Method for refining halogen-containing (meth) acrylate

Abstract

The present invention addresses the problem of providing a method for purifying a halogen-containing (meth) acrylate, said method being capable of highly removing an alcohol. This problem can be solved by a method for purifying a compound represented by formula (1) (wherein R1 and R2 are the same or different and are alkyl groups, fluoroalkyl groups, aryl groups which may have one or more substituents, halogen atoms, or hydrogen atoms, R3 is alkyl groups, fluoroalkyl groups, or aryl groups which may have one or more substituents, and X is fluoroalkyl groups or halogen atoms). The method comprises: (A) a step for obtaining a mixture by mixing a composition containing a compound represented by formula (1) and a compound represented by formula (2): R4-OH (R4 is an alkyl group, a fluoroalkyl group, or an aryl group which may have one or more substituents) with (i) a salt and / or (ii) a prescribed organic solvent; and (B) a step for separating the mixture into two or more phases in which the contents of the compounds represented by formula (1) are different from each other.

Description

[0001] This application is a divisional application of the same name filed on August 19, 2021, with the application number 202180050438.9. TECHNICAL FIELD

[0002] The present application relates to a refining method of halogen-containing (meth)acrylate. BACKGROUND

[0003] Halogen-containing (meth)acrylates are effective as synthetic intermediates for pharmaceuticals such as antibiotics, synthetic intermediates for sheath materials of optical fibers, synthetic intermediates for materials for paints, synthetic intermediates for semiconductor resists, and monomers for functional polymers, and the like.

[0004] In the production of halogen-containing (meth)acrylates, impurities can be mixed in a composition containing a target halogen-containing (meth)acrylate. As the impurities, for example, reaction solvents such as alcohols, catalysts, bases, cleaning solvents such as water, and the like can be listed.

[0005] Among these, for example, water can hydrolyze the halogen-containing (meth)acrylate, and thus can adversely affect the stability thereof. As a method for removing the water, for example, a method including a step of bringing a composition containing a halogen-containing (meth)acrylate and water into contact with a zeolite is known (Patent Literature 1).

[0006] In addition, as a method for removing alcohols, for example, a method including a step of bringing a composition containing a halogen-containing (meth)acrylate and an alcohol into contact with an acid anhydride is known (Patent Literature 2).

[0007] Prior Art Documents Patent Literature Patent Literature 1: Japanese Patent Application Laid-Open No. 2017-36272 Patent Literature 2: Japanese Patent Application Laid-Open No. 2017-36270 SUMMARY

[0008] Problem to be Solved by the Invention In the production of halogen-containing (meth)acrylates, alcohols as impurities can be mixed in a composition containing a halogen-containing (meth)acrylate. Even if the composition is subjected to water washing, the alcohols cannot be sufficiently removed. In a method in which the composition is brought into contact with an acid anhydride, there is room for improvement in terms of an increase in waste, an increase in cost due to the use of a large amount of acid anhydride, and the like.

[0009] The problem to be solved by the present application is to provide a refining method of halogen-containing (meth)acrylate capable of highly removing alcohols.

[0010] Technical Solution for Solving the Problem The present application includes the following.

[0011] Item 1. A method for refining a compound represented by formula (1), comprising: (A) a step of mixing a composition containing the compound represented by formula (1) and a compound represented by formula (2) with (i) a salt, (ii) an organic solvent (excluding the compound represented by formula (1) and the compound represented by formula (2) ), or (iii) the salt and the organic solvent to obtain a mixture; and (B) a step of separating the mixture into two or more phases having different contents of the compound represented by formula (1). (In the formulae, R 1 and R 2 are the same or different and are an alkyl group, a fluoroalkyl group, an aryl group which can have one or more substituents, a halogen atom, or a hydrogen atom, R 3 is an alkyl group, a fluoroalkyl group, or an aryl group which can have one or more substituents, X is a fluoroalkyl group or a halogen atom. R 4 -OH (2) (In the formulae, R 4 is an alkyl group, a fluoroalkyl group, or an aryl group which can have one or more substituents. Item 2. The method according to item 1, wherein the salt is one or more selected from inorganic salts and organic salts.

[0012] Item 3. The method according to item 1 or 2, wherein the salt is an inorganic salt.

[0013] Item 4. The method according to any one of items 1 to 3, wherein the cation of the salt is a metal cation, an ammonium which can have one or more substituents, a pyridinium which can have one or more substituents, an imidazolium which can have one or more substituents, or a phosphonium which can have one or more substituents.

[0014] Item 5. The method according to any one of items 1 to 4, wherein the cation of the salt contains at least one selected from monovalent metal cations and divalent metal cations.

[0015] Item 6. The method according to any one of items 1 to 4, wherein the cation of the salt is NR4 ＋ (each R can be the same or different and is H or an organic group having 1 to 10 carbon atoms).

[0016] Item 7. The method of any one of items 1 to 6, wherein the anion of the salt comprises at least one selected from sulfate ions, hydroxide ions, halide ions and nitrate ions.

[0017] Item 8. The method of any one of items 1 to 5, wherein the salt is at least one selected from LiCl, LiBr, LiI, NaI and CaCl2.

[0018] Item 9. The method of any one of items 1 to 8, wherein the amount of the salt used is in the range of 0.1 to 10 moles relative to 1 mole of the compound represented by formula (1) above.

[0019] Item 10. The method of any one of items 1 to 9, wherein the organic solvent is an aprotic solvent (but does not include the compound shown in formula (1) and the compound shown in formula (2)).

[0020] Item 11. The method of any one of items 1 to 10, wherein the organic solvent is an aprotic nonpolar solvent (but does not include the compound shown in formula (1) and the compound shown in formula (2)).

[0021] Item 12. The method of any one of items 1 to 10, wherein the organic solvent is at least one selected from aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers, esters (but not including compounds represented by formula (1) above), ketones, carbonates and nitriles.

[0022] Item 13. The method of any one of items 1 to 10, wherein the organic solvent is at least one selected from aromatic hydrocarbons and ethers.

[0023] Item 14. The method as described in any one of items 1 to 10, wherein the organic solvent is selected from C 5－16 Alkanes, C 5－10 Cycloalkanes can have at least one carbon atom. 1－4 Alkyl benzene, C 1－6 Haloalkanes, benzene having at least one halogen atom, di(C) 1－4 Alkyl ether, C 2－4 Di(C) of alkylene glycols 1－4 Alkyl ethers, polycarbonate 2－4 Di(C) of alkylene glycols 1－4 Alkyl ethers, 5-membered oxygen-containing heterocycles, C 1－6 Alkanoic acid C 1－4 Alkyl esters, di(C 1－4 Alkyl ketones, C6 carbonate 2－4 alkylene esters, C 1－6 At least one of cyanoalkane and benzene having at least one cyano group.

[0024] Item 15. The method of any one of items 1 to 10, wherein the organic solvent is selected from... Pentane, Hexane, Heptane, Octane, Nonane, Decane, Undecane, Dodecane, Tridecane, Tetradecane, Pentadecane, Hexadecane, Cyclopentane, Cyclohexane Benzene, xylene, toluene Dichloromethane, dichloroethane, dichloropropane, chlorobutane, chloroform, chlorobenzene, dichlorobenzene Diethyl ether, diisopropyl ether, tert-butyl methyl ether, dibutyl ether, monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, 1,4-dioxane, tetrahydrofuran, Ethyl acetate, butyl acetate, Methyl ethyl ketone, acetone, Ethylene carbonate, propylene carbonate, At least one of acetonitrile and benzyl nitrile.

[0025] Item 16. The method of any one of items 1 to 15, wherein the amount of the organic solvent used is in the range of 0.1 to 10 moles relative to 1 mole of the compound represented by formula (1) above.

[0026] Item 17. The method of any one of items 1 to 16, wherein step (A) is a step of mixing the above composition with (i) a salt, (ii) an organic solvent (but excluding the compound shown in formula (1) and the compound shown in formula (2) above) or (iii) the salt and the organic solvent above, and (iv) water to obtain a mixture.

[0027] Item 18. The method as described in Item 17, wherein the amount of the above-mentioned salt used is 150 mg or more relative to 1 mL of water.

[0028] Item 19. The method as described in Item 17 or 18, wherein the salt is LiCl, LiBr, LiI, NaI, or CaCl2. When the salt is LiCl, the amount of salt used is more than 150 mg per 1 mL of water. When the salt is LiBr, the amount of salt used is more than 310 mg per 1 mL of water. When the salt is LiI, the amount of salt used relative to 1 mL of water is 480 mg or more. When the salt mentioned above is NaI, the amount of the salt used relative to 1 mL of water is 540 mg or more. When the salt is CaCl2, the amount of salt used is more than 450 mg relative to 1 mL of water.

[0029] Item 20. The method of any one of items 1 to 19 further includes (C) a step of removing the phase in which the content of the compound represented by the above formula (1) is the lowest in the separated phase.

[0030] Item 21. The method as described in any one of items 1 to 20, performed in the range of -15 to 40°C.

[0031] Item 22. The method as described in any one of items 1 to 21, wherein R 1 It can be a hydrogen atom, an alkyl group, or a fluoroalkyl group.

[0032] Item 23. The method as described in any one of items 1 to 22, wherein R 2 It can be a hydrogen atom, an alkyl group, or a fluoroalkyl group.

[0033] Item 24. The method as described in any one of items 1 to 23, wherein R 3 It is an alkyl group.

[0034] Item 25. The method as described in any one of items 1 to 24, wherein R 3 C 1－4 alkyl.

[0035] Item 26. The method as described in any one of items 1 to 25, wherein R 4 It is an alkyl group.

[0036] Item 27. The method as described in any one of items 1 to 26, wherein R 4 C 1－4 alkyl.

[0037] Item 28. The method of any one of items 1 to 27, wherein X is a fluorine atom or a chlorine atom.

[0038] Item 29. A composition comprising a compound of formula (1), a compound of formula (2), and a salt, wherein the content of the salt is 2% by mass or less. (In the formula, R 1 and R 2 Whether the groups are the same or different, they can be alkyl, fluoroalkyl, aryl, halogen, or hydrogen atoms, which may have more than one substituent. R 3 It is an alkyl, fluoroalkyl, or aryl group that may have one or more substituents. X is a fluorinated alkyl group or a halogen atom. R 4 -OH (2) (where R) 4(It can be an alkyl group, a fluoroalkyl group, or an aryl group that may have one or more substituents.) Item 29a. The composition as described in Item 29, wherein the salt is the salt described in Item 2, 3 or 8.

[0039] Item 29b. The composition as described in Item 29, wherein the cation of the salt is any one of Items 4 to 6, and / or the anion of the salt is the anion described in Item 7.

[0040] Item 29c. The composition of claim 29, 29a or 29b further comprises an organic solvent.

[0041] Item 29d. The composition as described in Item 29c, wherein the organic solvent is any one of Items 10 to 15.

[0042] Item 29e. The composition as described in any one of items 29 and 29a to d, wherein R 1 It can be a hydrogen atom, an alkyl group, or a fluoroalkyl group.

[0043] Item 29f. The composition as described in any one of items 29 and 29a to e, wherein R 2 It can be a hydrogen atom, an alkyl group, or a fluoroalkyl group.

[0044] Item 29g. The composition as described in any one of items 29 and 29a to f, wherein R 3 It is an alkyl group.

[0045] Item 29h. The composition as described in any one of items 29 and 29a to g, wherein R 3 C 1－4 alkyl.

[0046] Item 29i. The composition as described in any one of items 29 and 29a to h, wherein R 4 It is an alkyl group.

[0047] Item 29j. The composition as described in any one of items 29 and 29a to i, wherein R 4 C 1－4 alkyl.

[0048] Item 29k. The composition as described in any one of items 29 and 29a to j, wherein X is a fluorine atom.

[0049] Item 30. A composition comprising a compound of formula (1) and at least one organic solvent selected from aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers, esters (excluding the compound of formula (1) above), ketones, carbonates and nitriles, wherein the content of the organic solvent is 20% by mass or less. (In the formula, R 1 and R 2 Whether the groups are the same or different, they can be alkyl, fluoroalkyl, aryl, halogen, or hydrogen atoms, which may have more than one substituent. R 3 It is an alkyl, fluoroalkyl, or aryl group that may have one or more substituents. X is a fluorinated alkyl group or a halogen atom. Item 30a. The composition as described in Item 30 further comprises a compound represented by formula (2).

[0050] R 4 -OH (2) (where R) 4 (It can be an alkyl group, a fluoroalkyl group, or an aryl group that may have one or more substituents.) Item 30b. The composition as described in item 30 or 30a, wherein R 1 It can be a hydrogen atom, an alkyl group, or a fluoroalkyl group.

[0051] Item 30c. The composition as described in items 30, 30a or 30b, wherein R 2 It can be a hydrogen atom, an alkyl group, or a fluoroalkyl group.

[0052] Item 30d. The composition as described in any one of items 30 and 30a to 30c, wherein R 3 It is an alkyl group.

[0053] Item 30e. The composition as described in any one of items 30 and 30a to d, wherein R 3 C 1－4 alkyl.

[0054] Item 30f. The composition as described in any one of items 30a to 30e, wherein R 4 It is an alkyl group.

[0055] Item 30g. The composition as described in any one of items 30a to 30f, wherein R 4 C 1－4 alkyl.

[0056] Item 30h. The composition as described in any one of items 30 and 30a to g, wherein X is a fluorine atom.

[0057] Invention Effects According to the present invention, a method for purifying halogenated (meth)acrylates capable of highly removing alcohols is provided. Detailed Implementation

[0058] The above summary of the present invention is not intended to describe all or all of the embodiments disclosed herein.

[0059] The following description of the present invention illustrates embodiments in more detail.

[0060] In some parts of this invention, guidance is provided by way of example, and such examples may be used in various combinations.

[0061] In all cases, the exemplified group serves as a non-exclusive and representative group.

[0062] All publications, patents and patent applications referenced in this specification may be incorporated herein by direct reference.

[0063] Terms Unless otherwise specified, the symbols and abbreviations in this specification may be understood, in the context of this specification, as commonly used in the technical field to which this invention pertains.

[0064] In this specification, the use of the word "contains" is intended to include both the expression "substantially constitutes" and the expression "consisting of".

[0065] Unless otherwise specified, the procedures, treatments or operations described in this manual may be performed at room temperature.

[0066] In this instruction manual, room temperature may refer to a temperature in the range of 10 to 40°C.

[0067] In this specification, the symbol "C" is used. n－m (where n and m are numbers) as commonly understood by those skilled in the art, means that the number of carbon atoms is n or more and m or less.

[0068] In this specification, the term "halogen atom" may include, for example, fluorine, chlorine, bromine, and iodine atoms.

[0069] In this specification, "organic group" refers to a group containing one or more carbon atoms.

[0070] Examples of this "organic group" include: Alkyl groups that can have more than one substituent Alkenes that can have more than one substituent Alkyne groups can have more than one substituent. Aryl groups can have more than one substituent. Aryl groups can have more than one substituent. Non-aromatic heterocyclic groups that can have more than one substituent Heteroaryl groups that can have more than one substituent cyano, Aldehyde group carboxyl, R r O-、 R r CO-、 R r COO-、 R r SO2−, R r OCO- and R r OSO2- (In these formulas, R) r Independently: Alkyl groups that can have more than one substituent Alkenes that can have more than one substituent Alkyne groups can have more than one substituent. Aryl groups can have more than one substituent. Aryl groups can have more than one substituent. Non-aromatic heterocyclic groups that may have one or more substituents, or (It can be a heteroaryl group with more than one substituent).

[0071] In this specification, "hydrocarbon group" may include alkyl, alkenyl, alkynyl, aryl, aralkyl and groups in combination thereof.

[0072] In this specification, "alkyl" can be a straight-chain, branched, or cyclic alkyl group.

[0073] In this specification, "alkyl" can be, for example, C10. 1－20 Alkyl, C 1－12 Alkyl, C 1－6 Alkyl, C 1－4 Alkyl or C 1－3 alkyl.

[0074] In this specification, the term "alkyl" may include, for example, straight-chain or branched alkyl groups such as methyl, ethyl, propyl (n-propyl, isopropyl), butyl (n-butyl, isobutyl, sec-butyl, tert-butyl), pentyl, and hexyl.

[0075] In this specification, the term "alkyl" may include, for example, cyclic alkyl or cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl (e.g., C14). 3－8 cycloalkyl groups).

[0076] In this specification, "fluoroalkyl" means an alkyl group in which at least one hydrogen atom is replaced by a fluorine atom.

[0077] In this specification, "fluoroalkyl" may have one or more fluorine atoms (e.g., 1 to 3, 1 to 6, 1 to 12 or 1 to the maximum number that can be substituted).

[0078] In this specification, "fluoroalkyl" can be, for example, C10. 1－20 Fluoroalkyl, C 1－12 Fluoroalkyl, C 1－6 Fluoroalkyl, C 1－4 Fluorinated alkyl or C 1－3 Fluorinated alkyl groups.

[0079] In this specification, "fluoroalkyl" can be either linear or branched.

[0080] In this specification, "fluoroalkyl" can be perfluoroalkyl or non-perfluoroalkyl.

[0081] In this specification, "fluoroalkyl" may be used to refer to, for example, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, tetrafluoropropyl (e.g., HCF2CF2CH2-), hexafluoropropyl (e.g., (CF3)2CH-), nonafluorobutyl, octafluoropentyl (e.g., HCF2CF2CF2CF2CH2-), and tridecafluorohexyl.

[0082] In this specification, "alkenyl" can be, for example, C 2－10 Alkenyl group.

[0083] In this specification, the term "alkenyl" may include, for example, straight-chain or branched alkenyl groups such as vinyl, 1-propen-1-yl, 2-propen-1-yl, isopropenyl, 2-buten-1-yl, 4-penten-1-yl, and 5-hexen-1-yl.

[0084] In this specification, the term "alkenyl" may include, for example, cyclic alkenyl or cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and cycloheptenyl (e.g., C10). 3－8 (Cycloalkenyl).

[0085] In this specification, "alkynyl group" can be, for example, C 2－10 Alkyne group.

[0086] In this specification, the term "alkynyl" may include, for example, straight-chain or branched alkynyl groups such as ethynyl, 1-propynyl-1-yl, 2-propynyl-1-yl, 4-pentynyl-1-yl, and 5-hexynyl-1-yl.

[0087] In this specification, "aryl" can be, for example, monocyclic, bicyclic, tricyclic or tetracyclic.

[0088] In this specification, "aryl" can be, for example, C 6－18 Aryl, C 6－16 Aryl, C 6－14 Aryl or C 6－12 Aryl.

[0089] In this specification, the term "aryl" may include, for example, phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl and 2-anthrayl.

[0090] In this specification, "aryl group" can be, for example, C10. 7－19 Aryl alkyl, C 7－17 Aryl alkyl, C 7－15 Aryl or C 7－13 Aryl alkyl group.

[0091] In this specification, "aralkyl" may include, for example, benzyl, phenethyl, diphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 2-biphenylmethyl, 3-biphenylmethyl and 4-biphenylmethyl.

[0092] In this specification, "non-aromatic heterocyclic group" can be, for example, monocyclic, bicyclic, tricyclic or tetracyclic.

[0093] In this specification, "non-aromatic heterocyclic group" can be, for example, a non-aromatic heterocyclic group that, in addition to containing carbon atoms, contains 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen atoms.

[0094] In this specification, "non-aromatic heterocyclic group" can be saturated or unsaturated.

[0095] In this specification, "non-aromatic heterocyclic group" may include, for example, tetrahydrofuranyl, oxazolidinyl, imidazolinyl, azirropropyl, azirrobutyl, pyrrolyl, piperidinyl, azepanyl, azocanyl, piperazine, diazepinyl, diazepinyl, tetrahydropyranyl, morpholinyl, thiomorpholinyl, 2-oxazolidinyl, dihydrofuranyl, dihydropyranyl, and dihydroquinolinyl, etc.

[0096] In this specification, "heteroaryl" may include, for example, monocyclic aromatic heterocyclic groups (e.g., 5- or 6-membered monocyclic aromatic heterocyclic groups) and aromatic fused heterocyclic groups (e.g., 5- to 18-membered aromatic fused heterocyclic groups).

[0097] In this specification, "5- or 6-membered monocyclic aromatic heterocyclic groups" may include, for example, pyrrole, furanyl, thiophene, pyrazolyl, imidazole, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, triazolyl, oxadiazolyl, thiazolyl, tetrazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, etc.

[0098] In this specification, "5- to 18-membered aromatic fused heterocyclic groups" may include, for example, isoindolyl, indolyl, benzofuranyl, benzothiophenyl, indazoleyl, benzoimidazolyl, 1,2-benzoisoxazolyl, benzoxazolyl, 1,2-benzoisothiazolyl, benzothiazolyl, isoquinolinyl, quinolinyl, cyclolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, pyrazolo[1,5-a]pyridyl, imidazo[1,2-a]pyridyl, etc.

[0099] In this specification, "R" r "O-" can include alkoxy groups, cycloalkoxy groups (such as cyclopentoxy, cyclohexyloxy, etc. C 3－8 Cycloalkoxy, aryloxy (e.g., phenoxy, naphthoxy, etc. C 6－18 Aryloxy groups and arylalkoxy groups (e.g., benzyloxy, phenylethoxy, etc.) 7－19 (aranealkyloxy group).

[0100] In this specification, "alkoxy" can be a group formed by the bonding of an oxygen atom with an alkyl group (alkyl-O-).

[0101] In this specification, "alkoxy" can be a straight-chain or branched alkoxy group.

[0102] In this specification, "alkoxy" may include, for example, straight-chain or branched C-type compounds such as methoxy, ethoxy, propoxy (n-propoxy, isopropoxy), butoxy (n-butoxy, isobutoxy, sec-butoxy, tert-butoxy), pentoxy, and hexoxy. 1－20 Alkyl group.

[0103] In this specification, "alkylthio" can be a group formed by the bonding of a sulfur atom with an alkyl group (alkyl-S-).

[0104] In this specification, "alkylthio" can be a straight-chain or branched alkylthio group.

[0105] In this specification, "alkathioyl" can refer to linear or branched C-type groups such as methylthioyl, ethylthioyl, propylthioyl (n-propylthioyl, isopropylthioyl), butylthioyl (n-butylthioyl, isobutylthioyl, sec-butylthioyl, tert-butylthioyl), pentylthioyl, and hexylthioyl. 1－20 Alkylthio group.

[0106] In this specification, "R" rCO-” can include, for example, alkyl carbonyl groups [such as acetyl, propionyl, butyryl, etc. (C 1－10 Alkyl carbonyl], aryl carbonyl [e.g., benzoyl, naphthyl, etc. (C 6－18 Aryl)carbonyl] and aralkylcarbonyl] such as benzylcarbonyl, phenethylcarbonyl, etc. (C 7－19 [Aryl group (carbonyl group)].

[0107] In this specification, "R" r COO-” can include, for example, alkyl carbonyl groups [such as acetoxy, propionyloxy, butyryloxy, etc. (C 1－10 Alkyl carbonyl group], aryl carbonyl group [e.g., benzoyloxy, naphthyloxy, etc. (C 6－18 [Aryl]carbonyloxy] and aralkylcarbonyloxy [e.g., benzylcarbonyloxy, phenethylcarbonyloxy, etc. (C 7－19 [Aryl group (carbonyl group)]

[0108] In this specification, "R" r SO2-” can include, for example, alkyl sulfonyl groups (such as methyl sulfonyl, ethyl sulfonyl, propyl sulfonyl, etc. C 1－10 alkylsulfonyl), arylsulfonyl (e.g., phenylsulfonyl, naphthylsulfonyl, etc. C 6－18 Arylsulfonyl) and aralkylsulfonyl (e.g., benzylsulfonyl, phenylethylsulfonyl, etc. C 7－19 Aryl alkyl sulfonyl group).

[0109] In this specification, "R" r OCO-” can include, for example, alkoxy carbonyl groups [such as methoxy carbonyl, ethoxy carbonyl, propoxy carbonyl, etc. (C 1－10 Alkoxy (carbonyl) [, aryloxy carbonyl [e.g. phenoxy carbonyl, naphthoxy carbonyl, etc. (C 6－18 [Aryloxy]carbonyl] and arylalkoxycarbonyl [e.g., benzyloxycarbonyl, phenethoxycarbonyl, etc. (C 7－19 [Arylalkoxy)carbonyl].

[0110] In this specification, "R" r OSO2-” can include, for example, alkoxysulfonyl groups (such as methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, etc.). 1－10 Alkoxysulfonyl), aryloxysulfonyl (e.g., phenoxysulfonyl, naphthoxysulfonyl, etc. C 6－18 Aryloxysulfonyl) and arylalkoxysulfonyl (e.g., benzyloxysulfonyl, phenylethoxysulfonyl, etc. C 7－19 (aranealkyloxysulfonyl group).

[0111] In this specification, examples of "substituents" in "hydrocarbon group that may have one or more substituents", "alkyl group that may have one or more substituents", "alkenyl group that may have one or more substituents", "alkynyl group that may have one or more substituents", "arylyl group that may have one or more substituents", "aralkyl group that may have one or more substituents", "non-aromatic heterocyclic group that may have one or more substituents", and "heteroaryl group that may have one or more substituents" can respectively include halogen, nitro, cyano, oxy, thio, carboxyl, sulfonyl, sulfamoyl, sulfinamoyl, sulfenamoyl, R r O-、R r CO-、R r COO-、R r SO2−, R r OCO- and R r OSO2- (in these formulas, R) r The meaning is the same as above.

[0112] Examples of "halogen" substituents include fluorine, chlorine, bromine, and iodine.

[0113] The number of substituents can range from 1 to the maximum number that can be substituted (e.g., 1, 2, 3, 4, 5, 6).

[0114] Refining method In one embodiment, the purification method of the compound represented by formula (1) includes: (A) A step of mixing a composition containing the compound shown in formula (1) and the compound shown in formula (2) with (i) a salt, (ii) an organic solvent (excluding the compound shown in formula (1) and the compound shown in formula (2), or (iii) the salt and the organic solvent to obtain a mixture; and (B) A process of separating the above mixture into two or more phases with different contents of the compound shown in formula (1). (In the formula, R 1 and R 2 Whether the groups are the same or different, they can be alkyl, fluoroalkyl, aryl, halogen, or hydrogen atoms, which may have more than one substituent. R 3 It is an alkyl, fluoroalkyl, or aryl group that may have one or more substituents. X is a fluorinated alkyl group or a halogen atom. R 4-OH (2) (where R) 4 (It can be an alkyl group, a fluoroalkyl group, or an aryl group that may have one or more substituents.) Process A There are no particular limitations as long as the composition contains the compound shown in formula (1) and the compound shown in formula (2). For example, the composition can be the compound shown in formula (1) (in bold) containing the compound shown in formula (2) as an impurity.

[0115] In equation (1), R 1 Preferably, it is a hydrogen atom, an alkyl group, or a fluoroalkyl group; more preferably, it is a hydrogen atom or a C group. 1－20 Alkyl (preferably C) 1－12 Alkyl, more preferably C 1－6 Alkyl, preferably C 1－4 Alkyl, and more preferably C 1－3 Alkyl, particularly preferred C1 or C2 alkyl) or C 1－20 Fluoroalkyl (preferably C) 1－12 Fluorinated alkyl, more preferably C 1－6 Fluorinated alkyl groups, preferably C 1－4 Fluorinated alkyl groups, with C being a further preferred option. 1－3 Fluorinated alkyl groups, particularly preferably C1 or C2 fluoroalkyl groups, and even more preferably hydrogen atoms.

[0116] In equation (1), R 2 Preferably, it is a hydrogen atom, an alkyl group, or a fluoroalkyl group; more preferably, it is a hydrogen atom or a C group. 1－20 Alkyl (preferably C) 1－12 Alkyl, more preferably C 1－6 Alkyl, preferably C 1－4 Alkyl, and more preferably C 1－3 Alkyl, particularly preferred C1 or C2 alkyl) or C 1－20 Fluoroalkyl (preferably C) 1－12 Fluorinated alkyl, more preferably C 1－6 Fluorinated alkyl groups, preferably C 1－4 Fluorinated alkyl groups, with C being a further preferred option. 1－3 Fluorinated alkyl groups, particularly preferably C1 or C2 fluoroalkyl groups, and even more preferably hydrogen atoms.

[0117] In equation (1), R 3 Preferably, it is an alkyl group, more preferably a straight-chain alkyl group. Additionally, R... 3 C is preferred 1－20 Alkyl, more preferably C 1－12 Alkyl, more preferably C 1－6 Alkyl, more preferably C 1－4 Alkyl groups, particularly preferably C4 groups1－3 Alkyl, particularly preferably methyl or ethyl, and even more preferably methyl.

[0118] In equation (1), X is preferably C. 1－20 Fluoroalkyl (preferably C) 1－12 Fluorinated alkyl, more preferably C 1－6 Fluorinated alkyl groups, preferably C 1－4 Fluorinated alkyl groups, with C being a further preferred option. 1－3 Fluorinated alkyl groups, particularly preferred C1 or C2 fluoroalkyl groups, fluorine atoms, or chlorine atoms.

[0119] X is more preferably a trifluoromethyl group, a fluorine atom, or a chlorine atom.

[0120] X is further preferably a fluorine atom or a chlorine atom.

[0121] X is particularly preferably a fluorine atom.

[0122] In equation (1), R is preferred. 3 C 1－20 Alkyl (preferably C) 1－12 Alkyl, more preferably C 1－6 Alkyl, preferably C 1－4 Alkyl, and more preferably C 1－3 Alkyl, particularly preferably methyl or ethyl), and X is trifluoromethyl, fluorine or chlorine.

[0123] In equation (1), R is more preferred. 3 X is methyl or ethyl (preferably methyl), and X is trifluoromethyl, fluorine or chlorine.

[0124] In equation (1), R is preferred. 1 For hydrogen atoms, R 2 For hydrogen atoms, R 3 X is methyl or ethyl (preferably methyl), and X is a fluorine atom or a chlorine atom.

[0125] The compound shown in formula (1) can be manufactured or based on a known manufacturing method, or can be obtained commercially.

[0126] The compound shown in formula (1) can be manufactured, for example, according to the manufacturing method described in Japanese Patent Publication No. 1-33098, International Publication No. 2014 / 034906, or a method based thereon.

[0127] In equation (2), R 4 Preferably, it is an alkyl group, more preferably a straight-chain alkyl group. Additionally, R... 4 C is preferred 1－20 Alkyl, more preferably C 1－12 Alkyl, more preferably C1－6 Alkyl, more preferably C 1－4 Alkyl groups, particularly preferably C4 groups 1－3 Alkyl, particularly preferably methyl or ethyl, and even more preferably methyl.

[0128] R 4 Can be used with R 3 They can be the same or different; it is preferable to use R. 3 same.

[0129] In the composition, the lower limit of the content of the compound represented by formula (1) is preferably 5% by mass, more preferably 10% by mass, and even more preferably 15% by mass.

[0130] In the composition, the upper limit of the content of the compound represented by formula (1) is preferably 50% by mass, more preferably 45% by mass, and even more preferably 40% by mass.

[0131] In the composition, the content of the compound represented by formula (1) is preferably in the range of 5 to 50% by mass, more preferably in the range of 10 to 45% by mass, and even more preferably in the range of 15 to 40% by mass.

[0132] In the composition, the lower limit of the content of the compound represented by formula (2) is preferably 50% by mass, more preferably 55% by mass, and even more preferably 60% by mass.

[0133] In the composition, the upper limit of the content of the compound represented by formula (2) is preferably 95% by mass, more preferably 90% by mass, and even more preferably 85% by mass.

[0134] In the composition, the content of the compound represented by formula (2) is preferably in the range of 50 to 95% by mass, more preferably in the range of 55 to 90% by mass, and even more preferably in the range of 60 to 85% by mass.

[0135] In the composition, the mass ratio of the compound shown in formula (1) to the compound shown in formula (2) is preferably in the range of 5:95 to 50:50, more preferably in the range of 10:90 to 40:60, and even more preferably in the range of 15:85 to 30:70.

[0136] In addition to the compounds shown in formula (1) and formula (2), the composition may contain one or more other substances. These other substances may include, for example, substances used to manufacture the compound shown in formula (1) (e.g., catalysts, bases), byproducts, etc.

[0137] Salt (i) is preferably a substance that can be separated into two or more phases with different contents of the compound shown in formula (1) by mixing with the composition. Salt (i) can be one or more selected from inorganic salts and organic salts, preferably inorganic salts.

[0138] The cation that serves as salt (i) can be, for example, a metal cation, an ammonium cation having one or more substituents, a pyridinium cation having one or more substituents, an imidazolium cation having one or more substituents, or a phosphonium cation having one or more substituents.

[0139] Examples of metal cations include monovalent metal cations (such as alkali metals like Li and Na), divalent metal cations (such as alkaline earth metals like Ca), and trivalent metal cations (such as metals in Group 13 of the periodic table like Al).

[0140] Ammonium compounds that can have more than one substituent can be exemplified by NR4. ＋ (The Rs can be the same or different from each other, and can be H or an organic group, or any two can be bonded together to form a ring that can have substituents). R is preferably H or a hydrocarbon group (e.g., alkyl, aryl). Additionally, R is also preferably H or an organic group having 1 to 10 carbon atoms (e.g., C). 1－10 Alkyl groups). Preferably, all R groups are organic groups (e.g., C10). 1－10 Alkyl groups and other hydrocarbon groups).

[0141] In pyridinium compounds that can have more than one substituent, examples of substituents include halogen atoms, amino groups, alkyl groups, monoalkylamino groups, dialkylamino groups, alkylcarbonyl groups, alkylcarbonylalkyl groups, aminocarbonyl groups, aminocarbonylalkyl groups, cyano groups, cyanoalkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. The number of substituents can be, for example, one, two, or three.

[0142] In imidazolium, which can have more than one substituent, examples of substituents include halogen atoms, alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. The number of substituents can be, for example, one, two, or three.

[0143] In phosphonium that can have more than one substituent, examples of substituents include alkyl, alkenyl, alkoxycarbonylalkyl, monoalkylaminoalkyl, dialkylaminoalkyl, cyanoalkyl, cycloalkyl, aryl, aralkyl, heteroaryl, etc. The number of substituents can be, for example, 1, 2, 3, or 4.

[0144] The cation of salt (i) is preferably a metal cation.

[0145] Examples of anions that can be used as salts (i) include carbonate ions, bicarbonate ions, carboxylate ions, sulfate ions, hydroxide ions, halide ions (e.g., bromide ions, chloride ions, iodide ions), nitrate ions, etc.

[0146] The anion of salt (i) is preferably a halide ion.

[0147] The salt (i) is preferably selected from at least one of LiCl, LiBr, LiI, NaI and CaCl2.

[0148] When the composition is mixed with salt (i) and water (iv), the lower limit of the amount of salt (i) used relative to 1 mL of water is preferably 150 mg, more preferably 170 mg.

[0149] For example, when the salt (i) is LiCl, the lower limit of the amount of salt (i) used relative to 1 mL of water is preferably 150 mg, more preferably 170 mg.

[0150] When the salt (i) is LiBr, the lower limit of the amount of salt (i) used relative to 1 mL of water is preferably 310 mg, more preferably 350 mg.

[0151] When the salt (i) is LiI, the lower limit of the amount of salt (i) used relative to 1 mL of water is preferably 480 mg, more preferably 500 mg, and even more preferably 540 mg.

[0152] When the salt (i) is NaI, the lower limit of the amount of salt (i) used relative to 1 mL of water is preferably 540 mg, more preferably 550 mg, further preferably 600 mg, and even more preferably 610 mg.

[0153] When the salt (i) is CaCl2, the lower limit of the amount of salt (i) used relative to 1 mL of water is preferably 400 mg, more preferably 450 mg.

[0154] The upper limit of the amount of salt (i) used relative to 1 mL of water is preferably 1360 mg, more preferably 1350 mg, even more preferably 1300 mg, even more preferably 1250 mg, and particularly preferably 1215 mg.

[0155] For example, when the salt (i) is LiCl, the upper limit of the amount of salt (i) used relative to 1 mL of water is preferably 350 mg, more preferably 340 mg.

[0156] When the salt (i) is LiBr, the upper limit of the amount of salt (i) used relative to 1 mL of water is preferably 790 mg, more preferably 750 mg, and even more preferably 705 mg.

[0157] When the salt (i) is LiI, the upper limit of the amount of salt (i) used relative to 1 mL of water is preferably 1220 mg, more preferably 1200 mg, even more preferably 1150 mg, even more preferably 1100 mg, and particularly preferably 1085 mg.

[0158] When the salt (i) is NaI, the upper limit of the amount of salt (i) used relative to 1 mL of water is preferably 1360 mg, more preferably 1350 mg, even more preferably 1300 mg, even more preferably 1250 mg, and particularly preferably 1215 mg.

[0159] When the salt (i) is CaCl2, the upper limit of the amount of salt (i) used relative to 1 mL of water is preferably 1000 mg, more preferably 950 mg, and even more preferably 900 mg.

[0160] The amount of salt (i) used relative to 1 mL of water is preferably in the range of 150 to 1360 mg, more preferably in the range of 170 to 1215 mg.

[0161] For example, when the salt (i) is LiCl, the amount of salt (i) used relative to 1 mL of water is preferably in the range of 150 to 350 mg, more preferably in the range of 170 to 340 mg.

[0162] When the salt (i) is LiBr, the amount of salt (i) used relative to 1 mL of water is preferably in the range of 310 to 790 mg, more preferably in the range of 350 to 705 mg.

[0163] When the salt (i) is LiI, the amount of salt (i) used relative to 1 mL of water is preferably in the range of 480 to 1220 mg, more preferably in the range of 540 to 1085 mg.

[0164] When the salt (i) is NaI, the amount of salt (i) used relative to 1 mL of water is preferably in the range of 540 to 1360 mg, more preferably in the range of 610 to 1215 mg.

[0165] When the salt (i) is CaCl2, the amount of salt (i) used relative to 1 mL of water is preferably in the range of 400 to 1000 mg, more preferably in the range of 450 to 900 mg.

[0166] When the concentration of the saturated aqueous solution at room temperature (e.g., 25°C) is set as A, the salt (i) can be used in an amount preferably 0.5 × A or more, more preferably 0.7 × A or more, and even more preferably 0.8 × A or more. Furthermore, the salt (i) is preferably used in an amount less than A.

[0167] The lower limit of the amount of salt (i) used is preferably 0.1 moles, more preferably 0.5 moles, relative to 1 mole of the compound shown in formula (1).

[0168] The upper limit of the amount of salt (i) used is preferably 10 moles, more preferably 9 moles, relative to 1 mole of the compound shown in formula (1).

[0169] The amount of salt (i) used is preferably in the range of 0.1 to 10 moles, more preferably in the range of 0.5 to 9 moles, relative to 1 mole of the compound shown in formula (1).

[0170] The lower limit of the amount of salt (i) used relative to 100 parts by mass of the composition is preferably 10 parts by mass, more preferably 15 parts by mass, and even more preferably 20 parts by mass.

[0171] The upper limit of the amount of salt (i) used relative to 100 parts by weight of the composition is preferably 100 parts by weight, more preferably 95 parts by weight, and even more preferably 90 parts by weight.

[0172] The amount of salt (i) used relative to 100 parts by weight of the composition is preferably in the range of 10 to 100 parts by weight, more preferably in the range of 15 to 95 parts by weight, and even more preferably in the range of 20 to 90 parts by weight.

[0173] There are no particular limitations on the organic solvent (ii) as long as it is not a compound represented by formula (1) or a compound represented by formula (2). The organic solvent (ii) is preferably a solvent that can be separated into two or more phases with different contents of the compound represented by formula (1) by mixing with the composition. The organic solvent (ii) can be, for example, an aprotic solvent, and as a specific example, at least one solvent selected from aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers, esters (but not including compounds represented by formula (1)), ketones, carbonates and nitriles.

[0174] As aliphatic hydrocarbons, C can be listed as an example. 5－16 Alkanes (e.g., pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane), C 5－10 Cycloalkanes (such as cyclopentane and cyclohexane), etc.

[0175] As aromatic hydrocarbons, examples that can have at least one carbon atom can be listed. 1－4 Alkyl benzenes, such as benzene, xylene, and toluene, can be cited as specific examples.

[0176] As a halohydrocarbon, C can be listed as an example. 1－6 Halogenated alkanes (e.g., dichloromethane, dichloroethane, dichloropropane, chlorobutane, chloroform), benzene having at least one halogen atom (e.g., chlorobenzene, dichlorobenzene), etc.

[0177] As an ether, examples include di(C) 1－4 Alkyl ethers (e.g., diethyl ether, diisopropyl ether, tert-butyl methyl ether, dibutyl ether), C 2－4 Di(C) of alkylene glycols 1－4 Alkyl ethers (e.g., monoethylene glycol dimethyl ether), poly(C) ethers 2－4 Di(C) of alkylene glycols 1－4 Alkyl ethers (e.g., diethylene glycol dimethyl ether, triethylene glycol dimethyl ether), 5-membered oxygen-containing heterocycles (e.g., 1,4-dioxane, tetrahydrofuran), etc.

[0178] As esters (but excluding compounds represented by formula (1), C can be listed as an example. 1－6 Alkanoic acid C 1－4 Alkyl esters, as specific examples, include ethyl acetate, butyl acetate, etc.

[0179] As ketones, examples include di(C) 1－4 Alkyl ketones, as specific examples, include methyl ethyl ketone, acetone, etc.

[0180] As carbonates, examples include carbonic acid (C6C). 2－4 Alkyl esters, as specific examples, include ethylene carbonate, propylene carbonate, etc.

[0181] As a nitrile, C can be listed as an example. 1－6 Cyanoalkanes (e.g., acetonitrile), benzenes having at least one cyano group (e.g., benzyl nitrile), etc.

[0182] In one embodiment, the organic solvent (ii) is preferably an aprotic, nonpolar solvent.

[0183] In one embodiment, the organic solvent (ii) is preferably at least one selected from aromatic hydrocarbons and ethers.

[0184] In one embodiment, the organic solvent (ii) is preferably selected from C. 5－16 Alkanes, C 5－10 Cycloalkanes can have at least one carbon atom. 1－4 Alkyl benzene, C 1－6 Haloalkanes, benzene having at least one halogen atom, di(C) 1－4 Alkyl ether, C 2－4 Di(C) of alkylene glycols 1－4 Alkyl ethers, polycarbonate 2－4 Di(C) of alkylene glycols 1－4 Alkyl ethers, 5-membered oxygen-containing heterocycles, C 1－6 Alkanoic acid C 1－4 Alkyl esters, di(C 1－4 Alkyl ketones, C6 carbonate 2－4 alkylene esters, C1－6 At least one of cyanoalkane and benzene having at least one cyano group.

[0185] In this embodiment, the organic solvent (ii) is more preferably selected from... Pentane, Hexane, Heptane, Octane, Nonane, Decane, Undecane, Dodecane, Tridecane, Tetradecane, Pentadecane, Hexadecane, Cyclopentane, Cyclohexane Benzene, xylene, toluene Dichloromethane, dichloroethane, dichloropropane, chlorobutane, chloroform, chlorobenzene, dichlorobenzene Diethyl ether, diisopropyl ether, tert-butyl methyl ether, dibutyl ether, monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, 1,4-dioxane, tetrahydrofuran, Ethyl acetate, butyl acetate, Methyl ethyl ketone, acetone, Ethylene carbonate, propylene carbonate, At least one of acetonitrile and benzyl nitrile.

[0186] In the composition, when the organic solvent (ii) is mixed alone without combining with salt (i), water (iv), etc., in order to separate the mixture into two or more phases with different contents of the compound shown in formula (1), it is preferable that the solubility parameter (SP value) of the organic solvent (ii) is, for example, smaller than the solubility parameter of the compound shown in formula (2), preferably 8.2 (cal / cm³). 3 ) 1 / 2 the following.

[0187] Solubility parameters can be values ​​recorded in literature (e.g., CM Hansen, Ind. Eng. Chem. Prod. Res.Dev., 1969, 8(1), pp 2-11) or estimated values ​​calculated according to the methods recorded in literature (e.g., RF Fedors, Polym.Eng. Sci., 1974, 14(2), pp.147-154).

[0188] The following indicates a solubility parameter of 8.2 (cal / cm³). 3 ) 1 / 2 The following are non-limiting examples of organic solvents. The organic solvent (ii) preferably has a boiling point of 100°C or higher at atmospheric pressure, more preferably 110°C or higher, and even more preferably 120°C or higher. By using an organic solvent (ii) with a high boiling point at atmospheric pressure, the compound represented by formula (1) can be separated from the organic solvent (ii) with high efficiency.

[0189] The lower limit of the amount of organic solvent (ii) used relative to 1 mole of the compound shown in formula (1) is preferably 0.1 moles, more preferably 0.5 moles, and even more preferably 1 mole.

[0190] The upper limit of the amount of organic solvent (ii) used relative to 1 mole of the compound shown in formula (1) is preferably 10 moles, more preferably 5 moles, and even more preferably 2 moles.

[0191] The amount of organic solvent (ii) used is preferably in the range of 0.1 to 10 moles relative to 1 mole of the compound shown in formula (1), more preferably in the range of 0.5 to 5 moles, and even more preferably in the range of 1 to 2 moles.

[0192] The lower limit of the amount of organic solvent (ii) used relative to 100 parts by weight of the composition is preferably 30 parts by weight, more preferably 35 parts by weight, and even more preferably 40 parts by weight.

[0193] The upper limit of the amount of organic solvent (ii) used relative to 100 parts by weight of the composition is preferably 200 parts by weight, more preferably 150 parts by weight, and even more preferably 100 parts by weight.

[0194] The amount of organic solvent (ii) used relative to 100 parts by weight of the composition is preferably in the range of 30 to 200 parts by weight, more preferably in the range of 35 to 150 parts by weight, and even more preferably in the range of 40 to 100 parts by weight.

[0195] By using both salt (i) and organic solvent (ii), the compound shown in formula (2) can be removed more effectively. The types and amounts of salt (i) and organic solvent (ii) can be the same as above.

[0196] Step A is preferably a step of mixing the composition with salt (i) and / or organic solvent (ii) and water (iv) to obtain a mixture.

[0197] The minimum amount of water used relative to 100 parts by weight of the composition is preferably 10 parts by weight, more preferably 15 parts by weight, and even more preferably 20 parts by weight.

[0198] The upper limit of the amount of water used relative to 100 parts by weight of the composition is preferably 200 parts by weight, more preferably 150 parts by weight, and even more preferably 100 parts by weight.

[0199] The amount of water used relative to 100 parts by weight of the composition is preferably in the range of 10 to 200 parts by weight, more preferably in the range of 15 to 150 parts by weight, and even more preferably in the range of 20 to 100 parts by weight.

[0200] Water may be added to the composition separately from salt (i) and / or organic solvent (ii) and mixed, or it may be added to the composition together with salt (i) and / or organic solvent (ii) (e.g., in the case of salt (i), as an aqueous solution) and mixed.

[0201] Process A is carried out in a range of -15 to 40°C, more preferably in the range of -15 to 35°C, further preferably in the range of -15 to 30°C, even more preferably in the range of -15 to 20°C, particularly preferably in the range of -15 to 15°C, particularly more preferably in the range of -15 to 10°C, and most preferably in the range of -15 to 5°C.

[0202] Process B There are no particular restrictions on process B as long as it can separate the mixture obtained from process A into two or more phases with different contents of the compounds shown in formula (1). Process B can be carried out continuously or intermittently, in a single stage or in multiple stages, and can be carried out using common methods, such as separation, countercurrent contact, or centrifugal separators such as decanters.

[0203] In one embodiment, it is preferable to separate the mixture obtained in step A into an upper phase and a lower phase. Depending on the type of organic solvent (ii) and whether water (iv) is used, the phase with a high content of the compound shown in formula (1) is sometimes the upper phase and sometimes the lower phase.

[0204] In one embodiment, it is preferable to use specific gravity to separate the mixture obtained in step A, preferably separating it into a low specific gravity phase and a high specific gravity phase. In this embodiment, sometimes the low specific gravity phase is the phase with a high content of the compound shown in formula (1), and sometimes the high specific gravity phase is the phase with a high content of the compound shown in formula (1). For example, when the composition is mixed with water and an aprotic solvent (e.g., xylene) with a specific gravity less than that of water, the upper phase (aprotic solvent phase) may be the phase with a high content of the compound shown in formula (1), and the lower phase (aqueous phase) may be the phase with a low content of the compound shown in formula (1). In addition, when the composition is mixed with water and an aprotic solvent (e.g., dichloromethane) with a specific gravity greater than that of water, the upper phase (aqueous phase) may be the phase with a low content of the compound shown in formula (1), and the lower phase (aprotic solvent phase) may be the phase with a high content of the compound shown in formula (1).

[0205] In addition, when the composition is mixed with salt (i), the upper phase may be the phase with a high content of the compound shown in formula (1) and the lower phase may be the phase with a low content of the compound shown in formula (1).

[0206] In one embodiment, it is preferable to separate the mixture obtained in step A into an organic phase and an aqueous phase. In this embodiment, the organic phase is the phase with a high content of the compound represented by formula (1). The organic phase is sometimes the upper phase and sometimes the lower phase.

[0207] In one embodiment, the mixture obtained in step A is preferably separated using polarity, preferably into a low-polarity phase and a high-polarity phase. In this embodiment, the low-polarity phase is the phase with a high content of the compound represented by formula (1). The low-polarity phase is sometimes the upper phase and sometimes the lower phase.

[0208] The amount of compound (1) in the phase with the highest content of the compound (e.g., a low-density phase, a high-density phase, a low-polarity phase, or an organic phase) relative to the total amount of the compound (1) and the compound (2) (the content ratio of the compound (1)) can be higher than the content ratio of the compound (1) in the composition. In this phase, the mass ratio of the compound (1) to the compound (2) is preferably in the range of 80:20 to 99.9:0.1, more preferably in the range of 85:15 to 99:1.

[0209] In phases other than those described above (e.g., high-density or low-density phases, highly polar phases, or aqueous phases), the mass ratio of the compound represented by formula (1) to the compound represented by formula (2) is preferably in the range of 0.1:99.1 to 10:90, and more preferably in the range of 1:99 to 8:92. According to the method of the present invention, the loss of the compound represented by formula (1) is minimal, and the yield is also satisfactory.

[0210] Process B can be carried out within the same temperature range as process A.

[0211] Process C The purification method for the compound represented by formula (1) preferably includes the following steps: (C) a step of removing the phase with the lowest content of the compound represented by formula (1) (or the phase other than the phase with the highest content of the compound represented by formula (1)) from the separated phases, or a step of recovering the phase with the highest content of the compound represented by formula (1) (or the phase other than the phase with the lowest content of the compound represented by formula (1)). The method of the present invention can improve the transfer rate of the compound represented by formula (2) to the phase with the lowest content of the compound represented by formula (1) (e.g., a highly polar phase, an aqueous phase), and can highly remove the compound represented by formula (2).

[0212] Process C can be carried out within the same temperature range as process A.

[0213] Optional additional process The purification method of the compound shown in formula (1) may also include additional steps.

[0214] In one embodiment, the purification method of the compound represented by formula (1) may further include the following steps: (D) The step of mixing the phase removed in step C with salt (i) and / or organic solvent (ii), and optionally water (iv) to obtain a mixture; and (E) A process that separates the mixture obtained from step D into two or more phases with different contents of the compound shown in formula (1).

[0215] In this embodiment, the purification method of the compound represented by formula (1) may further include the following steps: (F) a step of removing the phase with the lowest content of the compound represented by formula (1) (or the phase other than the phase with the highest content of the compound represented by formula (1)) from the phase separated in step E, or a step of recovering the phase with the highest content of the compound represented by formula (1) (or the phase other than the phase with the lowest content of the compound represented by formula (1)).

[0216] Operations D, E, and F can be performed in the same manner as operations A, B, and C, respectively.

[0217] Processes D to F are processes for recovering the compound represented by formula (1) from the phase removed in process C. By replacing the phase removed in process C with the phase removed in process F, a series of processes D to F can be repeated.

[0218] The purification method of the compound shown in formula (1) may include the following steps in addition to steps D to F: (G) a step of mixing the phase obtained in step C with the phase obtained in step F.

[0219] In one embodiment, the purification method of the compound represented by formula (1) may include the following steps: (H) a step of concentrating the phase obtained in step C (or the phase obtained in step F or step G).

[0220] Regarding the concentration method of process H, there are no particular restrictions as long as it can increase the content of the compound shown in formula (1), such as vacuum distillation.

[0221] The content of organic solvent (ii) in the concentrate is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less.

[0222] In one embodiment, the purification method for the compound represented by formula (1) may further include the following steps: (I) a step of recovering the salt (i) and / or organic solvent (ii) used in the purification. The recovered salt (i) and / or organic solvent (ii) may be reused in steps A and / or D.

[0223] Composition In one embodiment, the composition is a composition containing the compound shown in formula (1), the compound shown in formula (2), and salt (i), wherein the content of salt (i) is less than 2% by mass (hereinafter referred to as "composition a").

[0224] The content of salt (i) in composition a is preferably 1% by mass or less, more preferably 0.5% by mass or less. The content of salt (i) in composition a can be, for example, above the detection limit.

[0225] In composition a, the mass ratio of the compound represented by formula (1) to the salt (i) is preferably in the range of 25:1 to 160:1, more preferably in the range of 30:1 to 120:1, and even more preferably in the range of 40:1 to 80:1.

[0226] In composition a, the mass ratio of the compound represented by formula (1) to the compound represented by formula (2) is preferably in the range of 80:20 to 99.9:0.1, and more preferably in the range of 85:15 to 99:1.

[0227] Composition a may also contain an organic solvent (ii). The content of the organic solvent (ii) in composition a may be, for example, less than 20% by mass, or more than 20% by mass, more than 25% by mass, or more than 30% by mass.

[0228] In composition a, the compound represented by formula (1), the compound represented by formula (2), the salt (i), and the organic solvent (ii) may be selected from the compounds described in the above "purification method".

[0229] Composition a can be manufactured, for example, by the method described in the above "refining method" including steps A to C and optional steps D to G.

[0230] In other embodiments, the composition is a composition containing the compound of formula (1) and an organic solvent (ii), wherein the content of the organic solvent (ii) is 20% by mass or less (hereinafter referred to as "composition b").

[0231] The content of organic solvent (ii) in composition b is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and even more preferably 1% by mass or less. The content of organic solvent (ii) in composition b can be, for example, above the detection limit.

[0232] Composition b may also contain the compound shown in formula (2). In this case, the mass ratio of the compound shown in formula (1) to the compound shown in formula (2) is preferably in the range of 80:20 to 99.9:0.1, and more preferably in the range of 85:15 to 99:1.

[0233] In composition b, the compound represented by formula (1), the compound represented by formula (2), and the organic solvent (ii) may be selected from the compounds described in the above "purification method".

[0234] Composition b can be manufactured by the method described in the above "refining method", including steps A to C, optional steps D to G and step H, or by a method of concentrating composition a.

[0235] Example The following describes one embodiment of the present invention in more detail using examples, but the present invention is not limited thereto.

[0236] Synthesis Example 1 Methyl monofluoroacrylate was synthesized according to the methods described in the examples and reference examples of Japanese Patent Publication No. 1-33098.

[0237] Example 1 (I) To 20 g of a mixed solution of 20% by mass methyl monofluoroacrylate and 80% by mass methanol obtained in Synthesis Example 1, 10.5 g each of 47% by mass calcium chloride aqueous solution and xylene were added at 0 °C. After thorough stirring, the upper and lower phases were separated and extracted separately. The upper phase was 13 g and the lower phase was 28 g.

[0238] The upper phase was analyzed using GC, NMR, Karl Fischer titration, and elemental analysis, and its composition was as follows.

[0239] <Photography> 24% by mass of monofluoroacrylate Methanol 3% by mass Xylene 73% by mass Water 568ppm Ca < 5 ppm Similarly, the lower phase is also analyzed, and it consists of the following components.

[0240] <Lower Phase> 3% by mass of monofluoroacrylate Methanol 56% by mass Xylene 4% by mass Water 20% by mass Ca 17% by mass (II) Add 17 g of xylene to the lower phase obtained in (I) above at 0 °C. After thorough stirring, separate and extract the upper and lower phases. The upper phase weighs 18 g and the lower phase weighs 27 g.

[0241] The upper phase was analyzed using GC, NMR, Karl Fischer titration, and elemental analysis, and its composition was as follows.

[0242] <Photography> 4.6% by mass of monofluoroacrylate Methanol 1.4% by mass Xylene 94% by mass Water 304ppm Ca < 5 ppm For the lower phase, GC analysis was used, and the lower phase has the following composition.

[0243] <Lower Phase> 2% by mass of monofluoroacrylate Methanol 98% by mass (III) The upper phase obtained in (I) above and the upper phase obtained in (II) above are mixed to obtain a mixture having the following composition.

[0244] <Mixed Liquid> 13% by mass of monofluoroacrylate Methanol 2% by mass Xylene 85% by mass Water 872ppm Ca < 5 ppm (The mass ratio of monofluoroacrylate to methanol is 87:13) (IV) The mixed solution obtained in (III) above was subjected to vacuum distillation. A fraction was obtained with a 99% recovery of methyl monofluoroacrylate. The fraction was analyzed by GC and NMR, and its composition was as follows.

[0245] <Friction> 84% by mass of monofluoroacrylate Methanol 15% by mass Xylene 1% by mass <Composition of the residue at the bottom of the vessel> 2% by mass of monofluoroacrylate Methanol 1% by mass Xylene 97% by mass Example 2 12 g of a 47% calcium chloride aqueous solution was added to 20 g of a mixed solution of 30% by mass of methyl monofluoroacrylate and 70% by mass of methanol obtained in Synthesis Example 1 at 0 °C. After thorough stirring, the upper and lower phases were separated and extracted separately.

[0246] The upper phase was analyzed using GC, NMR, Karl Fischer titration, and elemental analysis, and its composition was as follows.

[0247] <Photography> 92% by mass of monofluoroacrylate Methanol 8% by mass Ca < 5 ppm For the lower phase, GC analysis was used, and the lower phase has the following composition.

[0248] <Lower Phase> 4% by mass of monofluoroacrylate Methanol 60% by mass Water 28% by mass Ca 8% by mass Comparative Example 1 Add 10.5 g of water to 20 g of a mixed solution of 20% by mass of monofluoroacrylate and 80% by mass of methanol obtained in Synthesis Example 1 and stir to obtain a single-phase solution.

[0249] Example 3 As shown in Table 1, a mixed solution (bold) of 7.68% by mass of methyl monofluoroacrylate, 90.33% by mass of methanol (MeOH), 0.04% by mass of methyl fluoroacetate, 0.02% by mass of dimethyl carbonate (DMC), and 1.93% by mass of triethylamine (TEA) obtained in Synthesis Example 1 was added with 47% by mass of calcium chloride aqueous solution and extraction solvent. After thorough stirring, the upper and lower phases were separated and extracted. The compositions of the upper and lower phases were analyzed by GC, NMR, Karl Fischer titration, and elemental analysis. The compositions of each phase (excluding the extraction solvent) are shown in Table 2.

[0250] [Table 1] [Table 2] Example 4 As shown in Table 3, a mixed solution (bold) of 29.5% by mass of methyl monofluoroacrylate, 69.1% by mass of methanol, and 1.4% by mass of triethylamine (TEA) obtained in Synthesis Example 1 was taken into a spiral tube, and an inorganic salt was added. The solution was then shaken and mixed to dissolve the solution. Extraction solvent was added to this solution, and extraction was performed by shaking and mixing. The compositions of the upper and lower phases were analyzed using GC, NMR, Karl Fischer titration, and elemental analysis. The compositions of each phase (excluding the extraction solvent) are shown in Table 4.

[0251] [Table 3] [Table 4]

Claims

1. A method for purifying the compound represented by formula (1), characterized in that, include: (A) A step of mixing a composition containing the compound of formula (1) and the compound of formula (2) with (i) an organic solvent or (ii) a salt and the organic solvent to obtain a mixture, wherein the organic solvent does not contain the compound of formula (1) and the compound of formula (2); and (B) The step of separating the mixture into two or more phases having different contents of the compound represented by formula (1). In equation (1), R 1 and R 2 Whether the groups are the same or different, they can be alkyl, fluoroalkyl, aryl, halogen, or hydrogen atoms, which may have more than one substituent. R 3 It is an alkyl, fluoroalkyl, or aryl group that may have one or more substituents. X is a fluoroalkyl or halogen atom; R 4 -OH (2) In equation (2), R 4 It is an alkyl, fluoroalkyl, or aryl group that may have one or more substituents. The cation of the salt is a metal cation, the anion of the salt is a halide ion, and the organic solvent is an aprotic solvent, wherein the aprotic solvent does not include the compound shown in formula (1) and the compound shown in formula (2).

2. The method as described in claim 1, characterized in that: The cation of the salt comprises at least one selected from monovalent metal cations and divalent metal cations.

3. The method as described in claim 1 or 2, characterized in that: The salt is at least one selected from LiCl, LiBr, LiI, NaI, and CaCl2.

4. The method according to any one of claims 1 to 3, characterized in that: The amount of salt used is in the range of 0.1 to 10 moles relative to 1 mole of the compound shown in formula (1).

5. The method according to any one of claims 1 to 4, characterized in that: The organic solvent is an aprotic nonpolar solvent, wherein the aprotic nonpolar solvent does not include the compound shown in formula (1) and the compound shown in formula (2).

6. The method according to any one of claims 1 to 4, characterized in that: The organic solvent is selected from at least one of aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers, esters, ketones, carbonates and nitriles, wherein the esters do not include the compounds represented by formula (1).

7. The method according to any one of claims 1 to 4, characterized in that: The organic solvent is at least one selected from aromatic hydrocarbons and ethers.

8. The method according to any one of claims 1 to 4, characterized in that: The organic solvent is selected from C. 5－16 Alkanes, C 5－10 Cycloalkanes can have at least one carbon atom. 1－4 Alkyl benzene, C 1－6 Haloalkanes, benzene having at least one halogen atom, di(C) 1－4 Alkyl ether, C 2－4 Di(C) of alkylene glycols 1－4 Alkyl ethers, polycarbonate 2－4 Di(C) of alkylene glycols 1－4 Alkyl ethers, 5-membered oxygen-containing heterocycles, C 1－6 Alkanoic acid C 1－4 Alkyl esters, di(C 1－4 Alkyl ketones, C6 carbonate 2－4 alkylene esters, C 1－6 At least one of cyanoalkane and benzene having at least one cyano group.

9. The method according to any one of claims 1 to 4, characterized in that: The organic solvent is selected from... Pentane, Hexane, Heptane, Octane, Nonane, Decane, Undecane, Dodecane, Tridecane, Tetradecane, Pentadecane, Hexadecane, Cyclopentane, Cyclohexane Benzene, xylene, toluene Dichloromethane, dichloroethane, dichloropropane, chlorobutane, chloroform, chlorobenzene, dichlorobenzene Diethyl ether, diisopropyl ether, tert-butyl methyl ether, dibutyl ether, monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, 1,4-dioxane, tetrahydrofuran, Ethyl acetate, butyl acetate, Methyl ethyl ketone, acetone, Ethylene carbonate, propylene carbonate, At least one of acetonitrile and benzyl nitrile.

10. The method according to any one of claims 1 to 9, characterized in that: The amount of organic solvent used is in the range of 0.1 to 10 moles relative to 1 mole of the compound represented by formula (1).

11. The method according to any one of claims 1 to 10, characterized in that: Step (A) is a step of mixing the composition with (i) the organic solvent or (ii) the salt and the organic solvent, and (iii) water to obtain a mixture.

12. The method as described in claim 11, characterized in that: The amount of salt used is more than 150 mg relative to 1 mL of water.

13. The method as described in claim 11 or 12, characterized in that: The salt is LiCl, LiBr, LiI, NaI, or CaCl2. When the salt is LiCl, the amount of salt used is 150 mg or more per 1 mL of water. When the salt is LiBr, the amount of salt used is 310 mg or more per 1 mL of water. When the salt is LiI, the amount of salt used is 480 mg or more per 1 mL of water. When the salt is NaI, the amount of salt used is 540 mg or more per 1 mL of water. When the salt is CaCl2, the amount of salt used is 450 mg or more relative to 1 mL of water.

14. The method according to any one of claims 1 to 13, characterized in that: It also includes (C) the step of removing the phase containing the compound of formula (1) with the lowest content from the separated phase.

15. The method according to any one of claims 1 to 14, characterized in that: Implemented within the temperature range of -15 to 40°C.

16. The method according to any one of claims 1 to 15, characterized in that: R 1 It can be a hydrogen atom, an alkyl group, or a fluoroalkyl group.

17. The method according to any one of claims 1 to 16, characterized in that: R 2 It can be a hydrogen atom, an alkyl group, or a fluoroalkyl group.

18. The method according to any one of claims 1 to 17, characterized in that: R 3 It is an alkyl group.

19. The method according to any one of claims 1 to 18, characterized in that: R 3 C 1－4 alkyl.

20. The method according to any one of claims 1 to 19, characterized in that: R 4 It is an alkyl group.

21. The method according to any one of claims 1 to 20, characterized in that: R 4 C 1－4 alkyl.

22. The method according to any one of claims 1 to 21, characterized in that: X is a fluorine atom or a chlorine atom.

23. A composition, characterized in that: The composition contains a compound of formula (1) and at least one organic solvent selected from aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers, esters, ketones, carbonates and nitriles, having a boiling point of 100°C or higher at normal pressure. The content of the organic solvent is less than 20% by mass, wherein the ester does not include the compound of formula (1). In equation (1), R 1 and R 2 Whether the groups are the same or different, they can be alkyl, fluoroalkyl, aryl, halogen, or hydrogen atoms, which may have more than one substituent. R 3 It is an alkyl, fluoroalkyl, or aryl group that may have one or more substituents. X is a fluoroalkyl or halogen atom.

24. A composition, characterized in that: The composition contains the compound shown in formula (1), the compound shown in formula (2), and an organic solvent, wherein the SP value, i.e., the solubility parameter, of the organic solvent is less than the SP value of the compound shown in formula (2), and is 8.2 (cal / cm³). 3 ) 1 / 2 the following, In equation (1), R 1 and R 2 Whether the groups are the same or different, they can be alkyl, fluoroalkyl, aryl, halogen, or hydrogen atoms, which may have more than one substituent. R 3 It is an alkyl, fluoroalkyl, or aryl group that may have one or more substituents. X is a fluoroalkyl or halogen atom. R 4 -OH (2) In equation (2), R 4 It is an alkyl, fluoroalkyl, or aryl group that may have one or more substituents.

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