.3 mol, more preferably 0.005 to 0.1 mol, and even more preferably 0.005 to 0.05 mol, relative to 1 mol of compound (2).

[0223] When compound (4-1) is used in step A, the amount of compound (4-1) is preferably in the range of 0.001 to 0.3 mol, more preferably 0.005 to 0.1 mol, and even more preferably 0.005 to 0.05 mol, based on 1 mol of compound (2).

[0224] When compound (4-2) is used in step A, the amount of compound (4-2) is preferably in the range of 0.005 to 0.05 mol, more preferably in the range of 0.005 to 0.045 mol, and even more preferably in the range of 0.005 to 0.04 mol relative to 1 mol of compound (2). By setting the amount of compound (4-2) used within this range, the selectivity of compound 1 is greatly improved, the yield and purity of compound 1 are improved, and the purification of compound 1 becomes simple. In addition, the product (e.g., product liquid) purified in step A can also be used directly for the synthesis of compound 5.

[0225] Step A is preferably carried out in the presence of an organic solvent. In step A, compounds (3) and (4) are considered to act as reactants in step A. The organic solvent in step A does not include compounds (3) and (4).

[0226] Examples of the organic solvent include aromatic solvents, ester solvents, ketone solvents, saturated hydrocarbon solvents, nitrile solvents, ether solvents, sulfoxide solvents, and halogenated hydrocarbon solvents. The organic solvent may be used alone or in combination of two or more.

[0227] Preferred examples of the organic solvent include ether solvents, ester solvents, halogenated hydrocarbon solvents, and nitrile solvents.

[0228] Preferred specific examples of the aromatic solvent include benzene, toluene, and xylene.

[0229] Preferred 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.

[0230] Preferred specific examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

[0231] Preferred specific examples of the saturated hydrocarbon solvent include n-pentane, n-hexane, cyclohexane, and n-heptane.

[0232] Preferred specific examples of the nitrile solvent include 1,4-dicyanobutane, acetonitrile, and benzonitrile.

[0233] Preferred 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, 1,2-dimethoxyethane, and crown ether.

[0234] Preferred specific examples of the sulfoxide-based solvent include dimethyl sulfoxide and sulfolane.

[0235] Preferred specific examples of the halogenated hydrocarbon solvent include dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,2-dichlorobenzene, chlorobenzene, and perfluorohexane.

[0236] Preferred 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, perfluorohexane, and acetonitrile.

[0237] The amount of the organic solvent used in step A can be set to an amount that can function as a solvent based on common technical knowledge, 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 even more preferably in the range of 0.1 to 10 mol, relative to 1 mol of compound (2).

[0238] 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 even more preferably in the range of -20 to 30°C. When the reaction temperature of step A is low, the selectivity of compound (1) tends to increase. When the reaction temperature of step A is high, the reactivity tends to increase.

[0239] The reaction time of step A is preferably within a range of 0.5 to 48 hours, more preferably within a range of 0.5 to 24 hours, and even more preferably within a range of 0.5 to 12 hours.

[0240] The reaction in step A may be carried out in the presence or absence of an inert gas (eg, nitrogen), but is preferably carried out in the absence of an inert gas.

[0241] Step A can be carried out under reduced pressure, atmospheric pressure or pressurized conditions.

[0242] Step A can be carried out by reacting Compound (2), Compound (3) and Compound (4) in an organic solvent. Preferably, Compound (3), Compound (4) and an organic solvent are mixed and cooled (eg, -10°C) and then Compound (2) is added thereto.

[0243] The compound (1) produced in step A can be isolated or purified as desired by conventional methods such as extraction, dissolution, concentration, precipitation, dehydration, adsorption, distillation, rectification, chromatography, or a combination thereof.

[0244] Step A preferably does not contain CsF (cesium fluoride). More preferably, step A does not contain at least one fluorine compound (9) selected from the group consisting of a compound represented by formula (9-1) (sometimes referred to as compound (9-1) in this specification), a compound represented by formula (9-2) (sometimes referred to as compound (9-2) in this specification, and hydrofluoric acid or a salt thereof (sometimes referred to as compound (9) in this specification).

[0245] MH n Fm (9-1)

[0246] [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.]

[0247] LR 91 4 F(9-2)

[0248] [wherein, L is a nitrogen atom or a phosphorus atom, R 91 Same or different, C 1－5 alkyl.]

[0249] For example, M is an alkali metal atom and n is 0 or 1, or M is an alkaline earth metal atom and n is 0.

[0250] For example, 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.

[0251] For example, 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.

[0252] Specific examples of the compound (9-1) are cesium fluoride, potassium hydrogen fluoride, calcium fluoride, sodium fluoride, potassium fluoride and sodium hydrogen fluoride.

[0253] For example, L is a nitrogen atom or a phosphorus atom, R 91 Same or different, C 1－4 alkyl.

[0254] For example, L is a nitrogen atom or a phosphorus atom, R 91 Same as C 1－4 alkyl.

[0255] For example, L is a nitrogen atom or a phosphorus atom, R 91 The same straight-chain C 1－4 alkyl.

[0256] For example, L is a nitrogen atom or a phosphorus atom, R 91 Equivalently methyl, ethyl or n-butyl.

[0257] Specific examples of the compound (9-2) include tetrabutylammonium fluoride, tetraethylammonium fluoride, tetramethylammonium fluoride, tetrabutylphosphonium fluoride, and triethylmethylammonium fluoride.

[0258] The salt of hydrofluoric acid includes amine salts, ammonium salts, imidazolium salts, pyridinium salts, phosphonium salts and the like. The salt may contain one or more substituents, and when there are multiple substituents, they may be the same or different.

[0259] The amine salt of hydrofluoric acid may be substituted. The number of substituents is, for example, 1 to 3, 2, 3, or 3. When there are multiple substituents, they may be the same or different. Examples of the substituent include C 1－10 Alkyl, C 1－5 Alkyl, C 1－4 alkyl.

[0260] Examples of amine salts of hydrofluoric acid include tri-C 1－4 Alkylamine hydrofluoride (HF － The number can be any integer from 1 to 7. ).

[0261] Specific examples of amine salts of hydrofluoric acid include trimethyl hydrofluoride (HF － The number of can be any integer from 1 to 7, for example, 3, 4, or 5. ), triethylamine hydrofluoride (HF － The number may be any integer from 1 to 7, for example, 3, 4, or 5. ).

[0262] When the ammonium salt of hydrofluoric acid is substituted, the number of substituents is, for example, 1 to 4, 2 to 4, 3, 4, or 4. When there are multiple substituents, they may be the same or different. Examples of the substituent include C 1－10 Alkyl, which can be C 1－5 Alkyl, C 1－4 alkyl.

[0263] Examples of ammonium salts of hydrofluoric acid include ammonium fluoride, ammonium bifluoride, tetra-C 1－4 Alkyl ammonium fluoride.

[0264] Specific examples of the ammonium salt of hydrofluoric acid include ammonium fluoride, ammonium hydrogen fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, and tetrabutylammonium fluoride.

[0265] The imidazolium salt of hydrofluoric acid may have a substituent on the nitrogen atom on the imidazolium ring. The number of substituents is, for example, 1 to 3, 2, or 3 or 2. When there are multiple substituents, they may be the same or different. As substituents, for example, C 1－10 Alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl), cyclohexyl, vinyl, or allyl. The substituent may be C 1－3 alkyl.

[0266] Specific examples of the imidazolium salt of hydrofluoric acid include 1-methyl-3-methylimidazolium fluoride and 1-ethyl-3-methylimidazolium fluoride.

[0267] The pyridinium salt of hydrofluoric acid may be substituted, and the number of substituents is, for example, 1 to 3, 1 or 2. When there are multiple substituents, they may be the same or different. Examples of the substituent include C 1－10Alkyl. The substituent may be C 1－5 Alkyl, can also be C 1－4 alkyl.

[0268] Specific examples of pyridinium salts of hydrofluoric acid include pyridinium poly(hydrogen fluoride) (HF － The number can be any integer from 1 to 9, for example, 1 or 9. ).

[0269] The phosphonium salt of hydrofluoric acid may be substituted, and the number of substituents is, for example, 1 to 4, 3, 4, or 4. Examples of the substituent include C 1－10 An alkyl group, a phenyl group which may have a substituent, or a benzyl group which may have a substituent. The substituent may be C 1－5 Alkyl, can also be C 1－4 alkyl.

[0270] 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.

[0271] In one embodiment of the present invention, a specific example of compound (9) is at least one fluorine compound selected from cesium fluoride, potassium bifluoride, calcium fluoride, sodium fluoride, potassium fluoride, sodium bifluoride, tetrabutylammonium fluoride, tetraethylammonium fluoride, tetramethylammonium fluoride, tetrabutylphosphonium fluoride, triethylmethylammonium fluoride, triethylamine 3 hydrofluoride, triethylamine 5 hydrofluoride, triethylamine 7 hydrofluoride, pyridinium poly(hydrogen fluoride), pyridine 1 hydrofluoride, pyridinium poly(hydrogen fluoride), pyridine 9 hydrofluoride, ammonium bifluoride and ammonium fluoride.

[0272] In the conventional method of producing compound (1) by reacting N,N-dimethylformamide with hexafluoropropylene oxide at 0°C (first reaction), the reaction is then heated at 140°C in diethylene glycol dimethyl ether in the presence of cesium fluoride (second reaction). In the first reaction, a large amount of difluoroamine is produced as a by-product. Difluoroamine converts the target compound (1) into other compounds, and therefore, it is necessary to capture and remove difluoroamine with HCl gas that is harmful to the human body before the second reaction. In step A of the present invention, by using a solvent, difluoroamine is transferred to the solvent, and contact between difluoroamine and compound (1) is suppressed, so that it is not necessary to capture difluoroamine with HCl gas.

[0273] In the method disclosed in Patent Document 1, it is difficult to operate and dangerous fluorine gas is used in the production of 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 and is not easy to purify. In contrast, in step A of the present invention, fluorine gas may not be used, and the resulting liquid obtained in step A is easy to purify, for example, by liquid separation.

[0274] Process B

[0275] The method for producing the compound represented by formula (1) of the present invention may further include step B of liquid separation in addition to step A. The reaction solution generated in step A can be obtained as two layers, an upper liquid layer and a lower liquid layer, and one layer (preferably the lower liquid layer) contains compound (1). Therefore, by liquid separation of the reaction solution, a liquid layer containing the target compound (1) can be easily obtained.

[0276] The method for separating compound (1) from the liquid layer may be conventional methods such as extraction, dissolution, concentration, precipitation, dehydration, adsorption, distillation, rectification, chromatography, or a combination thereof. Since the liquid layer containing compound (1) obtained in step B contains few impurity compounds having a boiling point close to that of compound (1), compound (1) can be easily obtained by distilling the liquid layer, and the liquid layer can be directly used for the synthesis of compound (5).

[0277] Method for producing the compound represented by formula (5)

[0278] 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).

[0279]

[0280] [Where R 1 is a fluorine atom or a fluorinated alkyl group.]

[0281] The method includes:

[0282] Step C of heating the compound represented by the formula (1) produced in the step A or B in the presence of at least one fluorine compound (9) selected from the group consisting of a compound represented by the formula (9-1), a compound represented by the formula (9-2), and hydrofluoric acid or a salt thereof (sometimes referred to as compound (9) in the present specification) to produce a compound represented by the formula (6) (sometimes referred to as compound (6) in the present specification);

[0283] 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

[0284] Step E: heating the compound represented by formula (8) (may be referred to as compound (8) in this specification) to produce the compound represented by formula (5).

[0285] MH n F m (9-1)

[0286] [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.]

[0287] LR 91 4 F(9-2)

[0288] [wherein, L is a nitrogen atom or a phosphorus atom, R 91 Same or different, C 1－5 alkyl.]

[0289]

[0290] [Where R 1 has the same meaning as above.]

[0291]

[0292] [Where R 81 is a group corresponding to the above base, R 1 has the same meaning as above.]

[0293] Compound (8) is a carboxylate salt of compound (6) corresponding to base (d).

[0294] 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.

[0295] In the present specification, step C, step D, step E and step F can be carried out 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 step A or B is used as a raw material in step C. The publications are incorporated herein by reference.

[0296] Process C

[0297] In step C, the compound (1) produced in step A or B is isomerized by heating in the presence of compound (9) to produce compound (6).

[0298] In step C, the compound (1) produced in step A or B may be isolated and used, or the liquid layer of the reaction solution obtained in step B containing compound (1) may be used.

[0299] The details of the compound (9) in step C are applicable to the details of the compound (9) in step (A) unless otherwise specified.

[0300] The amount of compound (9) 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, relative to 1 mol of compound (1).

[0301] Step C is preferably carried out in an organic solvent. Examples and preferred examples of the organic solvent are the same as those described above. Preferred 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.

[0302] The amount of the organic solvent used in step C can be set to an amount that can function as a solvent based on common technical knowledge and the like.

[0303] The reaction temperature in step C is preferably within a range of 50 to 300°C, more preferably within a range of 50 to 200°C, and even more preferably within a range of 100 to 180°C.

[0304] 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.

[0305] The compound (6) produced in step C can be isolated or purified as desired by conventional methods such as extraction, dissolution, concentration, precipitation, dehydration, adsorption, distillation, rectification, chromatography, or a combination thereof.

[0306] Process D

[0307] 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).

[0308] The base (d) is, for example, at least one selected from (1) alkali or alkaline earth metals, acetates, carbonates, bicarbonates, phosphates, hydrogenphosphates, alkoxides, hydroxide salts, hydride salts, ammonium salts or amide salts, (2) alkali metals and (3) amines.

[0309] Examples of the alkoxide include sodium methoxide, sodium ethoxide, sodium butoxide, potassium methoxide, potassium ethoxide, potassium butoxide, lithium methoxide, and lithium ethoxide.

[0310] Examples of hydroxide salts include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, and barium hydroxide.

[0311] Examples of hydride salts include sodium hydride, potassium hydride, lithium hydride and calcium hydride.

[0312] Examples of alkali metals include sodium, potassium and lithium.

[0313] Examples of the amine include aliphatic amines, alicyclic amines, aromatic amines, and heterocyclic amines. The amine may preferably be a tertiary amine.

[0314] 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.

[0315] The base (d) is more preferably at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, potassium hydrogen carbonate, sodium hydrocarbon, potassium carbonate and sodium carbonate.

[0316] Step D is preferably carried out in an organic solvent. Examples and preferred examples of the organic solvent are the same as those described above. Preferred 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.

[0317] 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).

[0318] The amount of the organic solvent used in step D can be set to an amount that can function as a solvent based on common technical knowledge and the like.

[0319] The reaction temperature in step D is preferably within a range of -50 to 120°C, more preferably within a range of -20 to 100°C, and even more preferably within a range of -10 to 70°C.

[0320] 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.

[0321] The compound (8) produced in step D can be isolated or purified as desired by conventional methods such as extraction, dissolution, concentration, precipitation, dehydration, adsorption, distillation, rectification, chromatography, or a combination thereof.

[0322] Process E

[0323] In step E, compound (8) is heated to generate compound (5) by thermal decomposition. Compound (5) is useful as an intermediate for producing a raw material of a resin material.

[0324] Step E can be carried out in an organic solvent or in the absence of a solvent. Examples and preferred examples of the organic solvent are the same as those described above. Preferred 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.

[0325] The amount of the organic solvent used in step E can be set to an amount that can function as a solvent based on common technical knowledge and the like.

[0326] 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 even more preferably in the range of 100 to 200° C. when a solvent is contained. When no solvent is contained, the reaction temperature is preferably in the range of 100 to 400° C., more preferably in the range of 150 to 400° C., and even more preferably in the range of 150 to 350° C.

[0327] The reaction time of step E is preferably within a range of 0.1 to 24 hours, more preferably within a range of 0.1 to 12 hours, and even more preferably within a range of 0.1 to 6 hours.

[0328] The reaction in step E may be carried out in the presence or absence of an inert gas (eg, nitrogen), but is preferably carried out in the absence of an inert gas.

[0329] Step E can be carried out under reduced pressure, atmospheric pressure or pressurized conditions.

[0330] The compound (5) produced in step E can be isolated or purified as desired by conventional methods such as extraction, dissolution, concentration, precipitation, dehydration, adsorption, distillation, rectification, chromatography, or a combination thereof.

[0331] One embodiment of the present invention is a method for producing the compound represented by the above formula (5), wherein the method includes replacing the above step D with:

[0332] Step D1 of reacting the compound represented by the above formula (6) with water or an alkanol to produce a compound represented by the formula (7) (sometimes referred to as compound (7) in this specification); and

[0333]

[0334] [Where R 71 is a hydrogen atom or an alkyl group, R 1 has the same meaning as above.]

[0335] 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).

[0336] 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.

[0337] Process D1

[0338] In step D1, compound (6) is reacted with water or an alkanol to be converted into the corresponding carboxylic acid or alkyl ester to produce compound (7).

[0339] In step D1, compound (6) may be isolated, or the product liquid containing compound (6) produced in step C may be used directly. The use of the product liquid is preferred because it has the advantage that purification of compound (6) is not required.

[0340] The alkanol is preferably a linear or branched C 1－10 Alkanol, more preferably a straight chain or branched chain C 1－5 Alkanol, more preferably a straight-chain or branched C 1－4 The alkanol is particularly preferably methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol or tert-butanol, and more particularly preferably methanol or ethanol.

[0341] The amount of water, alkanol, 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, and even more preferably 0.5 to 10 mol, based on 1 mol of compound (6).

[0342] In step D1, in addition to water and the above-mentioned alkanol, other organic solvents can also be used. Examples and preferred examples of organic solvents are the same as 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 can be preferably 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).

[0343] The reaction temperature in step D1 is preferably within a range of -50 to 50°C, more preferably within a range of -20 to 30°C, and even more preferably within a range of -20 to 20°C.

[0344] The reaction time of step D1 is preferably within a range of 0.1 to 24 hours, more preferably within a range of 0.1 to 12 hours, and even more preferably within a range of 0.1 to 6 hours.

[0345] The reaction in step D1 may be carried out in the presence or absence of an inert gas (eg, nitrogen), but is preferably carried out in the absence of an inert gas.

[0346] Step D1 can be carried out under reduced pressure, atmospheric pressure, or pressurized conditions.

[0347] The compound (7) produced in step D1 can be isolated or purified as desired by conventional methods such as extraction, dissolution, concentration, precipitation, dehydration, adsorption, distillation, rectification, chromatography, or a combination thereof.

[0348] It is preferred to react the above alkanol with compound (6) to generate compound (7) in the 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.

[0349] Process D2

[0350] In step D2, compound (7) is reacted with a base (d2) to produce compound (8).

[0351] Regarding the details of the base (d2) in step D2, the same description as in the details of the base in step D is applicable unless otherwise specified.

[0352] The amount of the base (d2) used in step D2 is preferably in the range of 0.1 to 20 mol, more preferably 0.5 to 15 mol, and even more preferably 1 to 10 mol, based on 1 mol of compound (7).

[0353] Step D2 is preferably carried out in the presence of an organic solvent. Examples and preferred examples of the organic solvent are the same as those described above.

[0354] 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.

[0355] The reaction temperature in step D2 is preferably within a range of -50 to 120°C, more preferably within a range of -20 to 100°C, and even more preferably within a range of -10 to 70°C.

[0356] The reaction time of step D2 is preferably within a range of 0.1 to 24 hours, more preferably within a range of 0.1 to 12 hours, and even more preferably within a range of 0.1 to 6 hours.

[0357] The reaction in step D2 may be carried out in the presence or absence of an inert gas (eg, nitrogen), but is preferably carried out in the absence of an inert gas.

[0358] Step D2 can be carried out under reduced pressure, atmospheric pressure, or pressurized conditions.

[0359] In step D2, compound (8) may be precipitated as a solid in a solvent, and after precipitation, the solvent may be removed, thereby allowing compound (8) to be easily isolated. The method for removing the solvent may be a known method.

[0360] One embodiment of the present invention is a method for producing a compound represented by the above formula (5), wherein the method further comprises a step D1a of purifying the product (preferably the product liquid) of the above step D1 to obtain a compound represented by the above formula (7). The purified compound (7) can be provided to the above step D2.

[0361] Process D1a

[0362] In step D1a, the product (e.g., reaction solution) generated in step D1 can be refined to obtain compound (7). Compound (7) can be separated 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 easily obtain compound (7). In the case of a large amount of the organic layer, since it does not contain or contains only a small amount of other substances having a boiling point near the boiling point of compound (7), it is suitable for refining by distillation.

[0363] One embodiment of the present invention is a method for producing a compound represented by the above formula (5), in which, instead of the above steps D and E, the method 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 produce a step F of the compound represented by the above formula (5).

[0364] Process F

[0365] In step F, compound (6) is heated in the presence of a base (f) to generate a compound represented by the above formula (5). Step F can be carried out by a known method, for example, according to the method described in U.S. Pat. No. 3,308,107 or U.S. Pat. No. 6,664,431. The publications are incorporated herein by reference.

[0366] In step F, compound (6) may be isolated, or the product liquid containing compound (6) produced in step C may be used directly. The use of the product liquid is preferred because it has the advantage that purification of compound (6) is not required.

[0367] Regarding the details of the base (f) in step F, the same description as in the details of the base in step D is applicable unless otherwise specified.

[0368] 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.

[0369] 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.

[0370] 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.

[0371] 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.

[0372] 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.

[0373] Specific examples of the alkali metal oxide include lithium oxide, sodium oxide, potassium oxide, rubidium oxide, and cesium oxide.

[0374] Specific examples of the alkaline earth metal oxide include magnesium oxide, calcium oxide, and barium oxide.

[0375] Step F can be carried out in an organic solvent or in the absence of a solvent. Examples and preferred examples of the organic solvent are the same as those described above. Preferred 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.

[0376] The amount of the base (f) used in step F is preferably within a range of 0.1 to 200 mol, more preferably 0.5 to 100 mol, and even more preferably 1 to 50 mol, based on 1 mol of compound (6).

[0377] 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).

[0378] The amount of the organic solvent used in step F can be set to an amount that can function as a solvent based on common technical knowledge and the like.

[0379] The reaction temperature of step F is preferably in the range of 80 to 400° C. when a solvent is present, more preferably in the range of 100 to 350° C., and even more preferably in the range of 100 to 300° C. When no solvent is present, the reaction temperature is preferably in the range of 100 to 400° C., more preferably in the range of 150 to 400° C., and even more preferably in the range of 150 to 350° C.

[0380] The reaction time of step F is preferably within a range of 0.01 to 24 hours, more preferably within a range of 0.01 to 12 hours, and even more preferably within a range of 0.01 to 6 hours.

[0381] The reaction in step F may be carried out in the presence or absence of an inert gas (eg, nitrogen), but is preferably carried out in the absence of an inert gas.

[0382] Step F can be carried out under reduced pressure, atmospheric pressure or pressurized conditions.

[0383] The compound (5) produced in step F can be isolated or purified as desired by conventional methods such as extraction, dissolution, concentration, precipitation, dehydration, adsorption, distillation, rectification, chromatography, or a combination thereof.

[0384] Composition

[0385] One embodiment of the present invention is a composition containing the compound represented by the above-mentioned formula (1), which further contains 0.00001 to 1 part by mass of a compound represented by formula (10) (sometimes referred to as compound (10) in this specification) and / or 0.00001 to 1 part by mass of a compound represented by formula (11) (sometimes referred to as compound (11) in this specification) relative to 100 parts by mass of the compound represented by formula (1).

[0386] Formula (10):

[0387]

[0388] [Where R 41 , R 42 , R 43 and R 44 are the same or different and are hydrogen atoms or alkyl groups, or R 41 , R 42 , R 43 and R 44 Two of them may be bonded to each other to form a ring which may have one or more substituents.]

[0389] Formula (11):

[0390]

[0391] [Wherein,

[0392] R 46 is a hydrogen atom, an organic group or an amino group which may have one or more substituents,

[0393] R 47 , R 48 , R 49 and R 50 are the same or different and are hydrogen atoms or alkyl groups, or R 47 and R 48 may be combined with each other to form a ring which may have one or more substituents, R 48 and R 50 may be combined with each other to form a ring which may have one or more substituents, R 49 and R 50 They may combine with each other to form a ring which may have one or more substituents.]

[0394] The method for producing the compound represented by formula (1) of the present invention can also produce the above composition. The above composition may further contain compound (3), compound (4-1), compound (4-2), a polymerization inhibitor, water or a polar solvent.

[0395] 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 compound (1) after its production.

[0396] Compound (10) and Compound (11) are produced, for example, by fluorinating Compound (4-1) and Compound (4-2), respectively, during the production process of Compound (1). 41 ~R 44 and R in formula (11) 46 ~R 50 R in formula (4-1) is applied respectively 41 ~R 44 and R in formula (4-2) 46 ~R 50 The fluorinated compounds of the above-mentioned preferred specific examples of compound (4-1) and compound (4-2) are preferred specific examples of compound (10) and compound (11), respectively.

[0397] 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, even more 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 (1).

[0398] The amount of compound (11) in the composition is preferably 0.00001 to 1 part by mass, more preferably 0.00001 to 0.8 part by mass, even more 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 (1).

[0399] The above composition may contain either or both of Compound (10) and Compound (11). Preferably, the composition contains 0.00001 to 0.8 parts by mass of Compound (10) and / or 0.00001 to 0.8 parts by mass of Compound (11) per 100 parts by mass of Compound (1), more preferably 0.00001 to 0.5 parts by mass of Compound (10) and / or 0.00001 to 0.5 parts by mass of Compound (11), and particularly preferably 0.0001 to 0.1 parts by mass of Compound (10) and / or 0.0001 to 0.1 parts by mass of Compound (11).

[0400] Preferred examples of the polar solvent include alcohol solvents, ether solvents, ester solvents, and nitrile solvents.

[0401] Preferred specific examples of the alcohol solvent include methanol, ethanol, isopropanol, and tert-butanol.

[0402] Preferred 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.

[0403] Preferred specific examples of the nitrile solvent include 1,4-dicyanobutane, acetonitrile, and benzonitrile.

[0404] Preferred 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.

[0405] Preferred 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.

[0406] Preferred 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.

[0407] The amount of compound (3) in the composition is preferably 0.00001 to 10 parts by mass, more preferably 0.00001 to 8 parts by mass, even more preferably 0.00001 to 5 parts by mass, particularly preferably 0.0001 to 1 part by mass, based on 100 parts by mass of compound (1).

[0408] The amount of compound (4-1) in the composition is preferably 0.00001 to 1 part by mass, more preferably 0.00001 to 0.8 part by mass, even more preferably 0.00001 to 0.5 part by mass, particularly preferably 0.0001 to 0.1 part by mass, relative to 100 parts by mass of compound (1).

[0409] The amount of compound (4-2) in the composition is preferably 0.00001 to 1 part by mass, more preferably 0.00001 to 0.8 part by mass, even more preferably 0.00001 to 0.5 part by mass, particularly preferably 0.0001 to 0.1 part by mass, relative to 100 parts by mass of compound (1).

[0410] The amount of the polar solvent in the composition is preferably 0.00001 to 1 part by mass, more preferably 0.00001 to 0.8 part by mass, even more preferably 0.00001 to 0.5 part by mass, and particularly preferably 0.0001 to 0.1 part by mass, relative to 100 parts by mass of compound (1).

[0411] The amount 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, even more 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 compound (1).

[0412] The amount of water in the composition is preferably 0.00001 to 0.1 part by mass, more preferably 0.00001 to 0.08 part by mass, even more preferably 0.00001 to 0.05 part by mass, and particularly preferably 0.00001 to 0.01 part by mass, relative to 100 parts by mass of compound (1).

[0413] When the composition of the present invention is within the above-mentioned quantitative ratio range, it can be suitably used as a raw material for producing compound (5), for example.

[0414] Although the embodiments have been described above, it should be understood that various changes may be made to the modes and details without departing from the gist and scope of the claims.

[0415] Example

[0416] Hereinafter, one embodiment of the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

[0417] The symbols and abbreviations in the examples are used as follows.

[0418] DMF: N,N-dimethylformamide

[0419] Diglyme: Diethylene glycol dimethyl ether

[0420] GC: Gas chromatography

[0421] HMPA: Hexamethylphosphoric acid triamide

[0422] CsF: Cesium Fluoride

[0423] Compound 1a: A compound represented by the following formula (1a)

[0424]

[0425] Compound 6a: A compound represented by the following formula (6a)

[0426]

[0427] Compound 8a: A compound represented by the following formula (8a)

[0428]

[0429] Compound 5a: A compound represented by the following formula (5a)

[0430]

[0431] Compound 8b: A compound represented by the following formula (8b):

[0432]

[0433] Compound 7a: A compound represented by the following formula (7a)

[0434]

[0435] Compound 12: The compound represented by the following formula (12)

[0436]

[0437] Example 1: Steps A and B

[0438] 0.8 g of tetramethylurea (7.0 mmol), 5.1 g of DMF (70 mmol) and 9.4 g of diethylenedioxime (70 mmol) were added to a reactor and cooled to -20°C. 24 g of hexafluoropropylene oxide (0.14 mol) was added to the above reactor at -20°C and stirred at room temperature for 1 hour. After the hexafluoropropylene oxide disappeared, the reaction liquid was recovered. The reaction liquid is a composition of the present invention. The reaction liquid is separated into two layers, an upper liquid and a lower liquid. The reaction liquid is separated and 19 g of the upper liquid and 20 g of the lower liquid are recovered respectively. The lower liquid is analyzed by GC. 73 GC% of compound 1a is obtained with a yield of 70%. The tetrafluoromethyl urea (compound (10)) in the lower layer is 0.1 GC%. In addition, the tetrafluoromethyl urea is a mixture of fluorides in which at least one hydrogen atom of the methyl group in the tetramethyl urea is replaced by a fluorine atom.

[0439] Example 2: Steps A and B

[0440] 0.3 g of HMPA (1.6 mmol), 5.7 g of DMF (78 mmol) and 10 g of diethyldioxime (78 mmol) were added to the reactor and cooled to -20°C. 26 g of hexafluoropropylene oxide (0.15 mol) was added to the above reactor at -20°C and stirred at room temperature for 1 hour. After the hexafluoropropylene oxide disappeared, the reaction liquid was recovered. The reaction liquid was separated into two layers of upper liquid and lower liquid. The reaction liquid was separated and 19 g of the upper liquid and 22 g of the lower liquid were recovered respectively. The lower liquid was analyzed by GC. Compound 1a was obtained at a yield of 54% with a GC% of 65. The compound (11) in the lower layer was 0.2 GC%.

[0441] Reference Example 1

[0442] 0.83 g of CsF (2.5 mmol), 9.03 g of DMF (0.12 mol) and 16.6 g of diethyldioxime (0.12 mol) were added to the reactor and cooled to -20°C. 44 g of hexafluoropropylene oxide (0.27 mol) was added to the above reactor and stirred for 2 hours. After the hexafluoropropylene oxide disappeared, the reaction liquid was recovered. The reaction liquid was separated into two layers of upper liquid and lower liquid. The reaction liquid was separated and 29 g of the upper liquid and 40 g of the lower liquid were recovered respectively. The lower liquid was analyzed by GC. Compound 1a was obtained with a yield of 52% and 63 GC%.

[0443] Comparative Example 1: Synthesis of Compound 1a in Two Stages

[0444] 4.27 g of DMF (0.06 mol) was added to the reactor and cooled to -27°C. 12 g of hexafluoropropylene oxide (0.07 mol) was added to the above reactor and stirred for 1 hour. After stirring, the reaction solution was recovered. The reaction solution was analyzed by NMR. 4-Fluoro-5-oxy-2,4-bis(trifluoromethyl)-1,3-dioxirane-2-carbonyl fluoride, a precursor of the target product, was obtained in a yield of 5%. It can be considered that HCl gas was not used in this synthesis, resulting in a low yield. Since the yield of the precursor was very low, the second step could not be implemented.

[0445] Example 3: Process C

[0446] 13 g of the lower layer liquid (containing 9 g of compound 1a) obtained by the same operation as in Example 1, 2.3 g of CsF (15 mmol), and 4.0 g of diglyoxime (30 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 were analyzed by GC. 12 g of compound 6a was obtained with a purity of 60%.

[0447] Example 4: Step D

[0448] 9.8 g of the lower layer liquid containing compound 6a with a purity of 74% obtained by the same operation as in Example 3 was added to 3.2 g of potassium carbonate (0.02 mol) and 23 g of dimethoxyethane (0.26 mol), and stirred at 60° C. for 2 hours to obtain a reaction liquid. The reaction liquid was filtered to obtain a filtrate, which was concentrated. The filtrate was analyzed by NMR, and a concentrate containing 8.8 g of compound 8a was obtained (yield 44%).

[0449] Example 5: Process E

[0450] 6.7 g of compound 8a obtained in the same manner as in Example 4 was added to the reactor and heated at 200°C for 4 hours and at 300°C for 1 hour. The product was recovered in a trap at -78°C and analyzed by NMR and GC to obtain compound 5a at a yield of 60% and a purity of 95%.

[0451] Example 6: Step E

[0452] The same operation as in Example 4 was performed except that potassium carbonate was replaced with 0.02 mol of sodium carbonate, and 8.1 g of the obtained compound 8b and 24 g of triethylene glycol dimethyl ether were added to a reactor and heated at 120° C. for 0.5 hours. The product was recovered in a trap at −78° C. and analyzed by NMR and GC. As a result, compound 5a was obtained with a conversion rate of 65% and a selectivity of 88%, and compound 12 was obtained with a selectivity of 12%.

[0453] Example 7: Step D1

[0454] 3.2 g (0.1 mol) of methanol and 10 g of water were added to 22 g of the liquid obtained in Example 3, and the mixture was stirred for 2 hours. The resulting liquid was separated into two layers, and the lower layer was recovered by separation to obtain compound 7a with a purity of 50% (GC). The yield was 58%.

[0455] Example 8: Step D2

[0456] In a glass reactor, 0.09 mol of sodium hydroxide was added to 70 g of methanol. 0.09 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 by a concentrator, and the generated solid was recovered. The solid was dried under reduced pressure to obtain compound 8b in a stoichiometric amount.

Claims

1. A method for producing a compound represented by formula (1), characterized in that: A step A comprising reacting a compound represented by formula (2), a compound represented by formula (3) and a compound represented by formula (4-1), In formula (1), the two R 1 The same, is a fluorine atom or C 1-10 The fluoroalkyl group, In formula (2), R 1 The meaning is the same as above, In formula (3), R 31 , R 32 and R 33 The same or different, hydrogen or C 1-5 of an alkyl group, or R 31 A hydrogen atom or C 1-5 The alkyl group, R 32 and R 33 Combined to form a pyrrolidine ring or a piperidine ring, or R 31 and R 32 Combined to form a pyrrolidone ring or a piperidone ring, R 33 is a hydrogen atom, a methyl group or an ethyl group, In formula (4-1), R 41 , R 42 , R 43 and R 44 The same or different, hydrogen or C 1-5 Alkyl, or R 41 and R 42 The same or different atoms are hydrogen or C 1-5 Alkyl, R 43 and R 44 They are bonded to each other to form a tetrahydropyrimidinone ring or an imidazolidinone ring having one or two substituents on the carbon atoms on the ring, and the substituents are methyl or ethyl.

2. The manufacturing method according to claim 1, characterized in that: Step A is carried out in the presence of an organic solvent, and the organic solvent does not contain the compound represented by the formula (3) and the compound represented by the formula (4-1).

3. The manufacturing method according to claim 1 or 2, characterized in that: The step A is a step of generating an upper liquid layer and a lower liquid layer, and the manufacturing method further includes a step B of separating the upper liquid layer and the lower liquid layer.

4. The manufacturing method according to claim 1 or 2, characterized in that: R 41 and R 42 Same or different, C 1－5 alkyl, R 43 and R 44 Same or different, C 1－5 Alkyl groups, or groups which are combined with each other to form a tetrahydropyrimidinone ring or an imidazolidinone ring having one or two substituents on the carbon atoms in the ring, wherein the substituents are methyl or ethyl.

5. The manufacturing method according to claim 1 or 2, characterized in that: The compound represented by the formula (4-1) is at least one compound selected from the group consisting of N,N′-dimethylpropylene urea, N,N′-dimethylethylene urea and tetramethyl urea.

6. The manufacturing method according to claim 1 or 2, characterized in that: In step A, the compound represented by formula (2) is supplied in the form of gas, the amount of the compound represented by formula (2) is 70% to 99.8% by mass relative to the weight of the gas, and the amount of the compound represented by formula (4-1) is 0.001 to 0.3 mol relative to 1 mol of the compound represented by formula (2).

7. The manufacturing method according to claim 1 or 2, characterized in that: The process A does not contain CsF.

8. The manufacturing method according to claim 1 or 2, characterized in that: The R 1 It is trifluoromethyl.

9. The manufacturing method according to claim 1 or 2, characterized in that: The R 41 , R 42 , R 43 and R 44 It is methyl.

10. The manufacturing method according to claim 1 or 2, characterized in that: The R 31 is a hydrogen atom, the R 32 and R 33 It is methyl.

11. The manufacturing method according to claim 2, characterized in that: The organic solvent is diglyoxime.

12. A method for producing a compound represented by formula (5), characterized in that: include: A step of producing a compound represented by formula (1) using the production method according to claim 1 or the production method according to claim 3; Step C: heating the compound represented by formula (1) produced in the step in the presence of a fluorine compound (9) to produce a compound represented by formula (6); Step D is to react the compound represented by formula (6) with a base to produce a compound represented by formula (8), wherein the base is at least one selected from acetates, carbonates, bicarbonates, phosphates, hydrogenphosphates, alkoxides, hydroxides, hydrides or amides of alkali metals or alkaline earth metals; and Step E: heating the compound represented by the formula (8) to generate the compound represented by the formula (5); In formula (5), R 1 is a fluorine atom or C 1-10 The fluoroalkyl group, In formula (1), the two R 1 The same, is a fluorine atom or C 1-10 The fluoroalkyl group, The fluorine compound (9) is at least one selected from hydrogen fluoride, cesium fluoride, potassium hydrogen fluoride, calcium fluoride, sodium fluoride, potassium fluoride, sodium hydrogen fluoride, tetrabutylammonium fluoride, tetraethylammonium fluoride, tetramethylammonium fluoride, tetrabutylphosphonium fluoride, triethylmethylammonium fluoride, triethylamine 3 hydrofluoride, triethylamine 5 hydrofluoride, triethylamine 7 hydrofluoride, pyridinium poly(hydrogen fluoride), ammonium hydrogen fluoride and ammonium fluoride, In formula (6), R 1 The meaning is the same as above, In formula (8), R 81 is an alkali metal atom or an alkaline earth metal atom corresponding to the base, R 1 The meaning is the same as above.

13. The manufacturing method according to claim 12, characterized in that: Instead of the step D, it comprises: Step D1: reacting the compound represented by formula (6) with water or alkanol to produce a compound represented by formula (7); and Step D2: reacting the compound represented by the formula (7) with a base to produce the compound represented by the formula (8); In formula (7), R 71 is a hydrogen atom or an alkyl group, R 1 The meaning is the same as above.

14. The manufacturing method according to claim 13, characterized in that: Also includes: Step D1a is a step of purifying the product of step D1 to obtain the compound represented by formula (7).

15. The manufacturing method according to claim 12, characterized in that: Replacing the steps D and E, comprising: Step F: heating the compound represented by the formula (6) in the presence of a base to produce the compound represented by the formula (5).

16. The manufacturing method according to any one of claims 12 to 15, characterized in that: The fluorine compound (9) is CsF.

17. The manufacturing method according to any one of claims 12 to 14, characterized in that: The R 81 is a sodium atom or a potassium atom.

18. The manufacturing method according to claim 13 or 14, characterized in that: The alkanol is methanol.

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