Method for producing phosphate compounds

Abstract

To provide a novel phosphate compound production method which enables a highly pure phosphate compound to be produced extremely easily.SOLUTION: A phosphate compound production method comprises a step (I) for producing a phosphate compound of formula (C) by reacting a phosphate ester of formula (A) with a raw material salt of formula (B) [Z represents C or Si; M represents an alkali metal or the like; X1 and X2 each independently represent a C1-10 alkyl group, a halogen atom or the like; X3 to X5 each independently represent a C1-10 alkyl group or the like; X6 represents a halogen atom or the like; and n represents a natural number of 1-4].SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing a phosphate compound. More specifically, the present invention relates to a method for producing a phosphate compound, which can produce a high-purity phosphate compound in an extremely simple manner by reacting a phosphoric acid ester with a raw material salt. [Background technology]

[0002] Phosphate compounds are used in a wide range of applications, such as surfactants in cleaning compositions, pharmaceuticals, antistatic agents, flame retardants, and additives for secondary batteries (Patent Documents 1 to 4), and various methods for producing phosphate compounds have been developed for each application.

[0003] For example, Patent Document 5 discloses a method for producing a phosphoric acid diester salt as a phosphate compound. According to this production method, a phosphoric acid triester is hydrolyzed in the presence of water to produce a phosphoric acid diester, and then the phosphoric acid diester is reacted with a hydroxide such as sodium hydroxide or potassium hydroxide to produce a phosphoric acid diester salt. However, this production method requires a complicated process for separating the unreacted phosphoric acid triester, the alcohol by-produced during the hydrolysis of the phosphoric acid triester, and the reaction solvent used during the reaction of the phosphoric acid triester with the hydroxide. In addition, it is disclosed that the phosphoric acid triester as the starting material can be obtained by reacting, for example, a monohalophosphoric acid diester with a hydroxy compound in the presence of an organic base such as triethylamine, but since a salt of the organic base is by-produced, a process for removing the salt of the organic base is also required. Therefore, the production method of the phosphoric acid diester salt described in Patent Document 5 has many problems in industrial production in terms of purification and separation processes and waste disposal.

[0004] Patent Document 6 discloses a method for producing a monohalogenophosphate ester salt or a phosphoric acid diester salt. According to this production method, a dihalogenophosphate salt is reacted with an alcohol or the like and an alkali metal base or the like to produce a monohalogenophosphate ester salt or the like. However, the reaction is not easy to control, and a mixture with a phosphoric acid diester salt is obtained as a product. Therefore, isolation and purification of the monohalogenophosphate ester salt or the like is required, but these steps are extremely difficult. On the other hand, when a phosphoric acid diester salt is obtained, the product may contain a monohalophosphate ester salt or an alkali metal salt depending on the reaction substrate. In that case, a step for isolating the phosphoric acid diester salt is required, but the production process becomes complicated. In addition, since an excess amount of alcohol is used as a reaction substrate and a solvent, when separating the phosphoric acid diester salt from the product, a large amount of alcohol must be distilled off by vacuum drying, heat drying, or the like. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2007-332355 A [Patent Document 2] JP 2008-231026 A [Patent Document 3] WO2016 / 158258 publication [Patent Document 4] Japanese Patent Application Publication No. 8-138733 [Patent Document 5] JP 2017-36273 A [Patent Document 6] JP 2019-135215 A Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention has been made in consideration of the above problems, and an object of the present invention is to provide a novel method for producing a phosphate compound, which is capable of producing a high-purity phosphate compound by an extremely simple method. [Means for solving the problem]

[0007] In order to solve the above-mentioned problems, the method for producing a phosphate compound according to the present invention is characterized by including at least a step (I) of reacting a phosphate ester represented by the following chemical formula (A) with a raw material salt represented by the following chemical formula (B) to produce a phosphate compound represented by the following chemical formula (C).

[0008] [ka] [In the formula, Z represents a carbon atom or a silicon atom. 1 and X 2 each independently represents a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms and at least one of a halogen atom, a hetero atom, or an unsaturated bond, or an alkoxy group having 1 to 10 carbon atoms and at least one of a halogen atom, a hetero atom, or an unsaturated bond. 3 ~X 5 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms and having at least one of a halogen atom, a hetero atom, or an unsaturated bond, or an alkoxy group having 1 to 10 carbon atoms and having at least one of a halogen atom, a hetero atom, or an unsaturated bond, 3 ~X 5 At least one of the is either the hydrocarbon group having 1 to 10 carbon atoms or the alkoxy group having 1 to 10 carbon atoms.]

[0009] [ka] [In the formula, M represents an alkali metal, an alkaline earth metal, aluminum, a transition metal, or an onium. 6represents a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a haloacyloxy group, or a sulfonyloxy group (-SOY group: the Y represents a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrocarbon group having 1 to 10 carbon atoms and having at least one of a halogen atom, a hetero atom, or an unsaturated bond). The n represents a natural number of 1 to 4.

[0010] [ka] [In the formula, M represents the same cation species as in the chemical formula (B). 1 and X 2 represents the same functional group as in the above chemical formula (A). The above n represents the same valence as in the above chemical formula (B).

[0011] In the above-mentioned structure, when Z in the above-mentioned chemical formula (A) is a silicon atom, it is preferable to include a step (II) of reacting a phosphoric acid compound represented by the following chemical formula (D) with a silicon compound represented by the following chemical formula (E) to produce a phosphoric acid silyl ester represented by the following chemical formula (F).

[0012] [ka] [In the formula, M' represents a hydrogen atom, an alkali metal, an alkaline earth metal, a primary hydrocarbon group having 1 to 10 carbon atoms, a secondary hydrocarbon group having 1 to 10 carbon atoms, a primary hydrocarbon group having 1 to 10 carbon atoms and at least one of a halogen atom, a hetero atom, or an unsaturated bond, or a secondary hydrocarbon group having 1 to 10 carbon atoms and at least one of a halogen atom, a hetero atom, or an unsaturated bond. 1 and X 2 represents the same functional group as in the above chemical formula (A). The above n represents the same valence as in the above chemical formula (B).

[0013] [ka] [Wherein, X 3 ~X 5 represents the same functional group as that of the above chemical formula (A). 7 is a leaving group, and represents a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a haloacyloxy group, or a sulfonyloxy group (-SOY group: the above Y represents a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrocarbon group having 1 to 10 carbon atoms and having at least one of a halogen atom, a heteroatom, or an unsaturated bond).

[0014] [ka] [Wherein, X 1 ~X 5 represents the same functional group as that represented by the above chemical formula (A).

[0015] Furthermore, in the above-mentioned configuration, it is preferable that the silicon compound represented by the chemical formula (E) is a by-product produced in the above-mentioned step (I).

[0016] In the above-mentioned structure, the phosphoric acid compound is the X in the chemical formula (D). 1 and X 2 are each independently an alkoxy group having 1 to 10 carbon atoms, and the M' is a hydrogen atom, making it a phosphate diester.

[0017] In the above-mentioned configuration, the phosphoric acid compound is the X in the chemical formula (D). 1 and X 2 It is preferable that one of the above is a fluorine atom and the other is an alkoxy group having 1 to 10 carbon atoms, and the above M' is a hydrogen atom.

[0018] Further, in the above-mentioned configuration, the phosphoric acid compound is the X in the chemical formula (D). 1 and X 2 is a fluorine atom, and the M' is a hydrogen atom, it is preferably a difluorophosphoric acid.

[0019] In the above-mentioned structure, the silicon compound is the X in the chemical formula (E). 3 ~X 5 are each independently a hydrocarbon group having 1 to 6 carbon atoms, 7 is preferably a trialkylsilyl halide where is a halogen atom.

[0020] In the above-mentioned configuration, M in the chemical formula (B) is preferably a lithium atom, a sodium atom, a magnesium atom, 1-methyl-1-propylpyrrolidinium, or 1-ethyl-3-methylimidazolium.

[0021] In the above-mentioned configuration, at least one of the steps (I) and (II) can be carried out in the absence of a solvent.

[0022] In the above-mentioned configuration, at least one of the steps (I) and (II) can be carried out in a non-aqueous solvent.

[0023] Furthermore, in the above-mentioned configuration, it is preferable that the non-aqueous solvent is an aprotic organic solvent. Effect of the Invention

[0024] According to the present invention, by reacting a phosphate ester represented by the chemical formula (A) with a starting salt represented by the chemical formula (B), a phosphate compound represented by the chemical formula (C) can be produced with high purity in a much simpler and more efficient manner than conventional production methods. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] (Method of producing phosphate compounds) The method for producing a phosphate compound according to the present embodiment will be described below. The method for producing a phosphate compound of the present embodiment includes at least a step (I) of reacting a phosphate ester represented by chemical formula (A) with a raw material salt represented by chemical formula (B) to produce a phosphate compound represented by chemical formula (C), as shown in the chemical reaction formula below.

[0026] [ka]

[0027] The reaction in step (I) is carried out by reacting X of a phosphate ester with 3 X 4 X 5 The Z-group is exchanged with M of the raw salt to produce a phosphate compound, and a by-product (E') is also produced in an equimolar amount to the phosphate compound.

[0028] <Phosphate ester> The phosphate ester is represented by the following chemical formula (A).

[0029] [ka]

[0030] In the chemical formula (A), Z represents a carbon atom or a silicon atom.

[0031] In the chemical formula (A), 1 and X 2 each independently represents a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms and having at least one of a halogen atom, a hetero atom, or an unsaturated bond (hereinafter sometimes referred to as a "hydrocarbon group having a halogen atom, etc."), or an alkoxy group having 1 to 10 carbon atoms and having at least one of a halogen atom, a hetero atom, or an unsaturated bond (hereinafter sometimes referred to as an "alkoxy group having a halogen atom, etc.").

[0032] In this specification, the "number of carbon atoms" in a functional group means the total number of carbon atoms in the functional group unless otherwise specified. In addition, in this specification, for example, a "hydrocarbon group having 1 to 10 carbon atoms" is a general term for hydrocarbon groups having 1, 2, 3, ..., or 10 carbon atoms, and this has the same meaning in other functional groups in which the number of carbon atoms is specified, unless otherwise specified.

[0033] X 1 and X 2 In the above, examples of the hydrocarbon group having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms. Furthermore, the alkyl group having 1 to 10 carbon atoms is not particularly limited, and examples thereof include linear alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups, and cyclic alkyl groups such as cyclopentyl and cyclohexyl groups. 1 and X 2 In the above, the hydrocarbon group having 1 to 10 carbon atoms is preferably a hydrocarbon group having 1, 2, 3, 4, 5 or 6 carbon atoms, and more preferably a hydrocarbon group having 1, 2 or 3 carbon atoms.

[0034] X 1 and X 2 The alkoxy group having 1 to 10 carbon atoms in the formula is not particularly limited, and examples thereof include linear alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, and hexoxy group, cyclic alkoxy groups such as cyclopentoxy group, and cyclohexoxy group, phenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, and 3,5-dimethylphenoxy group. 1 and X 2 In the above, the alkoxy group having 1 to 10 carbon atoms is preferably an alkoxy group having 1, 2, 3, 4, 5 or 6 carbon atoms, and more preferably an alkoxy group having 1, 2 or 3 carbon atoms.

[0035] X 1 and X 2In the above, the hydrocarbon group having 1 to 10 carbon atoms and containing a halogen atom means a functional group in which part or all of the hydrogen atoms in the hydrocarbon group are substituted with halogen atoms. The halogen atoms represent fluorine, chlorine, bromine, and iodine atoms. 1 and X 2 In the above, the hydrocarbon group having 1 to 10 carbon atoms and containing a halogen atom is preferably a hydrocarbon group having 1, 2, 3, 4, 5 or 6 carbon atoms and containing a halogen atom, more preferably a hydrocarbon group having 1, 2 or 3 carbon atoms and containing a halogen atom.

[0036] X 1 and X 2 In the above, the hydrocarbon group having 1 to 10 carbon atoms and a heteroatom means a functional group in which some or all of the hydrogen and carbon in the hydrocarbon group are substituted with a heteroatom. The heteroatom represents an atom such as oxygen, nitrogen, or sulfur. 1 and X 2 In the above, the hydrocarbon group having a heteroatom of 1 to 10 carbon atoms is preferably a hydrocarbon group having a heteroatom of 1, 2, 3, 4, 5 or 6 carbon atoms, and more preferably a hydrocarbon group having a heteroatom of 1, 2 or 3 carbon atoms.

[0037] X 1 and X 2Specific examples of the hydrocarbon group having a halogen atom or a hetero atom in the above formula (I) include an iodomethyl group, a bromomethyl group, a chloromethyl group, a fluoromethyl group, a diiodomethyl group, a dibromomethyl group, a dichloromethyl group, a difluoromethyl group, a triiodomethyl group, a tribromomethyl group, a trichloromethyl group, a trifluoromethyl group, a 2-iodoethyl group, a 2-bromoethyl group, a 2-chloroethyl group, a 2-fluoroethyl group, a 1,2-diiodoethyl group, a 1,2-dibromoethyl group, a chain-like halogenated alkyl groups such as 2-iodocyclohexyl, 2-bromocyclohexyl, 2-chlorocyclohexyl, and 2-iodoethyl groups, 1,2-dichloroethyl, 1,2-difluoroethyl, 2,2-diiodoethyl, 2,2-dibromoethyl, 2,2-dichloroethyl, 2,2-difluoroethyl, 2,2,2-tribromoethyl, 2,2,2-trichloroethyl, 2,2,2-trifluoroethyl, and hexafluoro-2-propyl groups; Cyclic halogenated alkyl groups such as a fluorocyclohexyl group, a 2-iodophenyl group, a 2-bromophenyl group, a 2-chlorophenyl group, a 2-fluorophenyl group, a 3-iodophenyl group, a 3-bromophenyl group, a 3-chlorophenyl group, a 3-fluorophenyl group, a 4-iodophenyl group, a 4-bromophenyl group, a 4-chlorophenyl group, a 4-fluorophenyl group, a 2,6-diiodophenyl group, a 2,6-dibromophenyl group, a 2,6-dichlorophenyl group, a 2,6-difluorophenyl group, and halogenated aryl groups such as fluorophenyl group, 3,5-diiodophenyl group, 3,5-dibromophenyl group, 3,5-dichlorophenyl group, 3,5-difluorophenyl group, pentaiodophenyl group, pentabromophenyl group, pentachlorophenyl group, and pentafluorophenyl group; and heteroaryl groups such as 2-nitrophenyl group, 4-nitrophenyl group, 2,4-dinitrophenyl group, 2,6-dinitrophenyl group, and 3-amino-2-naphthyl group.

[0038] X 1 and X 2In the above, the hydrocarbon group having 1 to 10 carbon atoms and an unsaturated bond means, for example, a hydrocarbon group having 1 to 10 carbon atoms and a double bond or triple bond between carbon atoms. Furthermore, as the hydrocarbon group having an unsaturated bond, a hydrocarbon group having 1, 2, 3, 4 or 5 unsaturated bonds is preferable, and a hydrocarbon group having 1, 2 or 3 unsaturated bonds is more preferable.

[0039] X 1 and X 2 Specific examples of the hydrocarbon group having 1 to 10 carbon atoms and having an unsaturated bond include, for example, an ethenyl group, a 1-propenyl group, a 2-propenyl group, an isopropenyl group, a 2-methyl-2-propenyl group, a 2-butenyl group, a 3-butenyl group, a 3-methyl-2-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4- Pentenyl group, penta-1,4-dienyl group, penta-2,4-dienyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, hexa-1,3-dienyl group, hexa-1,5-dienyl group, hexa-2,4-dienyl group, hexa-2,5-dienyl group, hexa-3,5-dienyl group, and 3-methyl chain alkenyl groups such as aryl-hexa-2,4-dienyl group; cyclic alkenyl groups such as 1-cyclopentenyl group, 2-cyclopentenyl group, 2,4-cyclopentadienyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group; aryl groups such as phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group, 1-naphthyl group, and 2-naphthyl group; and chain alkynyl groups such as ethynyl group, 2-propynyl group, butynyl group, 2-butynyl group, 3-butynyl group, pentynyl group, 2-pentynyl group, 3-pentynyl group, and 4-pentynyl group.

[0040] X 1 and X 2In the above, the alkoxy group having 1 to 10 carbon atoms and a halogen atom means a functional group in which part or all of the hydrogen atoms in the alkoxy group are substituted with halogen atoms. Here, the halogen atom means fluorine, chlorine, bromine, and iodine atoms, as in the above case. 1 and X 2 In the above, the alkoxy group having 1 to 10 carbon atoms and containing a halogen atom is preferably an alkoxy group having 1, 2, 3, 4, 5 or 6 carbon atoms and containing a halogen atom, and more preferably an alkoxy group having 1, 2 or 3 carbon atoms and containing a halogen atom.

[0041] In addition, the X 1 and X 2 In the above, the alkoxy group having a heteroatom and a carbon number of 1 to 10 means a functional group in which part or all of the hydrogen and carbon in the alkoxy group are replaced with a heteroatom. Here, the heteroatom means an atom such as oxygen, nitrogen, and sulfur, as in the above case. 1 and X 2 In the above, the alkoxy group having 1 to 10 carbon atoms and a heteroatom is preferably an alkoxy group having 1, 2, 3, 4, 5 or 6 carbon atoms, and more preferably an alkoxy group having 1, 2 or 3 carbon atoms.

[0042] X 1 and X 2Specific examples of the alkoxy group having a halogen atom or a hetero atom in the above formula (I) include an iodomethoxy group, a bromomethoxy group, a chloromethoxy group, a fluoromethoxy group, a diiodomethoxy group, a dibromomethoxy group, a dichloromethoxy group, a difluoromethoxy group, a triiodomethoxy group, a tribromomethoxy group, a trichloromethoxy group, a trifluoromethoxy group, a 2-iodoethoxy group, a 2-bromoethoxy group, a 2-chloroethoxy group, a 2-fluoroethoxy group, a 1,2-diiodoethoxy group, a 1,2-dibro chain-type halogenated alkoxy groups such as 2-iodocyclohexyloxy group, 2-bromocyclohexyloxy group, 2-chlorocyclohexyloxy group, 2-iodo-2-propoxy group, 1,2-dichloroethoxy group, 1,2-difluoroethoxy group, 2,2-diiodoethoxy group, 2,2-dibromoethoxy group, 2,2-dichloroethoxy group, 2,2-difluoroethoxy group, 2,2,2-tribromoethoxy group, 2,2,2-trichloroethoxy group, 2,2,2-trifluoroethoxy group, and hexafluoro-2-propoxy group; and 2-fluorocyclohexyloxy group and other cyclic halogenated alkoxy groups, 2-iodophenoxy group, 2-bromophenoxy group, 2-chlorophenoxy group, 2-fluorophenoxy group, 3-iodophenoxy group, 3-bromophenoxy group, 3-chlorophenoxy group, 3-fluorophenoxy group, 4-iodophenoxy group, 4-bromophenoxy group, 4-chlorophenoxy group, 4-fluorophenoxy group, 2,6-diiodophenoxy group, 2,6-dibromophenoxy group, 2,6-dichlorophenoxy group, 2, Examples of halogenated aryl groups include 6-difluorophenoxy group, 3,5-diiodophenoxy group, 3,5-dibromophenoxy group, 3,5-dichlorophenoxy group, 3,5-difluorophenoxy group, pentaiodophenoxy group, pentabromophenoxy group, pentachlorophenoxy group, and pentafluorophenoxy group; and heteroaryl groups such as 2-nitrophenoxy group, 4-nitrophenoxy group, 2,4-dinitrophenoxy group, 2,6-dinitrophenoxy group, and 3-amino-2-naphthoxy group.

[0043] X 1 and X 2In the above, the alkoxy group having 1 to 10 carbon atoms and an unsaturated bond means, for example, an alkoxy group having a double bond or a triple bond between carbon atoms. Furthermore, the alkoxy group having an unsaturated bond is preferably an alkoxy group having 1, 2, 3, 4 or 5 unsaturated bonds, and more preferably an alkoxy group having 1, 2 or 3 unsaturated bonds.

[0044] X 1 and X 2 Specific examples of the alkoxy group having an unsaturated bond and having 1 to 10 carbon atoms include, for example, an ethenyloxy group, a 1-propenyloxy group, a 2-propenyloxy group, an isopropenyloxy group, a 2-methyl-2-propenyloxy group, a 2-butenyloxy group, a 3-butenyloxy group, a 3-methyl-2-butenyloxy group, a 1-pentenyloxy group, a 2-pentenyloxy group, a 3-pentenyloxy group, a 4-pentenyloxy group, and and 3-methyloxy, penta-1,4-dienyloxy, penta-2,4-dienyloxy, 1-hexenyloxy, 2-hexenyloxy, 3-hexenyloxy, 4-hexenyloxy, 5-hexenyloxy, hexa-1,3-dienyloxy, hexa-1,5-dienyloxy, hexa-2,4-dienyloxy, hexa-2,5-dienyloxy, hexa-3,5-dienyloxy, and 3-methyloxy. -hexa-2,4-dienyloxy group and other linear alkenyloxy groups; 1-cyclopentenyloxy group, 2-cyclopentenyloxy group, 2,4-cyclopentadienyloxy group, 1-cyclohexenyloxy group, 2-cyclohexenyloxy group, 3-cyclohexenyloxy group and other cyclic alkenyloxy groups; phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,6-dimethylphenoxy group, and aryloxy groups such as arylphenoxy group, 3,5-dimethylphenoxy group, 2,4,6-trimethylphenoxy group, 1-naphthoxy group and 2-naphthoxy group; and chain alkynyloxy groups such as ethynyloxy group, 2-propynyloxy group, butynyloxy group, 2-butynyloxy group, 3-butynyloxy group, pentynyloxy group, 2-pentynyloxy group, 3-pentynyloxy group and 4-pentynyloxy group.

[0045] X 1 and X 2 may be the same or different from each other. 1 and X 2 The functional groups listed above as the functional groups are merely examples, and the present embodiment is not limited to these.

[0046] X in the above chemical formula (A) 3 ~X 5 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydrocarbon group having a halogen atom or the like, or an alkoxy group having a halogen atom or the like. 3 ~X 5 At least one of the above is either the hydrocarbon group having 1 to 10 carbon atoms or the alkoxy group having 1 to 10 carbon atoms.

[0047] The hydrocarbon group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms, the hydrocarbon group having a halogen atom or the like, and the alkoxy group having a halogen atom or the like are 1 and X 2 This is the same as that described in , and therefore the details are omitted.

[0048] X 3 ~X 5 may be the same or different from each other. 3 ~X 5 The functional groups listed above as the functional groups are merely examples, and the present embodiment is not limited to these.

[0049] Specific examples of the phosphate ester represented by the chemical formula (A) include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, 2-ethylhexyl diphenyl phosphate, triallyl phosphate, tripropargyl phosphate, tris(2-butoxyethyl)phosphate, tris(2-chloroethyl)phosphate, ethyl bis(2,2,2-trifluoroethyl)phosphate, diethyl 2,2,2-trifluoroethyl phosphate, tris(2,2,2-trifluoroethyl)phosphate, tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphate, dimethyl fluorophosphate, diethyl fluorophosphate, dipropyl fluorophosphate, dibutyl fluorophosphate, and the like. phosphate, dipentyl fluorophosphate, dihexyl fluorophosphate, 2-ethylhexylphenyl fluorophosphate, diallyl fluorophosphate, dipropargyl fluorophosphate, bis(2-butoxyethyl)fluorophosphate, bis(2-chloroethyl)fluorophosphate, bis(2,2,2-trifluoroethyl)fluorophosphate, bis(1,1,1,3,3,3-hexafluoro-2-propyl)fluorophosphate, methyl difluorophosphate, ethyl difluorophosphate, propyl difluorophosphate, allyl difluorophosphate, propargyl difluorophosphate, 2-butoxyethyl difluorophosphate, 2-chloroethyl difluorophosphate, 2,2,2-trifluoroethyl difluorophosphate, 1,1,1,3,3,3-Hexafluoro-2-propyl difluorophosphate, dimethyl trimethylsilyl phosphate, diethyl trimethylsilyl phosphate, trimethylsilyl dipropyl phosphate, dibutyl trimethylsilyl phosphate, trimethylsilyl dipentyl phosphate, dihexyl trimethylsilyl phosphate, trimethylsilyl diphenyl phosphate, diallyl trimethylsilyl phosphate, trimethylsilyl dipropargyl phosphate, bis(2-butoxyethyl)trimethylsilyl phosphate, bis(2-chloroethyl)trimethylsilyl phosphate, bis(2,2,2-trifluoroethyl)trimethylsilyl phosphate, bis(1,1,1,3,3,3-hexafluoro-2-propyl)trimethylsilyl phosphate, methyl trimethylsilyl fluorophosphate, ethyl trimethylsilyl fluorophosphate, trimethylsilyl(propyl)fluorophosphate, butyl trimethylsilyl fluorophore phosphate, trimethylsilyl (pentyl) fluorophosphate, hexyl trimethylsilyl fluorophosphate, trimethylsilyl (phenyl) fluorophosphate, allyl trimethylsilyl fluorophosphate, trimethylsilyl (propargyl) fluorophosphate, 2-butoxyethyl trimethylsilyl fluorophosphate, 2-chloroethyl trimethylsilyl fluorophosphate, 2,2,2-trifluoroethyl trimethylsilyl fluorophosphate, 1,1,1,3,3,3-hexafluoro-2-propyl trimethylsilyl fluorophosphate, trimethylsilyl difluorophosphate, dimethylvinylsilyl difluorophosphate, dimethylphenylsilyl difluorophosphate, triethylsilyl difluorophosphate, cyclohexyldimethylsilyl difluorophosphate, triisopropylsilyl difluorophosphate, methyldiphenylsilyl difluorophosphate, etc. However, the phosphate ester represented by the chemical formula (A) is not limited to these compound groups.

[0050] <Raw material salt> The raw material salt is represented by the following chemical formula (B).

[0051] [ka]

[0052] In the chemical formula (B), M represents an alkali metal, an alkaline earth metal, aluminum, a transition metal, or an onium.

[0053] The alkali metal is not particularly limited, and examples thereof include Li, Na, K, Rb, and Cs. Among these alkali metals, Li, Na, and K are preferred from the viewpoint of availability, and Li and Na are more preferred from the viewpoint of versatility of phosphate compounds.

[0054] The alkaline earth metal is not particularly limited, and examples thereof include Be, Mg, Ca, Sr, and Ba. Among these alkaline earth metals, Mg, Ca, and Ba are preferred from the viewpoints of availability and safety, and Mg is more preferred from the viewpoint of versatility of phosphate compounds.

[0055] The transition metal is not particularly limited, and examples thereof include Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn. Among these transition metals, Ti, Mn, Fe, Co, Ni, and Cu are preferred from the viewpoint of availability.

[0056] The onium is not particularly limited, and examples thereof include primary ammonium, secondary ammonium, tertiary ammonium, quaternary ammonium, quaternary phosphonium, and sulfonium.

[0057] The primary ammonium is not particularly limited, and examples thereof include methylammonium, ethylammonium, propylammonium, isopropylammonium, etc. These may be used alone or in combination of two or more.

[0058] The secondary ammonium is not particularly limited, and examples thereof include dimethylammonium, diethylammonium, dipropylammonium, dibutylammonium, ethylmethylammonium, methylpropylammonium, butylmethylammonium, butylpropylammonium, and diisopropylammonium.

[0059] The tertiary ammonium is not particularly limited, and examples thereof include trimethylammonium, triethylammonium, tripropylammonium ammonium, tributylammonium, ethyldimethylammonium, diethylmethylammonium, triisopropylammonium, dimethylisopropylammonium, diethylisopropylammonium, dimethylpropylammonium, butyldimethylammonium, 1-methylpyrrolidinium, 1-ethylpyrrolidinium, 1-propylpyrrolidinium, 1-butylpropylpyrrolidinium, 1-methylimidazolium, 1-ethylimidazolium, 1-propylimidazolium, 1-butylimidazolium, pyrazolium, 1-methylpyrazolium, 1-ethylpyrazolium, 1-propylpyrazolium, 1-butylpyrazolium, and pyridinium.

[0060] The quaternary ammonium is not particularly limited, and examples thereof include aliphatic quaternary ammoniums, imidazoliums, pyridiniums, pyrazoliums, and pyridaziniums.

[0061] Furthermore, the aliphatic quaternary ammoniums are not particularly limited, and examples thereof include tetraethylammonium, tetrapropylammonium, tetraisopropylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, trimethylpropylammonium, trimethylisopropylammonium, tetrabutylammonium, butyltrimethylammonium, trimethylpentylammonium, hexyltrimethylammonium, 1-methyl-1-propylpyrrolidinium, 1-ethyl-1-methyl-pyrrolidinium, 1-butyl-1-methylpyrrolidinium, 1-ethyl-1-methyl-piperidinium, and 1-butyl-1-methylpiperidinium.

[0062] The imidazoliums are not particularly limited, and examples thereof include 1,3-dimethyl-imidazolium, 1-ethyl-3-methylimidazolium, 1-n-propyl-3-methylimidazolium, 1-n-butyl-3-methylimidazolium, and 1-n-hexyl-3-methylimidazolium.

[0063] The pyridiniums are not particularly limited, and examples thereof include 1-methylpyridinium, 1-ethylpyridinium, and 1-n-propylpyridinium.

[0064] The pyrazoliums are not particularly limited, and examples thereof include 1,2-dimethylpyrazolium, 2-ethyl-1-methylpyrazolium, 2-methyl-1-propylpyrazolium, 2-butyl-1-methylpyrazolium, 1-methylpyrazolium, 3-methylpyrazolium, 4-methylpyrazolium, 4-iodopyrazolium, 4-bromopyrazolium, 4-iodo-3-methylpyrazolium, 4-bromo-3-methylpyrazolium, and 3-trifluoromethylpyrazolium.

[0065] The pyridaziniums are not particularly limited, and examples thereof include 1-methylpyridazinium, 1-ethylpyridazinium, 1-propylpyridazinium, 1-butylpyridazinium, 3-methylpyridazinium, 4-methylpyridazinium, 3-methoxypyridazinium, 3,6-dichloropyridazinium, 3,6-dichloro-4-methylpyridazinium, 3-chloro-6-methylpyridazinium, and 3-chloro-6-methoxypyridazinium.

[0066] Of the oniums given as examples, tetraethylammonium, triethylmethylammonium, 1-methyl-1-propylpyrrolidinium, 1-ethyl-3-methylimidazolium, and the like are preferred from the viewpoints of availability and versatility.

[0067] X 6 Examples of the halogen atom in include fluorine, chlorine, bromine, and iodine atoms. Among these halogen atoms, chlorine, bromine, and iodine atoms are preferred from the viewpoints of high elimination ability and reuse of by-products.

[0068] X 6 The alkoxy group having 1 to 10 carbon atoms in the formula (I) is not particularly limited, and examples thereof include linear alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexoxy groups, cyclic alkoxy groups such as cyclopentoxy and cyclohexoxy groups, phenoxy, 3-methylphenoxy, 4-methylphenoxy, and 3,5-dimethylphenoxy groups. 6 In the above, the alkoxy group having 1 to 10 carbon atoms is preferably an alkoxy group having 1, 2, 3, 4, 5 or 6 carbon atoms, and more preferably an alkoxy group having 1, 2 or 3 carbon atoms.

[0069] X 6The haloacyloxy group in the above is not particularly limited, but is preferably a functional group having 1 to 7 carbon atoms and having one or more hydrogen atoms substituted with halogen atoms. Specific examples include an iodoacetyl group, a bromoacetyl group, a chloroacetyl group, a fluoroacetyl group, a diiodoacetyl group, a dibromoacetyl group, a dichloroacetyl group, a difluoroacetyl group, a triiodoacetyl group, a tribromoacetyl group, a trichloroacetyl group, a trifluoroacetyl group, a 3,3,3-triiodopropanoyl group, a 3,3,3-tribromopropanoyl group, a 3,3,3-trichloropropanoyl group, a 3,3,3-trifluoropropanoyl group, a pentaiodopropanoyl group, a pentabromopropanoyl group, a pentachloropropanoyl group, a pentafluoropropanoyl group, a 4,4,4-trifluoroacetyl group, a 5,5,6-trifluoroacetyl group, a 6,6,7-trifluoroacetyl group, a 7,7,8-trifluoroacetyl group, a 8,8,9-trifluoroacetyl group, a 9,9,10-trifluoroacetyl group, a 10,11,12-trifluoroacetyl group, a 12,13,14-trifluoroacetyl group, a 14,15,16-trifluoroacetyl group, a 16,17,18-trifluoroacetyl group, a 18,19,19-trifluoroacetyl group, a 19,18,19-trifluoroacetyl group, a 20,13,14-trifluoroacetyl group, a 21,14,15-trifluoroacetyl group, a 22,16,17-trifluoroacetyl group, a 23,18,19-trifluoroacetyl group, a 24,19,18-trifluoroacetyl group, a 25,20,25-trifluoroacetyl group, a 26,11,12-trifluoroacetyl group, a Examples of the halogen atom include iodobutanoyl group, 4,4,4-tribromobutanoyl group, 4,4,4-trichlorobutanoyl group, 4,4,4-trifluorobutanoyl group, 3,3,4,4,4-pentaiodobutanoyl group, 3,3,4,4,4-pentabromobutanoyl group, 3,3,4,4,4-pentachlorobutanoyl group, 3,3,4,4,4-pentafluorobutanoyl group, heptaiodobutanoyl group, heptabromobutanoyl group, heptachlorobutanoyl group, heptafluorobutanoyl group, pentaiodobenzoyl group, pentabromobenzoyl group, pentachlorobenzoyl group, and pentafluorobenzoyl group. The halogen atom represents fluorine, chlorine, bromine, and iodine.

[0070] X 6 The sulfonyloxy group in the above formula is represented by a -SO3Y group, where Y represents a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrocarbon group having 1 to 10 carbon atoms and having at least one of a halogen atom, a heteroatom, or an unsaturated bond.

[0071] The halogen atom in Y includes fluorine, chlorine, bromine and iodine atoms.

[0072] The hydrocarbon group having 1 to 10 carbon atoms in Y is not particularly limited, and examples thereof include chain alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, and octyl group, and cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, etc. The hydrocarbon group having 1 to 10 carbon atoms in Y is preferably a hydrocarbon group having 1, 2, 3, 4, 5, or 6 carbon atoms, and more preferably a hydrocarbon group having 1, 2, or 3 carbon atoms.

[0073] The hydrocarbon group having a halogen atom and a carbon number of 1 to 10 in Y means a functional group in which part or all of the hydrogen atoms in the hydrocarbon group are substituted with halogen atoms. The halogen atom represents a fluorine, chlorine, bromine, or iodine atom. The hydrocarbon group having a halogen atom and a carbon number of 1 to 10 in Y is preferably a hydrocarbon group having a halogen atom and a carbon number of 1, 2, 3, 4, 5, or 6, more preferably a hydrocarbon group having a halogen atom and a carbon number of 1, 2, or 3.

[0074] The hydrocarbon group having a heteroatom with 1 to 10 carbon atoms in Y means a functional group in which some or all of the hydrogen and carbon in the hydrocarbon group are substituted with a heteroatom. The heteroatom represents an atom such as oxygen, nitrogen, or sulfur. The hydrocarbon group having a heteroatom with 1 to 10 carbon atoms in Y is preferably a hydrocarbon group having a heteroatom with 1, 2, 3, 4, 5, or 6 carbon atoms, and more preferably a hydrocarbon group having a heteroatom with 1, 2, or 3 carbon atoms.

[0075] Specific examples of the hydrocarbon group having 1 to 10 carbon atoms and having a halogen atom or a hetero atom in Y include an iodomethyl group, a bromomethyl group, a chloromethyl group, a fluoromethyl group, a diiodomethyl group, a dibromomethyl group, a dichloromethyl group, a difluoromethyl group, a triiodomethyl group, a tribromomethyl group, a trichloromethyl group, a trifluoromethyl group, a 2-iodoethyl group, a 2-bromoethyl group, a 2-chloroethyl group, a 2-fluoroethyl group, a 1,2-diphenylmethyl group, a 2-phenylethyl ... Chain halogenated alkyl groups such as iodoethyl group, 1,2-dibromoethyl group, 1,2-dichloroethyl group, 1,2-difluoroethyl group, 2,2-diiodoethyl group, 2,2-dibromoethyl group, 2,2-dichloroethyl group, 2,2-difluoroethyl group, 2,2,2-tribromoethyl group, 2,2,2-trichloroethyl group, 2,2,2-trifluoroethyl group, and hexafluoro-2-propyl group; 2-iodocyclohexyl group, 2-bromocyclohexyl group, 2-chlorocyclohexyl group, cyclic halogenated alkyl groups such as 2-cyclohexyl and 2-fluorocyclohexyl groups, 2-iodophenyl group, 2-bromophenyl group, 2-chlorophenyl group, 2-fluorophenyl group, 3-iodophenyl group, 3-bromophenyl group, 3-chlorophenyl group, 3-fluorophenyl group, 4-iodophenyl group, 4-bromophenyl group, 4-chlorophenyl group, 4-fluorophenyl group, 2,6-diiodophenyl group, 2,6-dibromophenyl group, 2,6-dichlorophenyl group, 2, Examples of halogenated aryl groups include a 6-difluorophenyl group, a 3,5-diiodophenyl group, a 3,5-dibromophenyl group, a 3,5-dichlorophenyl group, a 3,5-difluorophenyl group, a pentaiodophenyl group, a pentabromophenyl group, a pentachlorophenyl group, and a pentafluorophenyl group; and heteroaryl groups such as a 2-nitrophenyl group, a 4-nitrophenyl group, a 2,4-dinitrophenyl group, a 2,6-dinitrophenyl group, and a 3-amino-2-naphthyl group.

[0076] The hydrocarbon group for Y having 1 to 10 carbon atoms and an unsaturated bond means, for example, a hydrocarbon group having 1 to 10 carbon atoms and a double bond or triple bond between carbon atoms. Furthermore, the hydrocarbon group having an unsaturated bond is preferably a hydrocarbon group having 1, 2, 3, 4 or 5 unsaturated bonds, and more preferably a hydrocarbon group having 1, 2 or 3 unsaturated bonds.

[0077] Specific examples of the hydrocarbon group having 1 to 10 carbon atoms and an unsaturated bond in Y include, for example, an ethenyl group, a 1-propenyl group, a 2-propenyl group, an isopropenyl group, a 2-methyl-2-propenyl group, a 2-butenyl group, a 3-butenyl group, a 3-methyl-2-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, 4-pentenyl group, penta-1,4-dienyl group, penta-2,4-dienyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, hexa-1,3-dienyl group, hexa-1,5-dienyl group, hexa-2,4-dienyl group, hexa-2,5-dienyl group, hexa-3,5-dienyl group and 3-methyl-1,3-dienyl group. chain alkenyl groups such as ethyl-hexa-2,4-dienyl group; cyclic alkenyl groups such as 1-cyclopentenyl group, 2-cyclopentenyl group, 2,4-cyclopentadienyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group; aryl groups such as phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group, 1-naphthyl group, and 2-naphthyl group; and chain alkynyl groups such as ethynyl group, 2-propynyl group, butynyl group, 2-butynyl group, 3-butynyl group, pentynyl group, 2-pentynyl group, 3-pentynyl group, and 4-pentynyl group.

[0078] Specific examples of the raw material salt represented by the chemical formula (B) include, for example, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, cesium fluoride, cesium chloride, cesium bromide, cesium iodide, magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, calcium fluoride, calcium chloride, calcium bromide, calcium iodide, aluminum fluoride, aluminum chloride, aluminum bromide, aluminum iodide, manganese chloride (II), manganese bromide (II), manganese iodide (II), nickel chloride (II), nickel bromide (II), nickel iodide (II), cobalt chloride (II), cobalt bromide (II), cobalt iodide (II), salt Examples of the copper(II) chloride, copper(II) bromide, copper(II) iodide, tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, triethylmethylammonium fluoride, triethylmethylammonium chloride, triethylmethylammonium bromide, triethylmethylammonium iodide, 1-propyl-1-methylpyrrolidinium fluoride, 1-propyl-1-methylpyrrolidinium chloride, 1-propyl-1-methylpyrrolidinium bromide, 1-propyl-1-methylpyrrolidinium iodide, 1-ethyl-3-methylimidazolium fluoride, 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium iodide, etc. However, the raw material salt represented by the chemical formula (B) is not limited to these compound groups.

[0079] The above n is a valence number and represents a natural number of 1 to 4.

[0080] <Phosphate compounds> The phosphate compound is represented by the following chemical formula (C):

[0081] [ka]

[0082] In the chemical formula (C), M represents the same cation species as in the chemical formula (A). 1 and X 2 represents the same functional group as in the above chemical formula (A), and therefore, detailed explanations of these will be omitted.

[0083] Specific examples of the phosphate compound represented by the chemical formula (C) include, for example, lithium diethyl phosphate, sodium diethyl phosphate, potassium diethyl phosphate, magnesium diethyl phosphate, calcium diethyl phosphate, aluminum diethyl phosphate, manganese diethyl phosphate (II), nickel diethyl phosphate (II), cobalt diethyl phosphate (II), copper diethyl phosphate (II), tetraethylammonium diethyl phosphate, triethylmethylammonium diethyl phosphate, 1-propyl-1-methylpyrrolidinium diethyl phosphate, 1-ethyl-3-methylimidazolium diethyl phosphate, lithium dipropyl phosphate, sodium dipropyl phosphate, potassium dipropyl phosphate, magnesium dipropyl phosphate, calcium dipropyl phosphate, aluminum dipropyl phosphate, manganese dipropyl phosphate (II), nickel dipropyl phosphate (II), cobalt dipropyl phosphate (II), copper dipropyl phosphate (II), tetraethylammonium dipropyl phosphate, triethylmethylammonium dipropyl phosphate, 1-propyl-1-methylpyrrolidinium diethyl phosphate, ammonium dipropyl phosphate, 1-ethyl-3-methylimidazolium dipropyl phosphate, lithium dibutyl phosphate, sodium dibutyl phosphate, potassium dibutyl phosphate, magnesium dibutyl phosphate, calcium dibutyl phosphate, aluminum dibutyl phosphate, manganese(II) dibutyl phosphate, nickel(II) dibutyl phosphate, cobalt(II) dibutyl phosphate, copper(II) dibutyl phosphate, tetraethylammonium dibutyl phosphate, triethylmethylammonium dibutyl phosphate, 1-propyl-1-methylpyrrolidinyl 1-ethyl-3-methylimidazolium dibutyl phosphate, lithium bis(2,2,2-trifluoroethyl)phosphate, sodium bis(2,2,2-trifluoroethyl)phosphate, potassium bis(2,2,2-trifluoroethyl)phosphate, magnesium bis(2,2,2-trifluoroethyl)phosphate, calcium bis(2,2,2-trifluoroethyl)phosphate, aluminum bis(2,2,2-trifluoroethyl)phosphate, manganese(II) bis(2,2,2-trifluoroethyl)phosphate,2-trifluoroethyl) nickel(II) phosphate, bis(2,2,2-trifluoroethyl) cobalt(II) phosphate, bis(2,2,2-trifluoroethyl) copper(II) phosphate, tetraethylammonium bis(2,2,2-trifluoroethyl) phosphate, triethylmethylammonium bis(2,2,2-trifluoroethyl) phosphate, 1-propyl-1-methylpyrrolidinium bis(2,2,2-trifluoroethyl) phosphate, 1-ethyl-3-methylimidazolium bis(2,2,2-trifluoroethyl) phosphate phosphate, lithium ethyl(2,2,2-trifluoroethyl)phosphate, sodium ethyl(2,2,2-trifluoroethyl)phosphate, potassium ethyl(2,2,2-trifluoroethyl)phosphate, magnesium ethyl(2,2,2-trifluoroethyl)phosphate, calcium ethyl(2,2,2-trifluoroethyl)phosphate, aluminum ethyl(2,2,2-trifluoroethyl)phosphate, manganese(II) ethyl(2,2,2-trifluoroethyl)phosphate, nickel(II) ethyl(2 ,2,2-trifluoroethyl)cobalt(II) phosphate, ethyl(2,2,2-trifluoroethyl)copper(II) phosphate, tetraethylammonium ethyl(2,2,2-trifluoroethyl)phosphate, triethylmethylammonium ethyl(2,2,2-trifluoroethyl)phosphate, 1-propyl-1-methylpyrrolidinium ethyl(2,2,2-trifluoroethyl)phosphate, 1-ethyl-3-methylimidazolium ethyl(2,2,2-trifluoroethyl)phosphate, lithium 2,2,2-trifluoroethyl Fluorophosphates, Sodium 2,2,2-trifluoroethyl fluorophosphate, Potassium 2,2,2-trifluoroethyl fluorophosphate, Magnesium 2,2,2-trifluoroethyl fluorophosphate, Calcium 2,2,2-trifluoroethyl fluorophosphate, Aluminum 2,2,2-trifluoroethyl fluorophosphate, Manganese(II) 2,2,2-trifluoroethyl fluorophosphate, Nickel(II) 2,2,2-trifluoroethyl fluorophosphate, Cobalt(II) 2,2,2-Trifluoroethyl fluorophosphate, copper(II) 2,2,2-trifluoroethyl fluorophosphate, tetraethylammonium 2,2,2-trifluoroethyl fluorophosphate, triethylmethylammonium 2,2,2-trifluoroethyl fluorophosphate, 1-propyl-1-methylpyrrolidinium 2,2,2-trifluoroethyl fluorophosphate, 1-ethyl-3-methylimidazolium 2,2,2-trifluoroethyl fluorophosphate, lithium difluorophosphate, sodium difluorophosphate, potassium difluorophosphine phosphate, cesium difluorophosphate, magnesium difluorophosphate, calcium difluorophosphate, aluminum difluorophosphate, manganese (II) difluorophosphate, nickel (II) difluorophosphate, cobalt (II) difluorophosphate, copper (II) difluorophosphate, tetraethylammonium difluorophosphate, triethylmethylammonium difluorophosphate, 1-propyl-1-methylpyrrolidinium difluorophosphate, 1-ethyl-3-methylimidazolium difluorophosphate, etc. However, the phosphate compound represented by the chemical formula (C) is not limited to these compound groups.

[0084] <Reaction conditions for step (I)> The reaction molar ratio in the step (I) is not particularly limited and may be appropriately set according to the reactant. In the reaction molar ratio between the phosphoric acid ester and the raw material salt, the lower limit of the phosphoric acid ester is usually 1 mole or more per mole of the raw material salt. The upper limit of the phosphoric acid ester is usually 2.5 moles or less, and preferably 1.5 moles or less from the viewpoint of industrial production.

[0085] The reaction initiation temperature in the step (I) is not particularly limited as long as the reaction proceeds, and may be appropriately set according to the type of reaction. The lower limit of the reaction initiation temperature is usually 0°C or higher, and from the viewpoint of reactivity, it is preferably 20°C or higher, and more preferably 60°C or higher. The upper limit of the reaction initiation temperature is usually 150°C or lower, and from the viewpoint of reactivity, it is preferably 120°C or lower, and more preferably 100°C or lower. By setting the lower limit of the reaction initiation temperature to 0°C or higher, it is possible to prevent the reaction rate from significantly decreasing. On the other hand, by setting the upper limit of the reaction initiation temperature to 150°C or lower, it is possible to suppress the excess energy used in the reaction.

[0086] The means for adjusting the reaction initiation temperature is not particularly limited. For example, when the reaction initiation temperature is controlled by cooling so as to be within the above-mentioned temperature range, the reaction vessel into which the phosphoric acid ester and the raw material salt are charged can be ice-cooled. When the reaction initiation temperature is controlled by heating so as to be within the above-mentioned temperature range, the reaction initiation temperature can be controlled by using an oil bath set at an arbitrary temperature.

[0087] The reaction time of the step (I) is not particularly limited and may be appropriately set depending on the reactant. The lower limit of the reaction time is usually 1 hour or more. The upper limit of the reaction time is usually 10 hours or less, and from the viewpoint of industrial production, it is preferably 6 hours or less, more preferably 4 hours or less.

[0088] The reaction in step (I) can be carried out without a solvent or in a non-aqueous solvent. When the reaction in step (I) is carried out without a solvent, the phosphoric acid ester also functions as a reaction solvent.

[0089] The non-aqueous solvent is not particularly limited as long as it does not cause any trouble such as reaction with other reactants or products, but it is preferable to use an aprotic organic solvent.

[0090] The aprotic organic solvent is not particularly limited, and examples thereof include alcohols, nitriles, esters, ketones, ethers, halogenated hydrocarbons, etc. These may be used alone or in combination of two or more.

[0091] The alcohols are not particularly limited, and examples thereof include methanol, ethanol, propanol, 2-propanol, butanol, pentanol, hexanol, heptanol, octanol, 2-iodoethanol, 2-bromoethanol, 2-chloroethanol, 2-fluoroethanol, 1,2-diiodoethanol, 1,2-dibromoethanol, 1,2-dichloroethanol, 1,2-difluoroethanol, 2,2-diiodoethanol, 2,2-dibromoethanol, 2,2-dichloroethanol, 2,2-difluoroethanol, 2,2,2-tribromoethanol, 2,2,2-trichloroethanol, 2,2,2-trifluoroethanol, hexafluoro-2-propanol, etc. These may be used alone or in combination of two or more.

[0092] The nitriles are not particularly limited, and examples thereof include acetonitrile, propanenitrile, etc. These may be used alone or in combination of two or more.

[0093] The esters are not particularly limited, and examples thereof include dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, etc. These may be used alone or in combination of two or more.

[0094] The ketones are not particularly limited, and examples thereof include acetone, ethyl methyl ketone, isobutyl methyl ketone, cyclohexanone, etc. These may be used alone or in combination of two or more.

[0095] The ethers are not particularly limited, and examples thereof include diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane, etc. These may be used alone or in combination of two or more.

[0096] The halogenated hydrocarbon is not particularly limited, and examples thereof include dichloromethane, chloroform, 1,1,2,2-tetrachloroethane, chlorobenzene, etc. These may be used alone or in combination of two or more.

[0097] Other examples of non-aqueous solvents include toluene, N,N-dimethylformamide, dimethylsulfoxide, nitromethane, and nitroethane.

[0098] Among the non-aqueous solvents exemplified above, in the present invention, nitriles, esters, ketones, ethers and halogenated hydrocarbons are preferred from the viewpoints of solubility of the reaction substrates and easy availability.

[0099] The lower limit of the amount of the non-aqueous solvent used is preferably 1 mole or more, more preferably 10 moles or more, per mole of the phosphoric acid ester. The upper limit of the amount of the non-aqueous solvent used is preferably 10,000 moles or less, more preferably 1,000 moles or less, and even more preferably 100 moles or less, per mole of the phosphoric acid ester. By setting the lower limit of the amount of the non-aqueous solvent used to 1 mole or more, it is possible to prevent a decrease in the reactivity between the phosphoric acid ester and the raw material salt, and to suppress a decrease in the yield and purity of the phosphate compound. On the other hand, by setting the upper limit of the amount of the non-aqueous solvent used to 10,000 moles or less, it is possible to suppress the energy required for distilling off the non-aqueous solvent, and to prevent it from being disadvantageous in industrial production.

[0100] The phosphate compound obtained in the step (I) may be isolated and purified depending on its purity. The method is not particularly limited, and a known method can be adopted. Specific examples include atmospheric distillation, reduced pressure distillation, filtration, filtration, recrystallization, sublimation purification, silica gel column chromatography, preparative thin layer chromatography (PTLC), high performance liquid chromatography (HPLC), and ion chromatography (IC).

[0101] (Method of producing phosphoric ester) When Z is a silicon atom, the phosphoric acid ester can be obtained by a known production method using an acid anhydride or the like as a raw material. However, in this embodiment, as shown in the chemical reaction formula below, it is preferable to include a step (II) of reacting a phosphoric acid compound represented by chemical formula (D) with a silicon compound represented by chemical formula (E) to produce a phosphoric acid silyl ester represented by chemical formula (F). This makes it possible to efficiently obtain the phosphoric acid ester.

[0102] [ka]

[0103] The reaction of step (II) makes it possible to reuse the silicon compound by-produced in step (I) as the silicon compound represented by the chemical formula (E), thereby enabling the production of a phosphate compound with extremely high production efficiency and reduced production costs.

[0104] <Phosphate compounds> The phosphate compound is represented by the following chemical formula (D).

[0105] [ka]

[0106] In the chemical formula (D), 1 and X 2represents the same functional group as in the above chemical formula (A), and therefore, detailed explanations of these will be omitted.

[0107] In the chemical formula (D), M' represents a hydrogen atom, an alkali metal, an alkaline earth metal, a primary hydrocarbon group having 1 to 10 carbon atoms, a secondary hydrocarbon group having 1 to 10 carbon atoms, a primary hydrocarbon group having 1 to 10 carbon atoms and having at least one of a halogen atom, a hetero atom, or an unsaturated bond (hereinafter referred to as a "primary hydrocarbon group having a halogen atom, etc."), or a secondary hydrocarbon group having 1 to 10 carbon atoms and having at least one of a halogen atom, a hetero atom, or an unsaturated bond (hereinafter referred to as a "secondary hydrocarbon group having a halogen atom, etc.").

[0108] The alkali metals in M' include Li, Na, K, Rb, and Cs. Among these alkali metals, Li, Na, and K are preferred from the viewpoint of availability.

[0109] The alkaline earth metal in M' is not particularly limited, and examples thereof include Be, Mg, Ca, Sr, and Ba. Among these alkaline earth metals, Mg, Ca, and Ba are preferred from the viewpoints of availability and safety.

[0110] The primary hydrocarbon group having 1 to 10 carbon atoms in M' is not particularly limited, and examples thereof include primary alkyl groups. The secondary hydrocarbon group having 1 to 10 carbon atoms is not particularly limited, and examples thereof include secondary alkyl groups. The primary alkyl group having 1 to 10 carbon atoms and the secondary alkyl group having 1 to 10 carbon atoms are not particularly limited, and examples thereof include linear alkyl groups such as methyl, ethyl, propyl, butyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, and octyl groups, and cyclic alkyl groups such as cyclopentyl and cyclohexyl groups. The primary hydrocarbon group having 1 to 10 carbon atoms in M' is preferably a primary hydrocarbon group having 1, 2, 3, 4, 5, or 6 carbon atoms, and more preferably a primary hydrocarbon group having 1, 2, or 3 carbon atoms. The secondary hydrocarbon group having 1 to 10 carbon atoms in M' is preferably a secondary hydrocarbon group having 1, 2, 3, 4, 5 or 6 carbon atoms, more preferably a secondary hydrocarbon group having 1, 2 or 3 carbon atoms.

[0111] The primary hydrocarbon group having a carbon number of 1 to 10 and having a halogen atom or the like in M' and the secondary hydrocarbon group having a carbon number of 1 to 10 and having a halogen atom or the like are not particularly limited, and examples thereof include a 2-iodoethyl group, a 2-bromoethyl group, a 2-chloroethyl group, a 2-fluoroethyl group, a 1,2-diiodoethyl group, a 1,2-dibromoethyl group, a 1,2-dichloroethyl group, a 1,2-difluoroethyl group, a 2,2-diiodoethyl group, a 2,2-dibromoethyl group, a 2,2-dichloroethyl group, a 2,2-difluoroethyl group, a 2,2,2-tribromoethyl group, a 2,2,2-trichloroethyl group, and the like. chain-containing halogenated alkyl groups such as a 2,2,2-trifluoroethyl group and a hexafluoro-2-propyl group; cyclic halogenated alkyl groups such as a 2-iodocyclohexyl group, a 2-bromocyclohexyl group, a 2-chlorocyclohexyl group and a 2-fluorocyclohexyl group; chain-containing alkenyl groups such as a 2-propenyl group, a 2-butenyl group and a 3-butenyl group; cyclic alkenyl groups such as a 2-cyclopentenyl group, a 2-cyclohexenyl group and a 3-cyclohexenyl group; chain-containing alkynyl groups such as a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 2-pentynyl group, a 3-pentynyl group and a 4-pentynyl group. The primary hydrocarbon group having a carbon number of 1 to 10 and containing a halogen atom or the like in M' is preferably a primary hydrocarbon group having a carbon number of 1, 2, 3, 4, 5, or 6 and containing a halogen atom or the like, and more preferably a primary hydrocarbon group having a carbon number of 1, 2, or 3 and containing a halogen atom or the like. Furthermore, the secondary hydrocarbon group having a carbon number of 1 to 10 and containing a halogen atom or the like in M' is preferably a secondary hydrocarbon group having a carbon number of 1, 2, 3, 4, 5, or 6 and containing a halogen atom or the like, and more preferably a secondary hydrocarbon group having a carbon number of 1, 2, or 3 and containing a halogen atom or the like.

[0112] The unsaturated bond in M' means, for example, a carbon-carbon double bond or triple bond.

[0113] More specifically, the phosphoric acid compound represented by the chemical formula (D) is 1 and X 2are each independently an alkoxy group having 1 to 10 carbon atoms, ’ is a hydrogen atom, 1 and X 2 a fluorophosphoric acid ester in which one of X is a fluorine atom and the other is an alkoxy group having 1 to 10 carbon atoms, and M' is a hydrogen atom; and 1 and X 2 is a fluorine atom, and the M' is a hydrogen atom, it is preferably a difluorophosphoric acid.

[0114] Specific examples of the phosphoric acid compound represented by the chemical formula (D) include dimethyl phosphate, diethyl phosphate, dipropyl phosphate, dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diphenyl phosphate, diallyl phosphate, dipropargyl phosphate, bis(2-butoxyethyl)phosphate, bis(2-chloroethyl)phosphate, bis(2,2,2-trifluoroethyl)phosphate, bis(1,1,1,3,3,3-hexafluoro-2-propyl)phosphate, methyl fluoro phosphate, ethyl fluorophosphate, propyl fluorophosphate, butyl fluorophosphate, pentyl fluorophosphate, hexyl fluorophosphate, phenyl fluorophosphate, allyl fluorophosphate, propargyl fluorophosphate, 2-butoxyethyl fluorophosphate, 2-chloroethyl fluorophosphate, 2,2,2-trifluoroethyl fluorophosphate, 1,1,1,3,3,3-hexafluoro-2-propyl fluorophosphate, difluorophosphoric acid, etc. However, the phosphoric acid compound represented by the chemical formula (D) is not limited to these compound groups.

[0115] <Silicon compounds> The silicon compound is represented by the following chemical formula (E).

[0116] [ka]

[0117] In the chemical formula (E), 3 ~X 5 represents the same functional group as in the above chemical formula (A), and therefore, detailed explanations of these will be omitted.

[0118] X 7 is a leaving group, and represents a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a haloacyloxy group, or a sulfonyloxy group.

[0119] X 7 Examples of the halogen atom in include fluorine, chlorine, bromine, and iodine atoms. Among these halogen atoms, chlorine, bromine, and iodine atoms are preferred from the viewpoints of high elimination ability and reuse of by-products.

[0120] X 7 The alkoxy group having 1 to 10 carbon atoms in the formula (I) is not particularly limited, and examples thereof include linear alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexoxy groups, cyclic alkoxy groups such as cyclopentoxy and cyclohexoxy groups, phenoxy, 3-methylphenoxy, 4-methylphenoxy, and 3,5-dimethylphenoxy groups. 7 The alkoxy group having 1 to 10 carbon atoms is preferably an alkoxy group having 1, 2, 3, 4, 5 or 6 carbon atoms, and more preferably an alkoxy group having 1, 2 or 3 carbon atoms.

[0121] X 7The haloacyloxy group in the above is not particularly limited, but is preferably a functional group having 1 to 7 carbon atoms and having one or more hydrogen atoms substituted with halogen atoms.Specific examples of the haloacyloxy group include an iodoacetyl group, a bromoacetyl group, a chloroacetyl group, a fluoroacetyl group, a diiodoacetyl group, a dibromoacetyl group, a dichloroacetyl group, a difluoroacetyl group, a triiodoacetyl group, a tribromoacetyl group, a trichloroacetyl group, a trifluoroacetyl group, a 3,3,3-triiodopropanoyl group, a 3,3,3-tribromopropanoyl group, a 3,3,3-trichloropropanoyl group, a 3,3,3-trifluoropropanoyl group, a pentaiodopropanoyl group, a pentabromopropanoyl group, a pentachloropropanoyl group, a pentafluoropropanoyl group, a 4,4,4- Examples of the halogen atom include triiodobutanoyl group, 4,4,4-tribromobutanoyl group, 4,4,4-trichlorobutanoyl group, 4,4,4-trifluorobutanoyl group, 3,3,4,4,4-pentaiodobutanoyl group, 3,3,4,4,4-pentabromobutanoyl group, 3,3,4,4,4-pentachlorobutanoyl group, 3,3,4,4,4-pentafluorobutanoyl group, heptaiodobutanoyl group, heptabromobutanoyl group, heptachlorobutanoyl group, heptafluorobutanoyl group, pentaiodobenzoyl group, pentabromobenzoyl group, pentachlorobenzoyl group, pentafluorobenzoyl group, etc. The halogen atom represents fluorine, chlorine, bromine, and iodine.

[0122] X 7 The sulfonyloxy group in the above formula is represented by a -SO3Y group, where Y represents a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrocarbon group having 1 to 10 carbon atoms and having at least one of a halogen atom, a heteroatom, or an unsaturated bond.

[0123] The halogen atom in Y includes fluorine, chlorine, bromine and iodine atoms.

[0124] The hydrocarbon group having 1 to 10 carbon atoms in Y is not particularly limited, and examples thereof include chain alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, and octyl group, and cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, etc. The hydrocarbon group having 1 to 10 carbon atoms in Y is preferably a hydrocarbon group having 1, 2, 3, 4, 5, or 6 carbon atoms, and more preferably a hydrocarbon group having 1, 2, or 3 carbon atoms.

[0125] The hydrocarbon group having a halogen atom and a carbon number of 1 to 10 in Y means a functional group in which part or all of the hydrogen atoms in the hydrocarbon group are substituted with halogen atoms. The halogen atom represents a fluorine, chlorine, bromine, or iodine atom. The hydrocarbon group having a halogen atom and a carbon number of 1 to 10 in Y is preferably a hydrocarbon group having a halogen atom and a carbon number of 1, 2, 3, 4, 5, or 6, and more preferably a hydrocarbon group having a halogen atom and a carbon number of 1, 2, or 3.

[0126] The hydrocarbon group having a heteroatom with 1 to 10 carbon atoms in Y means a functional group in which some or all of the hydrogen and carbon in the hydrocarbon group are substituted with a heteroatom. The heteroatom represents an atom such as oxygen, nitrogen, or sulfur. The hydrocarbon group having a heteroatom with 1 to 10 carbon atoms in Y is preferably a hydrocarbon group having a heteroatom with 1, 2, 3, 4, 5, or 6 carbon atoms, and more preferably a hydrocarbon group having a heteroatom with 1, 2, or 3 carbon atoms.

[0127] The hydrocarbon group for Y having 1 to 10 carbon atoms and an unsaturated bond means, for example, a hydrocarbon group having 1 to 10 carbon atoms and a double bond or triple bond between carbon atoms. Furthermore, the hydrocarbon group having an unsaturated bond is preferably a hydrocarbon group having 1, 2, 3, 4 or 5 unsaturated bonds, and more preferably a hydrocarbon group having 1, 2 or 3 unsaturated bonds.

[0128] Specific examples of the hydrocarbon group having 1 to 10 carbon atoms and having a halogen atom, a hetero atom, or an unsaturated bond in Y include an iodomethyl group, a bromomethyl group, a chloromethyl group, a fluoromethyl group, a diiodomethyl group, a dibromomethyl group, a dichloromethyl group, a difluoromethyl group, a triiodomethyl group, a tribromomethyl group, a trichloromethyl group, a trifluoromethyl group, a 2-iodoethyl group, a 2-bromoethyl group, a 2-chloroethyl group, a 2-fluoroethyl group, a 1,2-diiodoethyl group, a 1,2-dibromoethyl group, a 1,2-dichloromethyl group, a 2-fluoroethyl group, a 1,2-diiodoethyl group, a 1,2-dibromoethyl group, a 1,2-dichloromethyl group, a 1,2-difluoro ...fluoroethyl group, a 1,2-difluoroethyl group, a 1,2-difluoroethyl group, a 1,2-difluoroethyl group, a 1,2-difluoroethyl group, chain-type halogenated alkyl groups such as 2-iodocyclohexyl, 2-bromocyclohexyl, 2-chlorocyclohexyl, and 2-fluorocyclohexyl groups; cyclic halogenated alkyl groups such as 2-iodocyclohexyl, 2-bromocyclohexyl, 2-chlorocyclohexyl, and 2-fluorocyclohexyl groups; ethenyl, 2-propenyl, and isopropenyl groups; chain alkenyl groups such as 2-butenyl and 3-butenyl groups; cyclic alkenyl groups such as 2-cyclopentenyl, 2-cyclohexenyl and 3-cyclohexenyl groups; chain alkynyl groups such as ethynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl and 4-pentynyl groups; phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,6-dimethylphenyl, 3,5-dimethylphenyl, 2,4,6-trimethylphenyl, 2- Aryl groups such as a nitrophenyl group, a 4-nitrophenyl group, a 2,4-dinitrophenyl group, and a 2,6-dinitrophenyl group; a 2-iodophenyl group, a 2-bromophenyl group, a 2-chlorophenyl group, a 2-fluorophenyl group, a 3-iodophenyl group, a 3-bromophenyl group, a 3-chlorophenyl group, a 3-fluorophenyl group, a 4-iodophenyl group, a 4-bromophenyl group, a 4-chlorophenyl group, a 4-fluorophenyl group, a 2,6-diiodophenyl group, a 2,6-dibromophenyl group, a 2,6-dichlorophenyl group, a 2,6-difluorophenyl group;Examples of halogenated aryl groups include 5-diiodophenyl, 3,5-dibromophenyl, 3,5-dichlorophenyl, 3,5-difluorophenyl, pentaiodophenyl, pentabromophenyl, pentachlorophenyl and pentafluorophenyl groups, and naphthyl groups such as 1-naphthyl and 2-naphthyl groups.

[0129] More specifically, the silicon compound represented by the chemical formula (E) is 3 ~X 5 are each independently a hydrocarbon group having 1 to 6 carbon atoms, 7 is preferably a trialkylsilyl halide where is a halogen atom.

[0130] Specific examples of the silicon compound represented by the chemical formula (E) include chlorodimethylsilane, chlorotrimethylsilane, chloro(ethyl)dimethylsilane, chlorotriethylsilane, diisopropylchlorosilane, chlorotriisopropylsilane, tributylchlorosilane, tert-butyldimethylchlorosilane, chlorodimethylisopropylsilane, chlorodimethylvinylsilane, chlorodiethylisopropylsilane, chlorodimethylpropylsilane, allylchlorodimethylsilane, butylchlorodimethylsilane, chloro(hexyl)dimethylsilane, chlorotrihexylsilane, chloro(cyclohexyl)dimethylsilane, chlorodimethylphenylsilane, benzylchlorodimethylsilane, diphenylmethylchlorosilane, chlorotriphenylsilane, chloro(methyl)(phenyl)(vinyl)silane, chloro(methyl)diphenylsilane, etc. However, the silicon compound represented by the chemical formula (E) is not limited to these compound groups.

[0131] <Reaction conditions for step (II)> The reaction molar ratio of the step (II) is not particularly limited, and may be appropriately set according to the type of reaction. In the reaction molar ratio of the phosphoric acid compound and the silicon compound, the lower limit of the silicon compound is usually 1 mole or more per mole of the phosphoric acid compound. The upper limit of the phosphoric acid compound is 5 moles or less, and from the viewpoint of industrial production, it is preferably 2.5 moles or less, more preferably 1.5 moles or less.

[0132] The reaction initiation temperature in the step (II) is not particularly limited as long as the reaction proceeds, and may be appropriately set according to the type of reaction. The lower limit of the reaction initiation temperature is usually 0°C or higher, and from the viewpoint of reactivity, it is preferably 20°C or higher, and more preferably 40°C or higher. The upper limit of the reaction initiation temperature is usually 150°C or lower, and from the viewpoint of reactivity, it is preferably 120°C or lower, and more preferably 100°C or lower. By setting the lower limit of the reaction initiation temperature to 0°C or higher, it is possible to prevent the reaction rate from significantly decreasing. On the other hand, by setting the upper limit of the reaction initiation temperature to 150°C or lower, it is possible to suppress the excess energy used in the reaction.

[0133] The means for adjusting the reaction initiation temperature is not particularly limited. For example, when the reaction initiation temperature is controlled by cooling so as to be within the above-mentioned temperature range, the reaction vessel into which the phosphoric acid compound and the silicon compound are put can be ice-cooled. When the reaction initiation temperature is controlled by heating so as to be within the above-mentioned temperature range, the reaction can be controlled by using an oil bath set at an arbitrary temperature.

[0134] The reaction time of the step (II) is not particularly limited and may be appropriately set depending on the reactant. The lower limit of the reaction time is usually 1 hour or more. The upper limit of the reaction time is usually 12 hours or less, and from the viewpoint of industrial production, it is preferably 6 hours or less, more preferably 3 hours or less.

[0135] The reaction in step (II) can be carried out without a solvent or in a non-aqueous solvent. When the reaction in step (II) is carried out without a solvent, the silicon compound also functions as a reaction solvent.

[0136] The non-aqueous solvent may be the same as the non-aqueous solvent described in the step (I), and therefore the details thereof will be omitted.

[0137] The lower limit of the amount of the non-aqueous solvent used is preferably 1 mole or more, more preferably 10 moles or more, relative to 1 mole of the phosphoric acid compound. The upper limit of the amount of the non-aqueous solvent used is preferably 10,000 moles or less, more preferably 1,000 moles or less, and even more preferably 100 moles or less, relative to 1 mole of the phosphoric acid compound. By setting the lower limit of the amount of the non-aqueous solvent used to 1 mole or more, it is possible to prevent the reactivity between the phosphoric acid compound and the silicon compound from decreasing, and to suppress the decrease in the yield and purity of the phosphoric acid silyl ester. On the other hand, by setting the upper limit of the amount of the non-aqueous solvent used to 10,000 moles or less, it is possible to suppress the energy required for distilling off the non-aqueous solvent, and to prevent it from being disadvantageous in industrial production.

[0138] The phosphoric acid ester obtained in the step (II) may be isolated and purified depending on its purity. The method is not particularly limited, and a known method can be adopted. Specific examples include atmospheric distillation, reduced pressure distillation, filtration, filtration, recrystallization, sublimation purification, silica gel column chromatography, preparative thin layer chromatography (PTLC), high performance liquid chromatography (HPLC), and ion chromatography (IC). EXAMPLES

[0139] Preferred examples of the present invention are described in detail below. However, the materials and amounts of ingredients described in the examples are not intended to limit the scope of the present invention unless otherwise specified.

[0140] In the following examples, the determination of purity and the measurements of physicochemical properties were carried out using the following apparatuses.

[0141] (purity) The purity of the phosphate compound was calculated from anion analysis by ion chromatography. The analytical device and measurement conditions are as follows: Equipment: 850 Professional IC Anion (Metrohm) Column: Dionex IonPac AS23 2x250mm (Thermo Fisher Scientific) Sample: 100 ppm sample aqueous solution Flow rate: 1mL / min Eluent: 4.5 mM Na2CO3 in H2O-acetonitrile (7:3) mixture

[0142] (NMR measurement) Benchtop Nuclear Magnetic Resonance Spectrometer: Spinsolve 60 ULTRA Phosphorus (Manufactured by Magritek)

[0143] Example 1 <Sodium ethyl (2,2,2-trifluoroethyl) phosphate (without solvent)> Sodium iodide (630 mg, 4.20 mmol, Fujifilm Wako Pure Chemical Industries, Ltd.) was placed as a raw salt in a 50 mL eggplant-shaped flask containing a stirrer, and diethyl 2,2,2-trifluoroethyl phosphate (1.18 g, 5.00 mmol) as a phosphate ester was added at room temperature. This mixed solution was heated at 120°C for 4 hours under a nitrogen stream. After the reaction mixture was allowed to cool to room temperature, it was filtered and the residue was dried overnight at 120°C under a nitrogen stream to obtain white solid sodium ethyl (2,2,2-trifluoroethyl) phosphate (930 mg, 96.1%) as a phosphate compound. The purity of sodium ethyl (2,2,2-trifluoroethyl) phosphate was 99.6%.

[0144] Example 2 <Bis(2,2,2-trifluoroethyl)copper(II)phosphate (without solvent)> Copper chloride (II) (980 mg, 7.29 mmol, Wako Pure Chemical Industries, Ltd.) was placed as a raw salt in a 100 mL eggplant-shaped flask containing a stirrer, and tris(2,2,2-trifluoroethyl)phosphate (50.0 g, 145 mmol) as a phosphate ester was added at room temperature. This mixed solution was heated and refluxed for 6 hours in a water bath at 155°C under a nitrogen stream. The reaction mixture was allowed to cool to room temperature, filtered, and the residue was dried overnight at 120°C under a nitrogen stream to obtain a pale blue solid bis(2,2,2-trifluoroethyl)copper(II)phosphate (4.06 g, 96.1%) as a phosphate compound. The purity of bis(2,2,2-trifluoroethyl)copper(II)phosphate was 98.4%.

[0145] Example 3 <1-Ethyl-3-methylimidazolium bis(2,2,2-trifluoroethyl)phosphate> In a 50 mL eggplant-shaped flask containing a stirrer, 1-ethyl-3-methylimidazolium bromide (760 mg, 3.11 mmol, manufactured by TCI) was placed as a raw salt, and then ethyl bis(2,2,2-trifluoroethyl)phosphate (905 mg, 3.12 mmol) as a phosphoric acid ester was added at room temperature. This mixed solution was heated at 120°C for 4 hours under a nitrogen stream. After the reaction mixture was allowed to cool to room temperature, it was concentrated using an evaporator, and the liquid was subsequently dried at 60°C for 1 hour to obtain colorless liquid 1-ethyl-3-methylimidazolium bis(2,2,2-trifluoroethyl)phosphate (1.49 g, quantitative) as a phosphate compound. The purity of 1-ethyl-3-methylimidazolium bis(2,2,2-trifluoroethyl)phosphate was 99.1%.

[0146] Example 4 <Synthesis of lithium bis(2,2,2-trifluoroethyl)phosphate (using non-aqueous solvent)> Lithium chloride (0.634 g, 15.0 mmol) as a raw salt and acetonitrile (40.0 g, 974 mmol, Kishida Chemical Co., Ltd.) as an aprotic organic solvent were placed in a 50 mL eggplant-shaped flask containing a stirrer, and then bis(2,2,2-trifluoroethyl)trimethylsilylphosphate (5.00 g, 15.0 mmol) as a phosphate ester was added at room temperature. This mixed solution was heated and refluxed at 82°C for 2 hours under a nitrogen stream. The reaction mixture was allowed to cool to room temperature, and then further cooled to 0°C. The precipitate was filtered, and the residue was washed with a small amount of acetonitrile. The residue was dried at 45°C for 20 minutes using an evaporator to obtain white solid bis(2,2,2-trifluoroethyl)lithium phosphate (2.28 g, 56.9%) as a phosphate compound. The purity of bis(2,2,2-trifluoroethyl)lithium phosphate was 99.9%.

[0147] Example 5 <Synthesis of lithium difluorophosphate 1 (without solvent)> Trimethylsilyl difluorophosphate (3.50g, 20.1mmol) as a phosphoric acid ester was added to a 50mL eggplant-shaped flask containing a stirrer under nitrogen protection, and then lithium chloride (568mg, 13.4mmol) as a raw salt was added at room temperature. This mixture was heated at 80°C for 1 hour under a nitrogen stream. After cooling to room temperature, the reaction mixture was filtered and the residue was washed with a small amount of DMC (dimethyl carbonate). The residue was dried at 120°C for 15 minutes using a dryer to obtain white solid lithium difluorophosphate (920mg, 63.6%) as a phosphate compound. The purity of the lithium difluorophosphate was 99.5%.

[0148] Example 6 <Synthesis of lithium difluorophosphate 2 (using non-aqueous solvent)> Trimethylsilyl difluorophosphate (50.0 g, 287 mmol) as a phosphoric acid ester was added to a 500 mL eggplant-shaped flask containing a stirrer under nitrogen protection, and then diluted with acetonitrile (150 g, 3.65 mol, Kishida Chemical Co., Ltd.) as an aprotic organic solvent. Furthermore, lithium chloride (11.8 g, 278 mmol) as a raw material salt was added at room temperature. This mixture was heated and refluxed at 82°C for 5 hours under a nitrogen stream. After cooling to room temperature, the reaction mixture was concentrated using an evaporator, and the resulting residue was filtered and washed with a small amount of DMC (dimethyl carbonate). The residue was dried at 120°C for 1 hour using a dryer to obtain white solid lithium difluorophosphate (27.4 g, 91.4%) as a phosphate compound. The purity of the lithium difluorophosphate was 99.4%.

[0149] Example 7 <Synthesis of bis(2,2,2-trifluoroethyl)trimethylsilyl phosphate (without solvent)> Chlorotrimethylsilane (16.6 g, 153 mmol, TCI) as a silicon compound was placed in a 50 mL eggplant-shaped flask equipped with a stirrer, and then bis(2,2,2-trifluoroethyl)phosphate (20.0 g, 76.3 mmol) as a phosphoric acid compound was added at room temperature. This mixed solution was heated and refluxed at 80°C for 6 hours under a nitrogen stream. Excess chlorotrimethylsilane was removed from the reaction mixture using an evaporator to obtain colorless liquid bis(2,2,2-trifluoroethyl)trimethylsilylphosphate (21.2 g, 83.1%) as a phosphoric acid ester. The purity of bis(2,2,2-trifluoroethyl)trimethylsilylphosphate was 99.7%.

[0150] The physicochemical properties of the obtained bis(2,2,2-trifluoroethyl)trimethylsilyl phosphate are as follows: 1 H-NMR (CDCl3, δ ppm): -0.06(s, 9H), 4.02(dq, 4H, J H-F =J H-P = 8.3Hz); 19 F-NMR (CDCl3, δ ppm): -74.8(t, 6F, J H-F =8.3Hz). 31 P-NMR (CDCl3, δ ppm): -10.1(tt, 1P, J H-P =8.3Hz).

[0151] Example 8 <Synthesis of trimethylsilyl difluorophosphate 1 (without solvent)> In a 200 mL eggplant-shaped flask equipped with a stirrer, chlorotrimethylsilane (48.7 g, 448 mmol, manufactured by TCI) as a silicon compound was placed, and difluorophosphoric acid (45.7 g, 448 mmol) as a phosphoric acid compound was added dropwise at room temperature. This mixed solution was stirred at 50°C for 6 hours under a nitrogen stream. The reaction mixture was distilled under normal pressure to obtain colorless liquid trimethylsilyl difluorophosphate (49.0 g, 62.7%) as a phosphoric acid ester. The purity of trimethylsilyl difluorophosphate was 95.6%.

[0152] Example 9 <Synthesis of trimethylsilyl difluorophosphate 2 (recycling of by-product chlorotrimethylsilane, without solvent)> In a 50 mL eggplant flask containing a stirrer, chlorotrimethylsilane {7.16 g, 65.9 mmol} as a silicon compound was added, and then difluorophosphoric acid (6.71 g, 65.8 mmol) as a phosphoric acid compound was added dropwise at room temperature. The mixed solution was stirred at 50° C. for 3 hours under a nitrogen stream. The reaction mixture was distilled at normal pressure to obtain colorless liquid trimethylsilyl difluorophosphate (7.12 g, 62.2%) as a phosphoric acid ester. The purity of trimethylsilyl difluorophosphate was 96.1%. In addition, the by-product (by-product (E') of step (I)) produced during the synthesis of lithium difluorophosphate in Example 5 was used as chlorotrimethylsilane.

[0153] The physicochemical properties of the obtained trimethylsilyl difluorophosphate are as follows: 1 H-NMR (CDCl3, δ ppm): 0.33(s, 9H); 19 F-NMR(CDCl3, δ ppm):-80.4(d, 2F, J=985.9Hz); 31 P-NMR (CDCl3, δ ppm): -29.1 (dd, 1P, J=985.9Hz).

[0154] Example 10 <Synthesis of dimethylvinylsilyl difluorophosphate (without solvent)> In a 100 mL eggplant-shaped flask equipped with a stirrer, chlorodimethylvinylsilane (10.1 g, 83.7 mmol, manufactured by TCI) as a silicon compound was placed, and difluorophosphoric acid (8.14 g, 79.8 mmol) as a phosphoric acid compound was added dropwise at room temperature. The mixed solution was stirred at 60° C. for 3 hours under a nitrogen stream. Dimethylvinylsilyl difluorophosphate (2.33 g, 15.7%) was obtained as a colorless liquid phosphoric acid ester by vacuum distillation of the reaction mixture. The purity of the dimethylvinylsilyl difluorophosphate was 97.9%.

[0155] The physicochemical properties of the obtained dimethylvinylsilyl difluorophosphate are as follows: 1 H-NMR (CDCl3, δ ppm): 0.44 (s, 7H), 6.02-6.13 (m, 2H); 19 F-NMR(CDCl3, δ ppm):-80.0(d, 2F, J=990.3Hz); 31 P-NMR (CDCl3, δ ppm): -28.4 (dd, 1P, J=990.3Hz).

[0156] Example 11 <Synthesis of dimethylphenylsilyl difluorophosphate (without solvent)> In a 100 mL eggplant flask equipped with a stirrer, chlorodimethylphenylsilane (16.8 g, 98.4 mmol, manufactured by TCI) as a silicon compound was placed, and difluorophosphoric acid (10.1 g, 99.0 mmol) as a phosphoric acid compound was added dropwise at room temperature. The mixed solution was stirred at 60° C. for 3 hours under a nitrogen stream. Dimethylphenylsilyl difluorophosphate (10.6 g, 45.6%) was obtained as a colorless liquid phosphoric acid ester by vacuum distillation of the reaction mixture. The purity of the dimethylphenylsilyl difluorophosphate was 97.5%.

[0157] The physicochemical properties of the obtained dimethylphenylsilyl difluorophosphate are as follows: 1 H-NMR (CDCl3, δ ppm): 0.37 (s, 6H), 7.07-7.47 (m, 5H); 19 F-NMR (CDCl3, δ ppm): -79.7(d, 2F, J=991.4Hz); 31 P-NMR (CDCl3, δ ppm): -30.0 (dd, 1P, J=991.4Hz).

[0158] Example 12 <Synthesis of triethylsilyl difluorophosphate (without solvent)> In a 50 mL eggplant-shaped flask equipped with a stirrer, chlorotriethylsilane (10.0 g, 66.3 mmol, manufactured by TCI) as a silicon compound was placed, and difluorophosphoric acid (6.69 g, 65.6 mmol) as a phosphoric acid compound was added dropwise at room temperature. This mixed solution was stirred at 60°C for 4 hours under a nitrogen stream. The reaction mixture was distilled under reduced pressure to obtain colorless liquid triethylsilyl difluorophosphate (7.29 g, 51.4%) as a phosphoric acid ester. The purity of triethylsilyl difluorophosphate was 98.3%.

[0159] The physicochemical properties of the obtained triethylsilyl difluorophosphate are as follows: 1H-NMR (CDCl3, δ ppm):0.40-1.11(m, 15H); 19 F-NMR(CDCl3, δ ppm):-80.9(d, 2F, J=986.4Hz); 31 P-NMR (CDCl3, δ ppm): -29.5 (dd, 1P, J=986.4Hz).

[0160] (Example 13) <Synthesis of cyclohexyldimethylsilyl difluorophosphate (without solvent)> In a 50 mL eggplant flask containing a stirrer, chloro(cyclohexyl)dimethylsilane (12.0 g, 67.9 mmol, manufactured by TCI) as a silicon compound was placed, and difluorophosphoric acid (6.83 g, 67.0 mmol) as a phosphoric acid compound was added dropwise at room temperature. The mixed solution was stirred at 60° C. for 4 hours under a nitrogen stream. The reaction mixture was distilled under reduced pressure to obtain colorless liquid cyclohexyldimethylsilyl difluorophosphate (9.92 g, 61.0%) as a phosphoric acid ester. The purity of the cyclohexyldimethylsilyl difluorophosphate was 93.6%.

[0161] The physicochemical properties of the obtained cyclohexyldimethylsilyl difluorophosphate are as follows: 1 H-NMR (CDCl3, δ ppm): 0.29 (s, 6H), 0.92-1.67 (br m, 11H); 19 F-NMR (CDCl3, δ ppm): -79.8 (d, 2F, J=989.0Hz); 31 P-NMR (CDCl3, δ ppm): -29.5 (dd, 1P, J=989.0Hz).

[0162] Example 14 <Synthesis of dimethylphenylsilyl difluorophosphate (using non-aqueous solvent)> Sodium difluorophosphate (5.01 g, 40.4 mmol) as a phosphoric acid compound and acetonitrile (20.0 g, 487 mmol, Kishida Chemical Co., Ltd.) as an aprotic organic solvent were added to a 50 mL screw vial containing a stirrer under nitrogen protection, and then chlorodimethylphenylsilane (6.82 g, 40.0 mmol, TCI Co., Ltd.) as a silicon compound was added dropwise at room temperature. The mixed solution was stirred at 60°C under a nitrogen atmosphere for 2 hours. After cooling to room temperature, the reaction mixture was filtered using a 0.45 μm membrane filter. Nitrogen gas was bubbled through the filtrate for 12 hours to remove acetonitrile. The residue was filtered using a 0.45 μm membrane filter to obtain a colorless liquid dimethylphenylsilyl difluorophosphate (7.79 g, 82.5%) as a phosphoric acid ester. The purity of the dimethylphenylsilyl difluorophosphate was 95.4%.

[0163] Example 15 <Synthesis of triisopropylsilyl difluorophosphate (using non-aqueous solvent)> Sodium difluorophosphate (2.02 g, 16.3 mmol) as a phosphoric acid compound and acetonitrile (9.13 g, 222 mmol, Kishida Chemical Co., Ltd.) as an aprotic organic solvent were added to a 50 mL screw vial containing a stirrer under nitrogen protection, and then chlorotriisopropylsilane (3.14 g, 16.3 mmol, TCI Co., Ltd.) as a silicon compound was added dropwise at room temperature. The mixed solution was stirred at 60°C under a nitrogen atmosphere for 2 hours. After cooling to room temperature, the reaction mixture was filtered using a 0.45 μm membrane filter. Nitrogen gas was bubbled through the filtrate for 12 hours to remove acetonitrile. The residue was filtered using a 0.45 μm membrane filter to obtain colorless liquid triisopropylsilyl difluorophosphate (1.00 g, 23.7%) as a phosphoric acid ester. The purity of triisopropylsilyl difluorophosphate was 97.4%.

[0164] The physicochemical properties of the obtained triisopropylsilyl difluorophosphate are as follows: 1 H-NMR (CDCl3, δ ppm):0.98-1.27(m, 21H); 19 F-NMR(CDCl3, δ ppm):-80.4(d, 2F, J=983.5Hz); 31 P-NMR (CDCl3, δ ppm): -29.5 (dd, 1P, J=989.0Hz).

[0165] Example 16 <Synthesis of methyldiphenylsilyl difluorophosphate (using non-aqueous solvent)> Sodium difluorophosphate (3.01 g, 24.3 mmol) as a phosphoric acid compound and acetonitrile (10.0 g, 244 mmol, Kishida Chemical Co., Ltd.) as an aprotic organic solvent were added to a 50 mL screw vial containing a stirrer under nitrogen protection, and then chloro(methyl)diphenylsilane (5.36 g, 23.0 mmol, TCI Co., Ltd.) as a silicon compound was added dropwise at room temperature. The mixed solution was stirred at 60°C under a nitrogen atmosphere for 11 hours. After cooling to room temperature, the reaction mixture was filtered using a 0.45 μm membrane filter. Nitrogen gas was bubbled through the filtrate for 12 hours to remove acetonitrile. The residue was filtered using a 0.45 μm membrane filter to obtain a colorless liquid methyldiphenylsilyl difluorophosphate (5.22 g, 76.1%) as a phosphoric acid ester. The purity of the methyldiphenylsilyl difluorophosphate was 88.0%.

[0166] The physicochemical properties of the obtained methyldiphenylsilyl difluorophosphate are as follows: 1 H-NMR (CDCl3, δ ppm): 0.92 (s, 3H), 7.29-7.73 (m, 10H); 19 F-NMR (CDCl3, δ ppm): -78.8 (d, 2F, J=995.6Hz); 31 P-NMR(CDCl3、δ ppm):-30.3(dd、1P、J=995.6Hz)。

Claims

1. A method for producing a phosphate compound, comprising at least a step (I) of reacting a phosphate ester represented by the following chemical formula (A) with a starting salt represented by the following chemical formula (B) to produce a phosphate compound represented by the following chemical formula (C). 【Chemistry 1】 [In the formula, Z represents a silicon atom. １ and X ２ each independently represents a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms and containing a halogen atom, or an alkoxy group having 1 to 10 carbon atoms and containing a halogen atom. ３ ~X ５ each independently represents a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms and containing a halogen atom, or an alkoxy group having 1 to 10 carbon atoms and containing a halogen atom, and ３ ~X ５ At least one of the is either the hydrocarbon group having 1 to 10 carbon atoms or the alkoxy group having 1 to 10 carbon atoms.] 【Chemistry 2】 [In the formula, M represents an alkali metal, a transition metal, or an imidazolium compound. ６ represents a halogen atom. The n represents a natural number from 1 to 4. 【Chemistry 3】 [In the formula, M is the same as that in the chemical formula (B). １ and X ２ represents the same functional group as in the chemical formula (A). The n represents the same valence as in the chemical formula (B).

2. A method for producing the phosphate compound of claim 1, comprising a step (II) of reacting a phosphate compound represented by the following chemical formula (D) with a silicon compound represented by the following chemical formula (E) to produce a phosphate silyl ester represented by the following chemical formula (F). 【Chemistry 4】 [In the formula, M′ represents a hydrogen atom or an alkali metal. １ and X ２ represents the same functional group as in the chemical formula (A). The n represents the same valence as in the chemical formula (B). 【Chemistry 5】 [Wherein, X ３ ~X ５ represents the same functional group as that in the above chemical formula (A). ７ is a leaving group and represents a halogen atom. 【Chemistry 6】 [Wherein, X １ ~X ５ represents the same functional group as that represented by the above chemical formula (A).

3. The method for producing a phosphate compound according to claim 2, wherein the silicon compound represented by the chemical formula (E) is a by-product produced in the step (I).

4. The phosphoric acid compound is represented by the formula (D) １ and X ２ are each independently an alkoxy group having 1 to 10 carbon atoms, ’ The method for producing a phosphate compound according to claim 2 or 3, which is a phosphate diester in which is a hydrogen atom.

5. The phosphoric acid compound is represented by the formula (D) １ and X ２ The method for producing a phosphate compound according to claim 2 or 3, which is a fluorophosphoric acid ester in which one of the above is a fluorine atom, the other is an alkoxy group having 1 to 10 carbon atoms, and M' is a hydrogen atom.

6. The phosphoric acid compound is represented by the formula (D) １ and X ２ The method for producing a phosphate compound according to claim 2 or 3, which is a difluorophosphoric acid in which M is a fluorine atom and M' is a hydrogen atom.

7. The silicon compound is represented by the formula (E) ３ ~X ５ are each independently a hydrocarbon group having 1 to 6 carbon atoms, ７ The method for producing a phosphate compound according to any one of claims 2 to 6, wherein is a trialkylsilyl halide in which is a halogen atom.

8. 8. The method for producing a phosphate compound according to claim 1, wherein M in the chemical formula (B) is a lithium atom, a sodium atom, a magnesium atom, or 1-ethyl-3-methylimidazolium.

9. The method for producing a phosphate compound according to any one of claims 2 to 8, wherein at least one of the steps (I) and (II) is carried out in the absence of a solvent.

10. The method for producing a phosphate compound according to any one of claims 2 to 8, wherein at least one of the steps (I) and (II) is carried out in a non-aqueous solvent.

11. The method for producing a phosphate compound according to claim 10, wherein the non-aqueous solvent is an aprotic organic solvent.

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