Purification method for halogenated (meth)acrylic acid esters

Abstract

A composition comprising a halogen-containing (meth)acrylic acid ester is provided. [Solution] Formula (1): TIFF2022101602000012.tif33129 (In the formula, R 1 and R 2 is an alkyl group, a fluoroalkyl group, an aryl group which may have one or more substituents, a halogen atom, or a hydrogen atom, and R 3 is an alkyl group, a fluoroalkyl group, or an aryl group which may have one or more substituents, and X is a fluoroalkyl group or a halogen atom.) and at least one organic solvent selected from undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, aromatic hydrocarbons, halogenated hydrocarbons, ethers, esters (excluding the compound represented by formula (1)), ketones, carbonates, and nitriles, wherein the content of the organic solvent is 20 mass % or less.

Description

[Technical Field]

[0001] This disclosure relates to a method for purifying halogenated (meth)acrylic acid esters. [Background technology]

[0002] Halogenated (meth)acrylic acid esters are useful as synthetic intermediates for pharmaceuticals (e.g., antibiotics), synthetic intermediates for sheath materials of optical fibers, synthetic intermediates for paint materials, synthetic intermediates for semiconductor resist materials, and monomers for functional polymers. In the production of halogenated (meth)acrylic acid esters, impurities may be present in the composition containing the target halogenated (meth)acrylic acid ester. Examples of impurities include reaction solvents (e.g., alcohols), catalysts, bases, and washing solvents (e.g., water). Of these, water, for example, can hydrolyze halogenated (meth)acrylic acid esters, potentially negatively affecting their stability. As a method for removing such water, a method is known that includes contacting a composition containing halogenated (meth)acrylic acid ester and water with a zeolite (Patent Document 1). Furthermore, a method for removing alcohol is known, for example, which includes a step of contacting a composition containing a halogenated (meth)acrylic acid ester and an alcohol with an acid anhydride (Patent Document 2). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2017-36272 [Patent Document 2] Japanese Patent Publication No. 2017-36270 [Overview of the project] [Problems that the invention aims to solve]

[0004] In the production of halogenated (meth)acrylic acid esters, alcohol may be present as an impurity in the composition containing the halogenated (meth)acrylic acid ester. Even if the composition is washed with water, the alcohol is not sufficiently removed. The method of contacting the composition with an acid anhydride has room for improvement, as it generates a large amount of waste and increases costs due to the large amount of acid anhydride used.

[0005] The object of this disclosure is to provide a method for purifying halogenated (meth)acrylic acid esters that can highly remove alcohol. [Means for solving the problem]

[0006] This disclosure encompasses the following aspects: Section 1. Formula (1): [ka] (In the formula, R 1 and R 2 These are, either identical or different, alkyl groups, fluoroalkyl groups, aryl groups which may have one or more substituents, halogen atoms, or hydrogen atoms. R 3 This is an alkyl group, a fluoroalkyl group, or an aryl group which may have one or more substituents. X is a fluoroalkyl group or a halogen atom. A method for purifying a compound represented by, (A) Compounds represented by formula (1) and formula (2): R 4 -OH (2) (In the formula, R 4 (This is an alkyl group, a fluoroalkyl group, or an aryl group which may have one or more substituents.) A composition containing a compound represented by the following: (i) Salt, (ii) Organic solvents (excluding compounds represented by formula (1) and compounds represented by formula (2)), (iii) the salt and the organic solvent A step of mixing with to obtain a mixture, and (B) A step of separating the mixture into two or more phases in which the content of the compound represented by formula (1) differs from one another. A method that includes this. Section 2. The method according to claim 1, wherein the salt is one or more selected from inorganic salts and organic salts. Section 3. The method according to item 1 or 2, wherein the salt is an inorganic salt. Section 4. The method according to any one of claims 1 to 3, wherein the cation of the salt is a metal cation, an ammonium which may have one or more substituents, a pyridinium which may have one or more substituents, an imidazolium which may have one or more substituents, or a phosphonium which may have one or more substituents. Section 5. The method according to any one of claims 1 to 4, wherein the cation of the salt comprises at least one selected from monovalent metal cations and divalent metal cations. Section 6. The cation of the salt is NR4 + The method according to any one of items 1 to 4, wherein each R may be the same or different from the others, and is H or an organic group having 1 to 10 carbon atoms. Section 7. The method according to any one of claims 1 to 6, wherein the anion of the salt comprises at least one selected from sulfate ions, hydroxide ions, halide ions, and nitrate ions. Section 8. The method according to any one of claims 1 to 5, wherein the salt is at least one selected from LiCl, LiBr, LiI, NaI, and CaCl2. Section 9. The method according to any one of claims 1 to 8, wherein the amount of salt used is in the range of 0.1 to 10 moles per mole of the compound represented by formula (1). Section 10. The method according to any one of items 1 to 9, wherein the organic solvent is an aprotic solvent (excluding the compound represented by the formula (1) and the compound represented by the formula (2)). Item 11. The method according to any one of items 1 to 10, wherein the organic solvent is an aprotic nonpolar solvent (excluding the compound represented by the formula (1) and the compound represented by the formula (2)). Method. Item 12. The method according to 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 (excluding the compound represented by the formula (1)), ketones, carbonates, and nitriles. Item 13. The method according to any one of items 1 to 10, wherein the organic solvent is at least one selected from aromatic hydrocarbons and ethers. Item 14. The organic solvent is C 5-16 alkane, C 5-10 cycloalkane, benzene optionally having at least one C 1-4 [[ID=2C]]alkyl group, C 1-6 haloalkane, benzene having at least one halogen atom, di(C 1-4 alkyl) ether, C 2-4 dialkyl ether of alkylene glycol, poly C 1-4 dialkyl ether of alkylene glycol, 5-membered oxygen-containing heterocycle, C 2-4 dialkyl ester of alkanoic acid C[[ID=C]] 1-4 alkyl ester, di(C 1-4 alkyl) ketone, C 2-4 alkylene carbonate, C 1-6 cyanoalkane, and at least one selected from benzene having at least one cyano group, the method according to any one of items 1 to 10. ​​​​​​​​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, t-butyl methyl ether, dibutyl ether, monoglime, diglyme, triglime, 1,4-dioxane, tetrahydrofuran, Ethyl acetate, butyl acetate, Methyl ethyl ketone, acetone, Ethylene carbonate, propylene carbonate, Acetonitrile and benzonitrile A method according to any one of items 1 to 10, wherein at least one is selected from the following. Section 16. The method according to any one of claims 1 to 15, wherein the amount of the organic solvent used is in the range of 0.1 to 10 moles per mole of the compound represented by formula (1). Section 17. Step (A) involves the composition, (i) Salt, (ii) Organic solvents (excluding compounds represented by formula (1) and compounds represented by formula (2)), (iii) the salt and the organic solvent, and (iv) water The method according to any one of claims 1 to 16, which involves mixing with to obtain a mixture. Section 18. The method according to item 17, wherein the amount of salt used is 150 mg or more per 1 mL of water. Section 19. The salt is LiCl, LiBr, LiI, NaI, or CaCl2. If the salt is LiCl, the amount of salt used is 150 mg or more per 1 mL of water. the law of nature, If the salt is LiBr, the amount of salt used is 310 mg or more per 1 mL of water. If the salt is LiI, the amount of salt used is 480 mg or more per 1 mL of water. If the salt is NaI, the amount of salt used is 540 mg or more per 1 mL of water. If the salt is CaCl2, the amount of salt used is 450 mg or more per 1 mL of water. The method described in paragraph 17 or 18. Section 20. (C) A step of removing the phase with the lowest content of the compound represented by formula (1) from the separated phases. The method described in any one of items 1 to 19, further including the method described in any one of items 1 to 19. Section 21. The method described in any one of items 1 to 20, carried out within the range of -15 to 40°C. Section 22. R 1 The method according to any one of claims 1 to 21, wherein is a hydrogen atom, an alkyl group, or a fluoroalkyl group. Section 23. R 2 The method according to any one of claims 1 to 22, wherein the atom is a hydrogen atom, an alkyl group, or a fluoroalkyl group. Section 24. R 3 The method according to any one of items 1 to 23, wherein the alkyl group is an alkyl group. Section 25. R 3 However, C 1-4 The method according to any one of items 1 to 24, wherein the alkyl group is an alkyl group. Section 26. R 4 The method according to any one of items 1 to 25, wherein the alkyl group is an alkyl group. Section 27. R 4 However, C 1-4 The method according to any one of items 1 to 26, wherein the alkyl group is an alkyl group. Section 28. The method according to any one of claims 1 to 27, wherein X is a fluorine atom or a chlorine atom. Section 29. Formula (1): [ka] (In the formula, R 1 and R 2 These are, either identical or different, alkyl groups, fluoroalkyl groups, aryl groups which may have one or more substituents, halogen atoms, or hydrogen atoms. R 3 This is an alkyl group, a fluoroalkyl group, or an aryl group which may have one or more substituents. X is a fluoroalkyl group or a halogen atom. Compounds represented by formula (2): R 4 -OH (2) (In the formula, R 4 (This is an alkyl group, a fluoroalkyl group, or an aryl group which may have one or more substituents.) A composition containing a compound represented by and a salt thereof, A composition having a salt content of 2% by mass or less. Section 29a. The composition according to item 29, wherein the salt is the salt described in item 2, 3, or 8. Section 29b. The cation of the salt is a cation described in any one of items 4 to 6, and / or The anion of the salt is the anion described in item 7. The composition described in item 29. Section 29c. The composition according to claim 29, 29a, or 29b, further comprising an organic solvent. Section 29d. The composition according to item 29c, wherein the organic solvent is an organic solvent according to any one of items 10 to 15. Section 29e. R 1 The composition according to any one of items 29 and 29a to d, wherein the atom is a hydrogen atom, an alkyl group, or a fluoroalkyl group. Section 29f. R2 The composition according to any one of items 29 and 29a to e, wherein the atom is a hydrogen atom, an alkyl group, or a fluoroalkyl group. Section 29g. R 3 The composition according to any one of items 29 and 29a to f, wherein the alkyl group is an alkyl group. Section 29h. R 3 However, C 1-4 A composition according to any one of items 29 and 29a to g, wherein the alkyl group is an alkyl group. Section 29i. R 4 The composition according to any one of items 29 and 29a-h, wherein the alkyl group is an alkyl group. Section 29j. R 4 However, C 1-4 A composition according to any one of items 29 and 29a to i, wherein the alkyl group is an alkyl group. Section 29k. The composition according to any one of items 29 and 29a to j, wherein X is a fluorine atom. Section 30. Formula (1): [ka] (In the formula, R 1 and R 2 These are, either identical or different, alkyl groups, fluoroalkyl groups, aryl groups which may have one or more substituents, halogen atoms, or hydrogen atoms. R 3 This is an alkyl group, a fluoroalkyl group, or an aryl group which may have one or more substituents. X is a fluoroalkyl group or a halogen atom. Compounds represented by, as well as aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, A A composition containing at least one organic solvent selected from tel, ester (excluding the compound represented by formula (1) above), ketone, carbonate, and nitrile, wherein the content of the organic solvent is 20% by mass or less. Section 30a. Furthermore, equation (2): R 4 -OH (2) (In the formula, R 4 (This is an alkyl group, a fluoroalkyl group, or an aryl group which may have one or more substituents.) The composition according to item 30, comprising a compound represented by [the specified compound]. Section 30b. R 1 The composition according to item 30 or 30a, wherein the atom is a hydrogen atom, an alkyl group, or a fluoroalkyl group. Section 30c. R 2 The composition according to item 30, 30a, or 30b, wherein the component is a hydrogen atom, an alkyl group, or a fluoroalkyl group. Section 30d. R 3 The composition according to any one of items 30 and 30a to c, wherein the alkyl group is an alkyl group. Section 30e. R 3 However, C 1-4 A composition according to any one of claims 30 and 30a to d, wherein the alkyl group is an alkyl group. Section 30f. R 4 The composition is an alkyl group, as described in any one of items 30a to e. Item 30g. R 4 However, C 1-4 A composition according to any one of items 30a to f, wherein the alkyl group is an alkyl group. Section 30h. The composition according to any one of items 30 and 30a to g, wherein X is a fluorine atom. [Effects of the Invention]

[0007] This disclosure provides a method for purifying halogenated (meth)acrylic acid esters that can highly remove alcohol. [Modes for carrying out the invention]

[0008] The foregoing summary of this disclosure is not intended to describe each of the disclosed embodiments or all implementations of this disclosure. The following description in this disclosure provides more specific examples of the embodiments. In several places in this disclosure guidance is provided through examples, and these examples can be used in various combinations. In each case, the exemplary group can function as a non-exclusive and representative group. All publications, patents, and patent applications cited herein are incorporated herein by direct reference.

[0009] term Unless otherwise specified, symbols and abbreviations used herein should be understood in the context of this specification and in the art to which this disclosure belongs as commonly used. In this specification, the phrase "contains" is used to include the phrases "essentially consist of" and "consist of". Unless otherwise specified, the processes, treatments, or operations described herein may be carried out at room temperature. In this specification, room temperature can mean a temperature within the range of 10 to 40°C. In this specification, the notation "C n-m (where n and m are numbers, respectively) represents, as is commonly understood by those skilled in the art, that the number of carbon atoms is n or greater and m or less.

[0010] In this specification, "halogen atoms" include, for example, fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0011] In this specification, "organic group" means a group containing one or more carbon atoms. Examples of such "organic groups" are: Alkyl molecules which may have one or more substituents, An alkenyl group which may have one or more substituents, An alkynyl group which may have one or more substituents, An aryl group which may have one or more substituents, An aralkyl group which may have one or more substituents, A non-aromatic heterocyclic group which may have one or more substituents, A heteroaryl group which may have one or more substituents, Cyano group, Aldehyde group, Carboxyl group, 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 molecules which may have one or more substituents, An alkenyl group which may have one or more substituents, An alkynyl group which may have one or more substituents, An aryl group which may have one or more substituents, An aralkyl group which may have one or more substituents, A non-aromatic heterocyclic group which may have one or more substituents, or (This is a heteroaryl group that may have one or more substituents.) It can include.

[0012] In this specification, "hydrocarbon group" can include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, aralkyl groups, and combinations thereof.

[0013] In this specification, "alkyl group" may be a linear, branched, or cyclic alkyl group. In this specification, "alkyl group" means, for example, C 1-20 Alkyl alkyl group, C 1-12 Alkyl alkyl group, C 1-6 Alkyl alkyl group, C1-4 Alkyl alkyl group, or C 1-3 It can be an alkyl group. In this specification, "alkyl group" refers to linear or branched alkyl groups such as methyl group, ethyl group, propyl group (n-propyl group, isopropyl group), butyl group (n-butyl group, isobutyl group, sec-butyl group, tert-butyl group), pentyl group, and hexyl group. In this specification, "alkyl group" refers to a cyclic alkyl group or cycloalkyl group (e.g., C) such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. 3-8 Examples include cycloalkyl groups.

[0014] In this specification, "fluoroalkyl group" refers to an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. In this specification, the number of fluorine atoms in a "fluoroalkyl group" can be one or more (e.g., 1 to 3, 1 to 6, 1 to 12, or the maximum number that can be substituted from 1). In this specification, "fluoroalkyl group" means, for example, C 1-20 Fluoroalkyl groups, C 1-12 Fluoroalkyl groups, C 1-6 Fluoroalkyl groups, C 1-4 Fluoroalkyl groups, or C 1-3 It can be a fluoroalkyl group. In this specification, "fluoroalkyl group" may be a linear or branched fluoroalkyl group. In this specification, "fluoroalkyl group" may be a perfluoroalkyl group or a non-perfluoroalkyl group. In this specification, "fluoroalkyl group" refers to, for example, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, a tetrafluoropropyl group (e.g., HCF2CF2CH2-), a hexafluoropropyl group (e.g., (CF3)2CH-), a nonafluorobutyl group, an octafluoropentyl group (e.g., HCF2CF2CF2CF2CH2-), and a tridecafluorohexyl group.

[0015] In this specification, "alkenyl group" means, for example, C 2-10 It can be an alkenyl group. In this specification, "alkenyl group" refers to linear or branched alkenyl groups such as vinyl group, 1-propen-1-yl group, 2-propen-1-yl group, isopropenyl group, 2-buten-1-yl group, 4-penten-1-yl group, and 5-hexen-1-yl group. In this specification, "alkenyl group" refers to a cyclic alkenyl group or cycloalkenyl group (e.g., C) such as a cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, or cycloheptenyl group. 3-8 Examples include cycloalkenyl groups.

[0016] In this specification, "alkynyl group" means, for example, C 2-10 It can be an alkynyl group. In this specification, "alkynyl group" refers to linear or branched alkynyl groups such as ethynyl, 1-propyne-1-yl, 2-propyne-1-yl, 4-pentin-1-yl, and 5-hexyne-1-yl.

[0017] In this specification, the "aryl group" may be, for example, monocyclic, dicyclic, tricyclic, or tetracyclic. In this specification, "aryl group" means, for example, C 6-18 Aryl group, C 6-16 Aryl group, C 6-14 Aryl group, or C 6-12 It can be an aryl group. In this specification, "aryl group" refers to, for example, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-biphenyl group, a 3-biphenyl group, a 4-biphenyl group, and a 2-anthuryl group.

[0018] In this specification, "aralkyl group" means, for example, C 7-19 Aralkyl group, C 7-17 Aralkyl group, C 7-15 Aralkyl group, or C 7-13 It can be an aralkyl group. In this specification, "aralkyl group" can include, for example, a benzyl group, a phenethyl group, a diphenylmethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 2,2-diphenylethyl group, a 3-phenylpropyl group, a 4-phenylbutyl group, a 5-phenylpentyl group, a 2-biphenylylmethyl group, a 3-biphenylylmethyl group, and a 4-biphenylylmethyl group.

[0019] In this specification, the "non-aromatic heterocyclic group" may be, for example, monocyclic, dicyclic, tricyclic, or tetracyclic. In this specification, "non-aromatic heterocyclic group" can be, for example, a non-aromatic heterocyclic group containing, as ring constituent atoms, 1 to 4 heteroatoms selected from oxygen, sulfur, and nitrogen atoms in addition to carbon atoms. In this specification, the "non-aromatic heterocyclic group" may be saturated or unsaturated. In this specification, "non-aromatic heterocyclic group" can include, for example, tetrahydrofuryl group, oxazolidinyl group, imidazolinyl group, azilidinyl group, azetidinyl group, pyrrolidinyl group, piperidinyl group, azepanyl group, azocanyl group, piperazinyl group, diazepinyl group, diazocanyl group, tetrahydropyranyl group, morpholinyl group, thiomorpholinyl group, 2-oxazolidinyl group, dihydrofuryl group, dihydropyranyl group, and dihydroquinolyl group.

[0020] In this specification, "heteroaryl group" can 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).

[0021] In this specification, "5 or 6-membered monocyclic aromatic heterocyclic group" can include, for example, pyrrolyl group, furyl group, thienyl group, pyrazolyl group, imidazolyl group, isoxazolyl group, oxazolyl group, isothiazolyl group, thiazolyl group, triazolyl group, oxadiazolyl group, thiadiazolyl group, tetrazolyl group, pyridyl group, pyridadinyl group, pyrimidinyl group, pyrazinyl group, and the like.

[0022] In this specification, "5-18 member aromatic condensed heterocyclic group" can include, for example, isoindolyl group, indolyl group, benzofuranyl group, benzothienyl group, indazolyl group, benzimidazolyl group, 1,2-benzoisoxazolyl group, benzoxazolyl group, 1,2-benzoisothiazolyl group, benzothiazolyl group, isoquinolyl group, quinolyl group, synnolinyl group, phthalazinyl group, quinazolinyl group, quinoxalinyl group, pyrazolo[1,5-a]pyridyl group, imidazo[1,2-a]pyridyl group, etc.

[0023] In this specification, "R r "O-" indicates an alkoxy group, a cycloalkoxy group (e.g., cyclopentoxy group, cyclohexoxy group, etc.) 3-8 Cycloalkoxy groups, aryloxy groups (e.g., phenoxy group, naphthoxy group, etc.) 6-18 C(aryloxy group) and aralkyloxy group (e.g., benzyloxy group, phenethyloxy group, etc.) 7-19 It can contain an aralkyloxy group.

[0024] In this specification, "alkoxy group" may be a group in which an oxygen atom is bonded to an alkyl group (alkyl-O-). In this specification, "alkoxy group" may be a linear or branched alkoxy group. In this specification, examples of the "alkoxy group" include linear or branched C 1-20 alkoxy groups such as methoxy group, ethoxy group, propoxy group (n-propoxy group, isopropoxy group), butoxy group (n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group), pentyloxy group, and hexyloxy group.

[0025] In this specification, the "alkylthio group" can be a group in which a sulfur atom is bonded to an alkyl group (alkyl-S-). In this specification, the "alkylthio group" can be a linear or branched alkylthio group. In this specification, examples of the "alkylthio group" include, for example, methylthio group, ethylthio group, propylthio group (n-propylthio group, isopropylthio group), butylthio group (n-butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group), pentylthio group, and hexylthio group, etc., which are linear or branched C 1-20 alkylthio groups.

[0026] In this specification, "R r CO-" can include, for example, an alkylcarbonyl group [e.g., an (C 1-10 alkyl)carbonyl group such as acetyl group, propionyl group, butyryl group, etc.], an arylcarbonyl group [e.g., an (C 6-18 aryl)carbonyl group such as benzoyl group, naphthoyl group, etc.], and an aralkylcarbonyl group [e.g., an (C 7-19 aralkyl)carbonyl group such as benzylcarbonyl group, phenethylcarbonyl group, etc.].

[0027] In this specification, "R r COO-" can include, for example, an alkylcarbonyloxy group [e.g., an (C 1-10 alkyl)carbonyloxy group such as acetyloxy group, propionyloxy group, butyryloxy group, etc.], an arylcarbonyloxy group [e.g., an (C 6-18(C)carbonyloxy groups, such as aryl(carbonyl)oxy groups, and aralkylcarbonyloxy groups, such as benzylcarbonyloxy and phenethylcarbonyloxy groups. 7-19 It can contain an aralkyl (carbonyloxy) group.

[0028] In this specification, "R r "SO2-" is, for example, an alkyl sulfonyl group (e.g., methyl sulfonyl group, ethyl sulfonyl group, propyl sulfonyl group, etc.). 1-10 C(alkylsulfonyl group), arylsulfonyl group (e.g., phenylsulfonyl group, naphthylsulfonyl group, etc.) 6-18 Aryl sulfonyl groups, and aralkyl sulfonyl groups (e.g., benzyl sulfonyl group, phenethyl sulfonyl group, etc.) 7-19 It can include an aralkylsulfonyl group.

[0029] In this specification, "R r "OCO-" is, for example, an alkoxycarbonyl group [e.g., methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, etc. (C 1-10 (C) Carbonyl group (alkoxy) group, aryloxycarbonyl group (e.g., phenoxycarbonyl group, naphthoxycarbonyl group, etc.) 6-18 (C)(oxy)carbonyl groups, and aralkyloxycarbonyl groups [e.g., benzyloxycarbonyl group, phenethyloxycarbonyl group, etc.] 7-19 It can contain an aralkyloxy carbonyl group.

[0030] In this specification, "R r "OSO2-" is, for example, a C alkoxysulfonyl group (e.g., methoxysulfonyl group, ethoxysulfonyl group, propoxysulfonyl group, etc.). 1-10 Alkoxysulfonyl groups, aryloxysulfonyl groups (e.g., phenoxysulfonyl group, naphthoxysulfonyl group, etc.) 6-18 C(aryloxysulfonyl group) and aralkyloxysulfonyl group (e.g., benzyloxysulfonyl group, phenethyloxysulfonyl group, etc.) 7-19 It can include an aralkyloxysulfonyl group.

[0031] In this specification, "Hydrogen groups which may have one or more substituents", "An alkyl group which may have one or more substituents", "An alkenyl group which may have one or more substituents", "An alkynyl group which may have one or more substituents", "An aryl group which may have one or more substituents", "An aralkyl group which may have one or more substituents", "A non-aromatic heterocyclic group which may have one or more substituents," and "A heteroaryl group which may have one or more substituents" Examples of "substituents" in this context are, respectively, halo group, nitro group, cyano group, oxo group, thioxo group, carboxyl group, sulfo group, sulfamoyl group, sulfinamoyl group, sulfenamoyl group, R r O-, R r CO-, R r COO-, R r SO2-, R r OCO- and R r OSO2-(In these formulas, R r This is synonymous with the above. ) can be included. Examples of the substituents referred to as "halo groups" include fluoro groups, chloro groups, bromo groups, and iodine groups. The number of substituents can range from one to the maximum number that can be substituted (e.g., 1, 2, 3, 4, 5, 6).

[0032] Purification method One embodiment, formula (1): [ka] (In the formula, R 1 and R 2These are, either identical or different, alkyl groups, fluoroalkyl groups, aryl groups which may have one or more substituents, halogen atoms, or hydrogen atoms. R 3 This is an alkyl group, a fluoroalkyl group, or an aryl group which may have one or more substituents. X is a fluoroalkyl group or a halogen atom. The purification method for the compound represented by is: (A) Compounds represented by formula (1) and formula (2): R 4 -OH (2) (In the formula, R 4 (This is an alkyl group, a fluoroalkyl group, or an aryl group which may have one or more substituents.) A composition containing a compound represented by the following: (i) Salt, (ii) Organic solvents (excluding compounds represented by formula (1) and compounds represented by formula (2)), (iii) the salt and the organic solvent A step of mixing with to obtain a mixture, and (B) A step of separating the mixture into two or more phases in which the content of the compound represented by formula (1) differs from one another. Includes.

[0033] Process A The composition is not particularly limited as long as it contains the compound represented by formula (1) and the compound represented by formula (2). The composition may be, for example, the compound represented by formula (1) (crude form) containing the compound represented by formula (2) as an impurity.

[0034] In equation (1), R 1 Preferably, hydrogen atom, Alkyl alkyl group, or Fluoroalkyl groups And, moreover, hydrogen atom, C 1-20 Alkyl alkyl group (preferably C 1-12Alkyl alkyl groups, more C 1-6 Alkyl alkyl groups, more preferably C 1-4 Alkyl alkyl groups, more preferably C 1-3 alkyl group, Particularly preferred is a C1 or C2 alkyl group), or C 1-20 Fluoroalkyl groups (preferably C 1-12 Fluoroalkyl groups, ufC 1-6 Fluoroalkyl groups, more preferably C 1-4 Fluoroalkyl groups, more preferably C 1-3 Fluoroalkyl groups, particularly preferably C1 or C2 fluoroalkyl groups) And more preferably, hydrogen atom That is the case.

[0035] In equation (1), R 2 Preferably, hydrogen atom, Alkyl alkyl group, or Fluoroalkyl groups And, moreover, hydrogen atom, C 1-20 Alkyl alkyl group (preferably C 1-12 Alkyl alkyl groups, more C 1-6 Alkyl alkyl groups, more preferably C 1-4 Alkyl alkyl groups, more preferably C 1-3 Alkyl alkyl groups, particularly preferably C1 or C2 alkyl groups), or C 1-20 Fluoroalkyl groups (preferably C 1-12 Fluoroalkyl groups, ufC 1-6 Fluoroalkyl groups, more preferably C 1-4 Fluoroalkyl groups, more preferably C 1-3 Fluoroalkyl groups, particularly preferably C1 or C2 fluoroalkyl groups) And more preferably, hydrogen atom That is the case.

[0036] In equation (1), R3 R is preferably an alkyl group, more preferably a linear alkyl group. 3 Preferably C 1-20 Alkyl alkyl groups, more C 1-12 Alkyl alkyl groups, more preferably C 1-6 Alkyl alkyl groups, more preferably C 1-4 Alkyl alkyl groups, particularly preferably C 1-3 The alkyl group is more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

[0037] In equation (1), X is preferably, C 1-20 Fluoroalkyl groups (preferably C 1-12 Fluoroalkyl groups, ufC 1-6 Fluoroalkyl groups, more preferably C 1-4 Fluoroalkyl groups, more preferably C 1-3 Fluoroalkyl groups, particularly preferably C1 or C2 fluoroalkyl groups), Fluorine atom, or chlorine atom That is the case. X is more preferably a trifluoromethyl group, a fluorine atom, or a chlorine atom. X is more preferably a fluorine atom or a chlorine atom. X is, in particular, a fluorine atom.

[0038] In formula (1), preferably, R 3 However, C 1-20 Alkyl alkyl group (preferably C 1-12 Alkyl alkyl groups, more C 1-6 Alkyl alkyl groups, more preferably C 1-4 Alkyl alkyl groups, more preferably C 1-3 Alkyl group, particularly preferably methyl or ethyl group, and X is a trifluoromethyl group, a fluorine atom, or a chlorine atom.

[0039] In formula (1), more preferably, R 3 However, it is a methyl group or an ethyl group (preferably a methyl group), and X is a trifluoromethyl group, a fluorine atom, or a chlorine atom.

[0040] In formula (1), preferably, R 1 However, it is a hydrogen atom, R 2 However, it is a hydrogen atom, R 3 However, it is a methyl group or an ethyl group (preferably a methyl group), and X is either a fluorine atom or a chlorine atom.

[0041] The compound represented by formula (1) can be produced by known manufacturing methods or similar methods, or is commercially available. The compound represented by formula (1) can be produced, for example, by the manufacturing method described in Japanese Patent Publication No. 1-33098, International Publication No. 2014 / 034906, or by a method equivalent thereto.

[0042] In equation (2), R 4 R is preferably an alkyl group, more preferably a linear alkyl group. 4 Preferably C 1-20 Alkyl alkyl groups, more C 1-12 Alkyl alkyl groups, more preferably C 1-6 Alkyl alkyl groups, more preferably C 1-4 Alkyl alkyl groups, particularly preferably C 1-3 The alkyl group is more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

[0043] R 4 R 3 It may be the same or different, R 3 It is preferable that it be the same as [the other option].

[0044] The lower limit of the content of the compound represented by formula (1) in the composition can be preferably 5% by mass, more preferably 10% by mass, and even more preferably 15% by mass. The upper limit of the content of the compound represented by formula (1) in the composition can be preferably 50% by mass, more preferably 45% by mass, and even more preferably 40% by mass. The content of the compound represented by formula (1) in the composition can preferably be 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.

[0045] The lower limit of the content of the compound represented by formula (2) in the composition can be preferably 50% by mass, more preferably 55% by mass, and even more preferably 60% by mass. The upper limit of the content of the compound represented by formula (2) in the composition can be preferably 95% by mass, more preferably 90% by mass, and even more preferably 85% by mass. The content of the compound represented by formula (2) in the composition can preferably be 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.

[0046] In the composition, the mass ratio of the compound represented by formula (1) to the compound represented by formula (2) can preferably be 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.

[0047] The composition may contain one or more other substances in addition to the compound represented by formula (1) and the compound represented by formula (2). These other substances may include, for example, substances used in the production of the compound represented by formula (1) (e.g., catalysts, bases), by-products, etc.

[0048] When salt (i) is mixed with the composition, the content of the compound represented by formula (1) is adjusted relative to each other. It is preferable that the solution can be separated into two or more different phases. Salt (i) is inorganic It can be one or more selected from salts and organic salts, and preferably an inorganic salt.

[0049] Examples of the cation of salt (i) include metal cations and cations having one or more substituents. It may be an ammonium compound, a pyridinium compound which may have one or more substituents, an imidazolium compound which may have one or more substituents, or a phosphonium compound which may have one or more substituents.

[0050] Examples of metal cations include monovalent metal cations (e.g., alkali metals such as Li and Na), divalent metal cations (e.g., alkaline earth metals such as Ca), and trivalent metal cations (e.g., Group 13 metals of the periodic table such as Al).

[0051] Examples of ammonium compounds that may have one or more substituents include NR4. + (Each R may be the same or different from the others, and may be H or an organic group, and any two of them may be bonded to each other to form a ring which may have substituents.) R is preferably H or a hydrocarbon group (e.g., alkyl group, aryl group). Also, R may be H or an organic group having 1 to 10 carbon atoms (e.g., C 1-10 It is also preferable that R is an alkyl group. 1-10 It is also preferable that the group be a hydrocarbon group such as an alkyl group.

[0052] In pyridinium which may have one or more substituents, 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, 1, 2, or 3.

[0053] Imidazolium may have one or more substituents, and 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.

[0054] Phosphonium may have one or more substituents. Examples of substituents include alkyl groups, alkenyl groups, alkoxycarbonylalkyl groups, monoalkylaminoalkyl groups, dialkylaminoalkyl groups, cyanoalkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and heteroaryl groups. The number of substituents can be, for example, 1, 2, 3, or 4.

[0055] The cation of salt (i) can preferably be a metal cation.

[0056] Examples of anions for salt (i) include carbonate ions, bicarbonate ions, and carboxylic acid ions. Examples include sulfate ions, hydroxide ions, halide ions (e.g., bromide ions, chloride ions, iodide ions), and nitrate ions. The anion of salt (i) can preferably be a halide ion.

[0057] Salt (i) is preferably made from LiCl, LiBr, LiI, NaI, and CaCl2. It is at least one of the selected types.

[0058] When the composition is mixed with salt (i) and water (iv), the minimum amount of salt (i) used is 1 mL of water. The amount can preferably be 150 mg, and more preferably 170 mg. For example, if salt (i) is LiCl, the lower limit of the amount of salt (i) used can be preferably 150 mg, more preferably 170 mg, per 1 mL of water. When salt (i) is LiBr, the lower limit of the amount of salt (i) used can be preferably 310 mg, more preferably 350 mg, per 1 mL of water. When salt (i) is LiI, the lower limit of the amount of salt (i) used can be preferably 480 mg, more preferably 500 mg, and even more preferably 540 mg per 1 mL of water. When salt (i) is NaI, the lower limit of the amount of salt (i) used can be preferably 540 mg, more preferably 550 mg, even more preferably 600 mg, and even more preferably 610 mg per 1 mL of water. When salt (i) is CaCl2, the lower limit of the amount of salt (i) used can be preferably 400 mg, more preferably 450 mg, per 1 mL of water.

[0059] The upper limit of the amount of salt (i) used is preferably 1360 mg, more preferably 1360 mg per 1 mL of water. The amount can be 1350 mg, more preferably 1300 mg, even more preferably 1250 mg, and particularly preferably 1215 mg. For example, if salt (i) is LiCl, the upper limit of the amount of salt (i) used can be preferably 350 mg, more preferably 340 mg, per 1 mL of water. When salt (i) is LiBr, the upper limit of the amount of salt (i) used can be preferably 790 mg, more preferably 750 mg, and even more preferably 705 mg per 1 mL of water. When salt (i) is LiI, the upper limit of the amount of salt (i) used can be preferably 1220 mg, more preferably 1200 mg, even more preferably 1150 mg, even more preferably 1100 mg, and particularly preferably 1085 mg per 1 mL of water. When salt (i) is NaI, the upper limit of the amount of salt (i) used can be preferably 1360 mg, more preferably 1350 mg, even more preferably 1300 mg, even more preferably 1250 mg, and particularly preferably 1215 mg per 1 mL of water. When salt (i) is CaCl2, the upper limit of the amount of salt (i) used can be preferably 1000 mg, more preferably 950 mg, and even more preferably 900 mg per 1 mL of water.

[0060] The amount of salt (i) used is preferably in the range of 150 to 1360 mg per 1 mL of water. More preferably, the amount can be in the range of 170 to 1215 mg. For example, if salt (i) is LiCl, the amount of salt (i) used can be preferably in the range of 150 to 350 mg, more preferably in the range of 170 to 340 mg, per 1 mL of water. When salt (i) is LiBr, the amount of salt (i) used can be preferably in the range of 310 to 790 mg, more preferably in the range of 350 to 705 mg, per 1 mL of water. When salt (i) is LiI, the amount of salt (i) used can be preferably in the range of 480 to 1220 mg, more preferably in the range of 540 to 1085 mg, per 1 mL of water. When salt (i) is NaI, the amount of salt (i) used can be preferably in the range of 540 to 1360 mg, more preferably in the range of 610 to 1215 mg, per 1 mL of water. When salt (i) is CaCl2, the amount of salt (i) used can be preferably in the range of 400 to 1000 mg, more preferably in the range of 450 to 900 mg, per 1 mL of water.

[0061] When the concentration of salt (i) in a saturated aqueous solution at room temperature (e.g., 25°C) is A, it is preferably It can be used in an amount such that it is 0.5 × A or more, more preferably 0.7 × A or more, and even more preferably 0.8 × A or more. Also, salt (i) is preferably less than or equal to A. It can be used in various quantities.

[0062] The lower limit of the amount of salt (i) used is preferably 0 per mole of the compound represented by formula (1). It can be 0.1 mole, more preferably 0.5 moles. The upper limit for the amount of salt (i) used is preferably 1 per mole of the compound represented by formula (1). It can be 0 moles, more preferably 9 moles. The amount of salt (i) used is preferably 0.1 to 1 mole of the compound represented by formula (1). It can be in the range of 10 moles, more preferably in the range of 0.5 to 9 moles.

[0063] The lower limit of the amount of salt (i) used is preferably 10 parts by mass per 100 parts by mass of the composition. Preferably, it can be 15 parts by mass, and even more preferably 20 parts by mass. The upper limit of the amount of salt (i) used is preferably 100 parts by mass per 100 parts by mass of the composition. More preferably, it may be 95 parts by mass, and even more preferably 90 parts by mass. The amount of salt (i) used is preferably 10 to 100 parts by mass per 100 parts by mass of the composition. It can be within a range, preferably within the range of 15 to 95 parts by mass, and more preferably within the range of 20 to 90 parts by mass.

[0064] The organic solvent (ii) is not particularly limited, as long as it is not the compound represented by formula (1) or the compound represented by formula (2). Preferably, the organic solvent (ii) is a solvent that, when mixed with the composition, can separate into two or more phases with different concentrations of the compound represented by formula (1). The organic solvent (ii) can be, for example, an aprotic solvent, and specific examples include at least one solvent selected from aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers, esters (except the compound represented by formula (1)), ketones, carbonates, and nitriles.

[0065] Examples of aliphatic hydrocarbons include C 5-16 Alkanes (e.g., pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane), C 5-10Examples include cycloalkanes (e.g., cyclopentane, cyclohexane). Examples of aromatic hydrocarbons include, for example, at least one carbon atom. 1-4 Examples of benzenes that may have alkyl groups include benzene, xylene, toluene, and the like. Examples of halogen hydrocarbons include C 1-6 Examples include haloalkanes (e.g., dichloromethane, dichloroethane, dichloropropane, chlorobutane, chloroform) and benzenes having at least one halogen atom (e.g., chlorobenzene, dichlorobenzene). As for ether, for example, di(C) 1-4 Alkyl ethers (e.g., diethyl ether, diisopropyl ether, t-butyl methyl ether, dibutyl ether), C 2-4 Alkylene glycol (C 1-4 Alkyl ethers (e.g., monoglycerides), polycarbonate C 2-4 Alkylene glycol (C 1-4 Examples include alkyl ethers (e.g., diglyme, triglyme) and five-membered oxygen-containing heterocycles (e.g., 1,4-dioxane, tetrahydrofuran). Examples of esters (excluding compounds represented by formula (1)) include C 1-6 Alkanic Acid C 1-4 Examples include alkyl esters, with specific examples including ethyl acetate and butyl acetate. Examples of ketones include di(C) 1-4 Examples include alkyl ketones, with specific examples including methyl ethyl ketone and acetone. Examples of carbonates include C 2-4 Examples include alkylene carbonates, with specific examples including ethylene carbonate and propylene carbonate. For example, C 1-6 Examples include cyanoalkanes (e.g., acetonitrile) and benzenes having at least one cyano group (e.g., benzonitrile).

[0066] In one embodiment, organic solvent (ii) can preferably be an aprotic nonpolar solvent.

[0067] In one embodiment, the organic solvent (ii) may preferably be at least one selected from aromatic hydrocarbons and ethers.

[0068] In one embodiment, the organic solvent (ii) is preferably, C 5-16 Alkane, C 5-10 Cycloalkane, at least one C 1-4 Benzene, which may have an alkyl group, C 1-6 Haloalkanes, benzenes having at least one halogen atom, di(C) 1-4 Alkyl ether, C 2-4 Alkylene glycol (C 1-4 Alkyl ether, polyC 2-4 Alkylene glycol (C 1-4 Alkyl ether, 5-membered oxygen-containing heterocycle, C 1-6 Alkanic Acid C 1-4 Alkyl ester, di(C) 1-4 Alkyl ketone, C 2-4 Alkylene carbonate, C 1-6 Cyanoalkanes and benzenes having at least one cyano group It can be at least one of the following. In this embodiment, the organic solvent (ii) is more preferably, 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, t-butyl methyl ether, dibutyl ether, monoglime, diglyme, triglime, 1,4-dioxane, tetrahydrofuran, Ethyl acetate, butyl acetate, Methyl ethyl ketone, acetone, Ethylene carbonate, propylene carbonate, Acetonitrile and benzonitrile It can be at least one of the following.

[0069] The organic solvent (ii) is mixed into the composition alone, without being combined with salt (i), water (iv), etc. In the case of mixing, in order to separate the mixture into two or more phases with different concentrations of the compound represented by formula (1), it is preferable that the solubility parameter (SP value) of organic solvent (ii) is smaller than, for example, the solubility parameter of the compound represented by formula (2), which is 8.2 (cal / cm³). 3 ) 1 / 2 The following is preferable: Solubility parameters can be found, for example, in literature (e.g., CM Hansen, Ind. Eng. Chem. Prod. Res.). The values ​​may be those listed in Dev., 1969, 8(1), pp. 2-11, or estimates calculated using the methods described in the literature (e.g., RF Fedors, Polym. Eng. Sci., 1974, 14(2), pp. 147-154). Cut. The solubility parameter is 8.2 (cal / cm³). 3 ) 1 / 2 The following are some non-specific examples of organic solvents. TIFF0007848037000005.tif72131

[0070] The boiling point of organic solvent (ii) at atmospheric pressure is preferably 100°C or higher, more preferably 110°C or higher, and even more preferably 120°C or higher. By using organic solvent (ii) with a high boiling point at atmospheric pressure, the compound represented by formula (1) can be highly separated from organic solvent (ii).

[0071] The lower limit of the amount of organic solvent (ii) used can be preferably 0.1 moles, more preferably 0.5 moles, and even more preferably 1 mole per mole of the compound represented by formula (1). The upper limit of the amount of organic solvent (ii) used can be preferably 10 moles, more preferably 5 moles, and even more preferably 2 moles, per mole of the compound represented by formula (1). The amount of organic solvent (ii) used can be preferably in the range of 0.1 to 10 moles, more preferably in the range of 0.5 to 5 moles, and even more preferably in the range of 1 to 2 moles, per mole of the compound represented by formula (1).

[0072] The lower limit of the amount of organic solvent (ii) used can be preferably 30 parts by mass, more preferably 35 parts by mass, and even more preferably 40 parts by mass, per 100 parts by mass of the composition. The upper limit of the amount of organic solvent (ii) used may be preferably 200 parts by mass, more preferably 150 parts by mass, and even more preferably 100 parts by mass, per 100 parts by mass of the composition. The amount of organic solvent (ii) used may be preferably in the range of 30 to 200 parts by mass, preferably in the range of 35 to 150 parts by mass, and more preferably in the range of 40 to 100 parts by mass, per 100 parts by mass of the composition.

[0073] By using salt (i) and organic solvent (ii) in combination, the compound represented by formula (2) can be further processed. It can be removed to an even higher degree. The types and amounts of salt (i) and organic solvent (ii) used are as follows: It can be the same as the note.

[0074] Step A involves mixing the composition with salt (i) and / or organic solvent (ii), and water (iv). It is preferable that the process involves obtaining a mixture.

[0075] The lower limit of the amount of water used can be preferably 10 parts by mass, more preferably 15 parts by mass, and even more preferably 20 parts by mass, per 100 parts by mass of the composition. The upper limit of the amount of water used can be preferably 200 parts by mass, more preferably 150 parts by mass, and even more preferably 100 parts by mass, per 100 parts by mass of the composition. The amount of water used is preferably in the range of 10 to 200 parts by mass, preferably in the range of 15 to 150 parts by mass, and more preferably in the range of 20 to 100 parts by mass, per 100 parts by mass of the composition. It can be.

[0076] Water may be added to the composition separately from salt (i) and / or organic solvent (ii) and mixed together. They may be added to the composition together with salt (i) and / or organic solvent (ii) (for example, in the form of an aqueous solution in the case of salt (i)) and mixed.

[0077] Step A can be carried out preferably in the range of -15 to 40°C, more preferably in the range of -15 to 35°C, even more 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.

[0078] Process B Step B is not particularly limited as long as the mixture obtained in Step A can be separated into two or more phases with different concentrations of the compound represented by formula (1). Step B can be carried out in a continuous or batch process, in a single or multi-stage manner, and conventional methods such as liquid-liquid separatory, countercurrent contact, or centrifugation using a decanter can be employed.

[0079] 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 or not water (iv) is used, the phase with a higher content of the compound represented by formula (1) may become the upper phase or the lower phase. In one embodiment, it is preferable to separate the mixture obtained in step A by specific gravity, and it is preferable to separate it into a low-specific gravity phase and a high-specific gravity phase. In this embodiment, the low-specific gravity phase may be the phase with a high content of the compound represented by formula (1), or the high-specific gravity phase may be the phase with a high content of the compound represented by formula (1). For example, when the composition is mixed with an aprotic solvent (e.g., xylene) having a lower specific gravity than water and water, the upper phase (aprotic solvent phase) may be the phase with a high content of the compound represented by formula (1), and the lower phase (aqueous phase) may be the phase with a low content of the compound represented by formula (1). Also, when the composition is mixed with an aprotic solvent (e.g., dichloromethane) having a higher specific gravity than water and water, the upper phase (aqueous phase) may be the phase with a low content of the compound represented by formula (1), and the lower phase (aprotic solvent phase) may be the phase with a high content of the compound represented by formula (1). Furthermore, when the composition is mixed with salt (i), the upper phase contains the compound represented by formula (1). The lower phase can be a phase with a high concentration of the compound represented by formula (1), and the lower phase can be a phase with a low concentration of the compound represented by formula (1).

[0080] 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 may be the upper phase or the lower phase.

[0081] In one embodiment, it is preferable to separate the mixture obtained in step A by polarity, and more preferably to separate it 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 may be the upper phase or the lower phase.

[0082] In the phase with the highest content of the compound represented by formula (1) (e.g., low-density phase or high-density phase, low-polarity phase, or organic phase), the amount of the compound represented by formula (1) relative to the total amount of the compounds represented by formula (1) and formula (2) (the content ratio of the compound represented by formula (1)) can be higher than the content ratio of the compound represented by formula (1) in the composition. In the phase, the mass ratio of the compound represented by formula (1) to the compound represented by formula (2) can preferably be in the range of 80:20 to 99.9:0.1, and more preferably in the range of 85:15 to 99:1.

[0083] In phases other than those described above (e.g., high-density or low-density phase, high-polarity phase, or aqueous phase), the mass ratio of the compound represented by formula (1) to the compound represented by formula (2) can preferably be in the range of 0.1:99.1 to 10:90, and more preferably in the range of 1:99 to 8:92. The method disclosed herein exhibits minimal loss of the compound represented by formula (1) and is also superior in terms of yield.

[0084] Process B can be carried out within the same temperature range as process A.

[0085] Process C The purification method for the compound represented by formula (1) is as follows: (C) A step of removing the phase with the lowest content of the compound represented by formula (1) (or a 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 a phase other than the phase with the lowest content of the compound represented by formula (1)). It is preferable that the above be included. The method disclosed herein can increase 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., highly polar phase, aqueous phase), and can highly remove the compound represented by formula (2). Process C can be carried out within the same temperature range as process A.

[0086] Optional additional steps The purification method of the compound represented by formula (1) can further include additional steps.

[0087] In one embodiment, the purification method of the compound represented by formula (1) can further include the following steps: (D) A step of mixing the phase removed in step C with salt (i) and / or an organic solvent (ii), and optionally water (iv) to obtain a mixture, and (E) A step of separating the mixture obtained in step D into two or more phases with different contents of the compound represented by formula (1). In this embodiment, the purification method of the compound represented by formula (1) can further include the following steps: (F) A step of removing the phase with the lowest content of the compound represented by formula (1) among the phases separated in step E (or a phase other than the phase with the highest content of the compound represented by formula (1)), or a step of recovering the phase with the highest content of the compound represented by formula (1) (or a phase other than the phase with the lowest content of the compound represented by formula (1)).

[0088] Steps D, E, and F can be performed in the same manner as steps A, B, and C, respectively.

[0089] Steps D to F are steps of recovering the compound represented by formula (1) in the phase removed in step C. By using the phase removed in step F instead of the phase removed in step C of step D, a series of steps D to F may be repeatedly performed.

[0090] In addition to steps D to F, the purification method of the compound represented by formula (1) includes the following step: (G) A step of mixing the phase obtained in step C with the phase obtained in step F can be included.

[0091] In one embodiment, the purification method of the compound represented by formula (1) includes the following step: (H) A step of concentrating the phase obtained in step C (or the phase obtained in step F or step G) can be included.

[0092] The concentration method of Project H is not particularly limited as long as the content rate of the compound represented by Formula (1) can be increased, and examples thereof include vacuum distillation and the like. The content of the organic solvent (ii) in the concentrate can preferably be 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less.

[0093] In one embodiment, the purification method of the compound represented by Formula (1) further includes the following steps: (I) A step of recovering the salt (i) and / or the organic solvent (ii) used for purification can be included. The recovered salt (i) and / or organic solvent (ii) can be reused in Step A and / or Step D.

[0094] composition In one embodiment, the composition is a composition containing the compound represented by Formula (1), the compound represented by Formula (2), and the salt (i), and the content of the salt (i) is 2% by mass or less (hereinafter referred to as "Composition a").

[0095] The content of the salt (i) in Composition a can preferably be 1% by mass or less, more preferably 0.5% by mass or less. The content of the salt (i) in Composition a can be, for example, above the detection limit and can be present. 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 still more preferably in the range of 40:1 to 80:1.

[0096] 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, more preferably in the range of 85:15 to 99:1.

[0097] ​Composition a may further contain an organic solvent (ii). The content of organic solvent (ii) in composition a may be, for example, 20% by mass or less, or 20% by mass or more, 25% by mass or more, or 30% by mass or more.

[0098] In composition a, a compound represented by formula (1), a compound represented by formula (2), and salt (i) The organic solvent (ii) and the organic solvent (ii) can each be selected from those described in the "Purification Method" above.

[0099] Composition a can be produced, for example, by a method comprising steps A to C and any steps D to G described in the "purification method" above.

[0100] In another embodiment, the composition is a composition containing a compound represented by 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").

[0101] The content of organic solvent (ii) in composition b is preferably 15% by mass or less, more preferably 10% by mass or less, even more 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.

[0102] Composition b may further contain a compound represented by formula (2). In this case, 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. It is possible.

[0103] In composition b, the compound represented by formula (1), the compound represented by formula (2), and the organic solvent (ii) can each be selected from those described in the "purification method" above.

[0104] Composition b can be produced by a method including steps A to C, optional steps D to G, and step H described in the "Purification Method", or by a method of concentrating composition a.

Example

[0105] Hereinafter, an embodiment of the present disclosure will be described in more detail by way of examples, but the present disclosure is not limited thereto.

[0106] Synthesis Example 1 , methyl monofluorinated acrylate was synthesized according to the methods described in the examples and reference examples of Japanese Patent Publication No. 1-33098.

[0107] Example 1 (I) To 20 g of a mixed solution of 20% by mass of methyl monofluorinated acrylate obtained in Synthesis Example 1 and 80% by mass of methanol, 10.5 g each of a 47% by mass aqueous calcium chloride solution and xylene were added at 0 °C. After sufficient stirring, the upper and lower phases were separated respectively. The upper phase was 13 g and the lower phase was 28 g. The upper phase was analyzed by GC, NMR, Karl Fischer, and elemental analysis, and the upper phase had the following composition. <Upper phase> Methyl monofluorinated acrylate 24% by mass Methanol 3% by mass Xylene 73% by mass Water 568 ppm Ca <5 ppm Similarly, when the lower phase was analyzed, the lower phase had the following composition. <Lower phase> Methyl monofluorinated acrylate 3% by mass Methanol 56% by mass Xylene 4% by mass Water 20% by mass Ca 17% by mass

[0108] (II) 17 g of xylene was added to the lower phase obtained in (I) above at 0 °C. After sufficient stirring​ Next, the upper and lower phases were separated. The upper phase weighed 18g and the lower phase weighed 27g. Analysis of the upper phase by GC, NMR, Karl Fischer assay, and elemental analysis revealed the following composition. <Upper phase> Methyl monofluorinated acrylate 4.6% by mass Methanol 1.4% by mass Xylene 94% by mass Water 304ppm Ca < 5 ppm Analysis of the lower phase by GC revealed the following composition: <Lower phase> Methyl monofluorinated acrylate 2% by mass Methanol 98% by mass

[0109] (III) The upper phase obtained in (I) above and the upper phase obtained in (II) above were mixed to obtain a mixed solution having the following composition. <Mixed liquid> Methyl monofluorinated acrylate 13% by mass Methanol 2% by mass Xylene 85% by mass Water 872ppm Ca < 5 ppm (The mass ratio of methyl monofluorinated acrylate to methanol is 87:13)

[0110] (IV) The mixed solution obtained in (III) above was subjected to vacuum distillation. Monofluorinated acrylic acid A fraction was obtained with a methyl ester recovery rate of 99%. The fraction was analyzed by GC and NMR, and its composition was as follows. <Dividend> Methyl monofluorinated acrylate 84% by mass Methanol 15% by mass Xylene 1% by mass <Composition of residual material in the boiler> Methyl monofluorinated acrylate 2% by mass Methanol 1% by mass Xylene 97% by mass

[0111] Example 2 To 20 g of a mixed solution of 30% by mass of monofluorinated methyl acrylate and 70% by mass of methanol obtained in Synthesis Example 1, 12 g of 47% by mass aqueous calcium chloride solution was added at 0°C. After thorough stirring, the upper and lower phases were separated. Analysis of the upper phase by GC, NMR, Karl Fischer assay, and elemental analysis revealed the following composition. <Upper phase> Methyl monofluorinated acrylate 92% by mass Methanol 8% by mass Ca < 5 ppm Analysis of the lower phase by GC revealed the following composition: <Lower phase> Methyl monofluorinated acrylate 4% by mass Methanol 60% by mass Water 28% by mass Ca 8% by mass

[0112] Comparative Example 1 When 10.5 g of water was added to 20 g of a mixed solution of 20% by mass of monofluorinated methyl acrylate and 80% by mass of methanol obtained in Synthesis Example 1 and stirred, a one-phase solution was obtained.

[0113] Example 3 As shown in Table 1, 7.68% by mass of monofluorinated methyl acrylate obtained in Synthesis Example 1, Methanol (MeOH) 90.33% by mass, Methyl fluoroacetate 0.04% by mass, Dimethyl carbonate (DMC) 0.02% by mass, and A 1.93% by mass mixed solution (crude) of triethylamine (TEA) was mixed with a 47% by mass aqueous calcium chloride solution and an extraction solvent. After thorough stirring, the upper and lower phases were separated. The compositions of the upper and lower phases were analyzed by GC, NMR, Karl Fischer assay, and elemental analysis. The compositions of each phase (excluding the extraction solvent) are shown in Table 2.

[0114] [Table 1]

[0115] [Table 2]

[0116] Example 4 As shown in Table 3, a mixed solution (crude) of 29.5% by mass of monofluorinated methyl acrylate, 69.1% by mass of methanol, and 1.4% by mass of triethylamine (TEA) obtained in Synthesis Example 1 was taken into a screw tube, and the inorganic salt was added and shaken to dissolve it. Extraction solvent was added to this solution and shaken to perform extraction. The compositions of the upper and lower phases were analyzed by GC, NMR, Karl Fischer assay, and elemental analysis. The compositions of each phase (excluding the extraction solvent) are shown in Table 4.

[0117] [Table 3]

[0118] [Table 4]

Claims

1. Formula (1): 【Chemistry 1】 (In the formula, R １ and R ２ These are, either identical or different, a methyl group, an ethyl group, or a hydrogen atom. R ３ This is a methyl group or an ethyl group, X is either a fluorine atom or a chlorine atom. Compounds represented by, Formula (2): R ４ -OH (2) (In the formula, R ４ Compounds represented by (where C1-4 alkyl group is), At least one organic solvent selected from aromatic hydrocarbons and ethers A composition containing, The mass ratio of the compound represented by formula (1) to the compound represented by formula (2) is 85:15 to 99.9:0.

1. A composition wherein the organic solvent has a boiling point of 120°C or higher at normal pressure, and the content of the organic solvent is 1% by mass or more and 20% by mass or less.

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