Process for producing phosphate compounds

Abstract

The present application provides a novel method for producing a phosphate compound capable of producing a high-purity phosphate compound by a very simple method. The method for producing a phosphate compound of the present application is characterized by comprising a step (I) of reacting a phosphate ester represented by formula (A) with a raw material salt represented by formula (B) to produce a phosphate compound represented by formula (C). [In the reaction formula, Z represents C or Si. M represents an alkali metal or the like. X 1 and X 2 each independently represents a halogen atom or the like. X 3 ~ X 5 each independently represents a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or the like, and at least one of them is any one of a hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. X 6 represents a halogen atom or the like. n represents a natural number of 1 to 4.

Description

TECHNICAL FIELD

[0001] The present application relates to a method for producing a phosphate compound. More specifically, it relates to a method for producing a phosphate compound which can be extremely simply produced in high purity by a reaction of a phosphoric acid ester with a raw material salt. BACKGROUND

[0002] The use of phosphate compounds involves surfactants in cleaning agent compositions, pharmaceuticals, antistatic agents, flame retardants, and additives for secondary batteries, among other things (Patent Documents 1 to 4), and various methods for producing phosphate compounds have been developed for each use.

[0003] For example, a method for producing a phosphoric acid diester salt as a phosphate compound is disclosed in Patent Document 5. 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, in this production method, a complicated process for separating unreacted phosphoric acid triester, alcohol produced as a byproduct upon hydrolysis of the phosphoric acid triester, and a reaction solvent used upon reaction of the phosphoric acid triester with the hydroxide is required. In addition, it is disclosed that the phosphoric acid triester used as a starting material is obtained, for example, by reacting a monohalogenated phosphoric acid diester or the like with a hydroxyl compound in the presence of an organic base such as triethylamine, but since a salt of the organic base is produced as a byproduct, a process for removing the salt of the organic base is also required. Therefore, in the production method for the phosphoric acid diester salt described in Patent Document 5, there are many problems in industrial production from the viewpoint of purification and separation processes, and waste treatment.

[0004] A method for producing a monohalogenated phosphoric acid ester salt or a phosphoric acid diester salt is disclosed in Patent Document 6. According to this production method, a dihalogenated phosphoric acid salt, an alcohol, or the like is reacted with an alkali metal base or the like to produce a monohalogenated phosphoric acid ester salt or the like. However, the reaction control is not easy, and a mixture of the phosphoric acid diester salt is obtained as a product. Therefore, a process for isolating and purifying the monohalogenated phosphoric acid ester salt or the like is required, but these processes become extremely difficult. On the other hand, in the case where the phosphoric acid diester salt is obtained, depending on the reaction substrate, the monohalogenated phosphoric acid ester salt or the alkali metal salt is sometimes contained in the product. In this case, a process 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, a large amount of alcohol needs to be distilled off by vacuum drying, heat drying, or the like when the phosphoric acid diester salt is separated from the product.

[0005] PRIOR ART DOCUMENTS

[0006] PATENT DOCUMENTS

[0007] Patent Document 1: Japanese Patent Application Publication No. 2007-332355

[0008] Patent Literature 2: Japanese Patent Application Laid-Open No. 2008-231026

[0009] Patent Literature 3: WO 2016 / 158258

[0010] Patent Literature 4: Japanese Patent Application Laid-Open No. Hei 8-138733

[0011] Patent Literature 5: Japanese Patent Application Laid-Open No. 2017-36273

[0012] Patent Literature 6: Japanese Patent Application Laid-Open No. 2019-135215 SUMMARY

[0013] The present application has been achieved in view of the above problems, and an object thereof is to provide a novel method for producing a phosphate compound, which can produce a high-purity phosphate compound by an extremely simple method.

[0014] To solve the above problems, the method for producing a phosphate compound of the present application is characterized by at least including 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).

[0015] [Chemical Formula 1]

[0016]

[0017] [In the formula, the above Z represents a carbon atom or a silicon atom. The above X 1 and X 2 each independently represents 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 any one selected from a halogen atom, a hetero atom, or an unsaturated bond, or an alkoxy group having 1 to 10 carbon atoms and having at least any one selected from a halogen atom, a hetero atom, or an unsaturated bond. The above X 3 to 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 any one selected from a halogen atom, a hetero atom, or an unsaturated bond, or an alkoxy group having 1 to 10 carbon atoms and having at least any one selected from a halogen atom, a hetero atom, or an unsaturated bond, and at least one of the above X 3 to X 5 is any one of the above hydrocarbon group having 1 to 10 carbon atoms or the above alkoxy group having 1 to 10 carbon atoms.]

[0018] [Chemical Formula 2]

[0019] MX 6 n (B)

[0020] [In the formula, the above M represents an alkali metal, an alkaline earth metal, aluminum, a transition metal, or onium. The above X 6 represents a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a halogenated acyloxy group, a sulfonyloxy group (-SO3Y 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 any one selected from a halogen atom, a hetero atom, or an unsaturated bond). The above n represents a natural number of 1 to 4.]

[0021] [Chemical Formula 3]

[0022]

[0023] [In the formula, the above M represents the same cation species as the above Chemical Formula (B). The above X 1 and X 2 represent the same functional group as the above Chemical Formula (A). The above n represents the same valence as the above Chemical Formula (B).]

[0024] In the above configuration, in the case where the above Z in the above Chemical Formula (A) is a silicon atom, it is preferable to include a step (II) of allowing a phosphoric acid compound represented by the following Chemical Formula (D) to react with a silicon compound represented by the following Chemical Formula (E) to produce a silyl phosphonate represented by the following Chemical Formula (F).

[0025] [Chemical Formula 4]

[0026]

[0027] [In the formula, the above 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 any one selected from a halogen atom, a hetero atom, or an unsaturated bond, or a secondary hydrocarbon group having 1 to 10 carbon atoms and having at least any one selected from a halogen atom, a hetero atom, or an unsaturated bond. The above X 1 and X 2 represent the same functional group as the above Chemical Formula (A). The above n represents the same valence as the above Chemical Formula (B).]

[0028] [Chemical Formula 5]

[0029]

[0030] [In the formula, the above X 3 to X 5represents the same functional group as the above-described Chemical Formula (A). The above-described X 7 is a leaving group, and represents a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a halogenated acyloxy group, or a sulfonyloxy group (-SO3Y group: the above-described 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 any one selected from a halogen atom, a hetero atom, or an unsaturated bond).

[0031] [Chemical Formula 6]

[0032]

[0033] [In the formula, the above-described X 1 to X 5 represents the same functional group as the above-described Chemical Formula (A).

[0034] Further, in the above-described configuration, the silicon compound represented by the above-described Chemical Formula (E) is preferably a by-product generated in the above-described process (I).

[0035] In the above-described configuration, the above-described phosphoric acid compound is preferably any one of the above-described X 1 and X 2 each independently is an alkoxy group having 1 to 10 carbon atoms, a phosphoric acid diester when the above-described M' is a hydrogen atom.

[0036] Further, in the above-described configuration, the above-described phosphoric acid compound is preferably any one of the above-described X 1 and X 2 each independently is an alkoxy group having 1 to 10 carbon atoms, a phosphoric acid diester when the above-described M' is a hydrogen atom.

[0037] Further, in the above-described configuration, the above-described phosphoric acid compound is preferably any one of the above-described X 1 and X 2 each independently is an alkoxy group having 1 to 10 carbon atoms, a phosphoric acid diester when the above-described M' is a hydrogen atom.

[0038] In the above-described configuration, the above-described silicon compound is preferably any one of the above-described X 3 to X 5 each independently is a hydrocarbon group having 1 to 6 carbon atoms, the above-described X 7 is a halogen atom, a trialkylsilyl halide.

[0039] Further, in the above-described configuration, the above-described M in the above-described Chemical Formula (B) is preferably a lithium atom, a sodium atom, a magnesium atom, 1-methyl-1-propylpyrrolidinium, or 1-ethyl-3-methylimidazolium.

[0040] In the above configuration, at least either of the above process (I) and process (II) can be performed without a solvent.

[0041] In the above configuration, at least either of the above process (I) and process (II) can be performed in a non-aqueous solvent.

[0042] In the above configuration, the above non-aqueous solvent is preferably an aprotic organic solvent.

[0043] According to the present application, by reacting the phosphate ester represented by the above chemical formula (A) with the raw salt represented by the above chemical formula (B), the phosphate salt compound represented by the above chemical formula (C) can be manufactured in high purity extremely simply and efficiently compared to the conventional manufacturing method. DETAILED DESCRIPTION

[0044] The manufacturing method of the phosphate salt compound of the present embodiment will be described below.

[0045] The manufacturing method of the phosphate salt compound of the present embodiment includes at least process (I) of reacting the phosphate ester represented by chemical formula (A) with the raw salt represented by chemical formula (B) to generate the phosphate salt compound represented by chemical formula (C), as shown in the following chemical reaction formula.

[0046] [Chemical formula 7]

[0047] (Manufacturing method of phosphate salt compound)

[0048]

[0049] The reaction of process (I) is a reaction of the phosphate ester of X 3 X 4 X 5 The reaction of the Z-group of the phosphate ester and M of the raw salt to generate the phosphate salt compound also generates a by-product (E’) in an equimolar amount to the phosphate salt compound.

[0050] <Phosphate ester>

[0051] The above phosphate ester is represented by the following chemical formula (A).

[0052] [Chemical formula 8]

[0053]

[0054] In the above chemical formula (A), the Z represents a carbon atom or a silicon atom.

[0055] In the above chemical formula (A), the X 1 and X 2each independently represents a halogen atom, a hydrocarbon group having a carbon number of 1 to 10, an alkoxy group having a carbon number of 1 to 10, a hydrocarbon group having a carbon number of 1 to 10 and having at least any one selected from a halogen atom, a hetero atom, or an unsaturated bond (hereinafter, sometimes referred to as "a hydrocarbon group having a halogen atom or the like"), or an alkoxy group having a carbon number of 1 to 10 and having at least any one selected from a halogen atom, a hetero atom, or an unsaturated bond (hereinafter, sometimes referred to as "an alkoxy group having a halogen atom or the like").

[0056] Note that, in the present specification, "carbon number" in a functional group means the total number of carbon atoms of the functional group, unless otherwise specified. Also, in the present specification, for example, "a hydrocarbon group having a carbon number of 1 to 10" means the total of hydrocarbon groups having a carbon number of 1, 2, 3,..., or 10, and this has the same meaning in other functional groups in which the carbon number is specified, unless otherwise specified.

[0057] As the hydrocarbon group having a carbon number of 1 to 10 in the above X 1 and X 2 , for example, an alkyl group having a carbon number of 1 to 10 or the like can be given. Also, as the alkyl group having a carbon number of 1 to 10, there is no particular limitation, and for example, a chain alkyl group including a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group, a cyclic alkyl group including a cyclopentyl group and a cyclohexyl group, and the like can be given. As the hydrocarbon group having a carbon number of 1 to 10 in the above X 1 and X 2 , a hydrocarbon group having a carbon number of 1, 2, 3, 4, 5, and 6 is preferred, and a hydrocarbon group having a carbon number of 1, 2, and 3 is more preferred.

[0058] As the alkoxy group having a carbon number of 1 to 10 in the above X 1 and X 2 , there is no particular limitation, and for example, a chain alkoxy group including a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, and a hexyloxy group, a cyclic alkoxy group including a cyclopentoxy group and a cyclohexyloxy group, a phenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, a 3,5-dimethylphenoxy group, and the like can be given. As the alkoxy group having a carbon number of 1 to 10 in the above X 1 and X 2 , an alkoxy group having a carbon number of 1, 2, 3, 4, 5, and 6 is preferred, and an alkoxy group having a carbon number of 1, 2, and 3 is more preferred.

[0059] The hydrocarbon group having a halogen atom having a carbon number of 1 to 10 in the above X 1 and X 2 means a functional group in which a part or all of hydrogens in the hydrocarbon group are substituted with halogen atoms. The above halogen atom represents an atom of fluorine, chlorine, bromine, and iodine. As the hydrocarbon group having a halogen atom having a carbon number of 1 to 10 in the above X 1 and X2 having a halogen atom, preferably a hydrocarbon group having a halogen atom having 1, 2, 3, 4, 5 and 6 carbon atoms, more preferably a hydrocarbon group having a halogen atom having 1, 2 and 3 carbon atoms.

[0060] the above X 1 and X 2 having a hetero atom having 1 to 10 carbon atoms means a functional group in which a part or all of hydrogen and carbon in the hydrocarbon group are substituted with a hetero atom. The above hetero atom means an atom such as oxygen, nitrogen and sulfur. As the above X 1 and X 2 having a hetero atom having 1 to 10 carbon atoms, preferably a hydrocarbon group having a hetero atom having 1, 2, 3, 4, 5 and 6 carbon atoms, more preferably a hydrocarbon group having a hetero atom having 1, 2 and 3 carbon atoms.

[0061] As the above X 1 and X 2 having a halogen atom or a hetero atom, for example, chain halogen-containing alkyl groups such as iodomethyl, bromomethyl, chloromethyl, fluoromethyl, diiodomethyl, dibromomethyl, dichloromethyl, difluoromethyl, triiodomethyl, tribromomethyl, trichloromethyl, trifluoromethyl, 2-iodoethyl, 2-bromoethyl, 2-chloroethyl, 2-fluoroethyl, 1,2-diiodoethyl, 1,2-dibromoethyl, 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, cyclic halogen-containing alkyl groups such as 2-iodocyclohexyl, 2-bromocyclohexyl, 2-chlorocyclohexyl and 2-fluorocyclohexyl, halogen-containing aryl groups such as 2-iodophenyl, 2-bromophenyl, 2-chlorophenyl, 2-fluorophenyl, 3-iodophenyl, 3-bromophenyl, 3-chlorophenyl, 3-fluorophenyl, 4-iodophenyl, 4-bromophenyl, 4-chlorophenyl, 4-fluorophenyl, 2,6-diiodophenyl, 2,6-dibromophenyl, 2,6-dichlorophenyl, 2,6-difluorophenyl, 3,5-diiodophenyl, 3,5-dibromophenyl, 3,5-dichlorophenyl, 3,5-difluorophenyl, pentaiodophenyl, pentabromophenyl, pentachlorophenyl and pentafluorophenyl, hetero-containing aryl groups such as 2-nitrophenyl, 4-nitrophenyl, 2,4-dinitrophenyl, 2,6-dinitrophenyl and 3-amino-2-naphthyl, and the like.

[0062] the above X 1 and X 2The hydrocarbon group having an unsaturated bond having 1 to 10 carbon atoms in the above-mentioned X

[0063] The above-mentioned X 1 and X 2 having 1 to 10 carbon atoms having an unsaturated bond, for example, vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 2-methyl-2-propenyl group, 2-butenyl group, 3-butenyl group, 3-methyl-2-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, pent-1,4-dienyl group, pent-2,4-dienyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, hex-1,3-dienyl group, hex-1,5-dienyl group, hex-2,4-dienyl group, hex-2,5-dienyl group, hex-3,5-dienyl group, 3-methyl-hex-2,4-dienyl group, and the like chain alkenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 2,4-cyclopentadienyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group, and the like cyclic alkenyl group, 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, 2-naphthyl group, and the like aryl group, ethynyl group, 2-propynyl group, butynyl group, 2-butynyl group, 3-butynyl group, pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, and the like chain alkynyl group, and the like.

[0064] The above-mentioned X 1 and X 2 having 1 to 10 carbon atoms having a halogen atom mean a functional group in which a part or all of hydrogens in the alkoxy group are substituted with a halogen atom. Here, the halogen atom means the same as the above-mentioned case, that is, fluorine, chlorine, bromine, and iodine atom. The alkoxy group having a halogen atom having 1 to 10 carbon atoms in the above-mentioned X 1 and X 2 is preferably an alkoxy group having a halogen atom having 1, 2, 3, 4, 5, and 6 carbon atoms, and more preferably an alkoxy group having a halogen atom having 1, 2, and 3 carbon atoms.

[0065] Further, the alkoxy group having 1 to 10 carbon atoms having a hetero atom in the above-mentioned X 1 and X 2 means a functional group in which a part or all of hydrogens and carbons in the alkoxy group are substituted with a hetero atom. Here, the hetero atom means the same as the above-mentioned case, that is, oxygen, nitrogen, sulfur, and the like atom. The alkoxy group having 1 to 10 carbon atoms having a hetero atom in the above-mentioned X 1 and X 2having a hetero atom, the number of carbon atoms of which is 1 to 10, preferably a hetero atom-containing alkoxy group having 1, 2, 3, 4, 5, and 6 carbon atoms, more preferably a hetero atom-containing alkoxy group having 1, 2, and 3 carbon atoms.

[0066] as X 1 and X 2 Specific examples of the halogen atom- or hetero atom-containing alkoxy group in the above X 1 and X 2 having 1 to 10 carbon atoms and having an unsaturated bond include, for example, chain halogen atom- or hetero atom-containing alkoxy groups such as iodomethoxy, bromomethoxy, chloromethoxy, fluoromethoxy, diiodomethoxy, dibromomethoxy, dichloromethoxy, difluoromethoxy, triiodomethoxy, tribromomethoxy, trichloromethoxy, trifluoromethoxy, 2-iodoethoxy, 2-bromoethoxy, 2-chloroethoxy, 2-fluoroethoxy, 1,2-diiodoethoxy, 1,2-dibromoethoxy, 1,2-dichloroethoxy, 1,2-difluoroethoxy, 2,2-diiodoethoxy, 2,2-dibromoethoxy, 2,2-dichloroethoxy, 2,2-difluoroethoxy, 2,2,2-triiodoethoxy, 2,2,2-tribromoethoxy, 2,2,2-trichloroethoxy, 2,2,2-trifluoroethoxy, and hexafluoro-2-propoxy, cyclic halogen atom- or hetero atom-containing alkoxy groups such as 2-iodocyclohexyloxy, 2-bromocyclohexyloxy, 2-chlorocyclohexyloxy, and 2-fluorocyclohexyloxy, halogen atom- or hetero atom-containing aryl groups such as 2-iodophenoxy, 2-bromophenoxy, 2-chlorophenoxy, 2-fluorophenoxy, 3-iodophenoxy, 3-bromophenoxy, 3-chlorophenoxy, 3-fluorophenoxy, 4-iodophenoxy, 4-bromophenoxy, 4-chlorophenoxy, 4-fluorophenoxy, 2,6-diiodophenoxy, 2,6-dibromophenoxy, 2,6-dichlorophenoxy, 2,6-difluorophenoxy, 3,5-diiodophenoxy, 3,5-dibromophenoxy, 3,5-dichlorophenoxy, 3,5-difluorophenoxy, pentaiodophenoxy, pentabromophenoxy, pentachlorophenoxy, and pentafluorophenoxy, and hetero atom-containing aryl groups such as 2-nitrophenoxy, 4-nitrophenoxy, 2,4-dinitrophenoxy, 2,6-dinitrophenoxy, and 3-amino-2-naphthyloxy.

[0067] as X 1 and X 2 having 1 to 10 carbon atoms and having an unsaturated bond include, for example, chain halogen atom- or hetero atom-containing alkoxy groups such as iodomethoxy, bromomethoxy, chloromethoxy, fluoromethoxy, diiodomethoxy, dibromomethoxy, dichloromethoxy, difluoromethoxy, triiodomethoxy, tribromomethoxy, trichloromethoxy, trifluoromethoxy, 2-iodoethoxy, 2-bromoethoxy, 2-chloroethoxy, 2-fluoroethoxy, 1,2-diiodoethoxy, 1,2-dibromoethoxy, 1,2-dichloroethoxy, 1,2-difluoroethoxy, 2,2-diiodoethoxy, 2,2-dibromoethoxy, 2,2-dichloroethoxy, 2,2-difluoroethoxy, 2,2,2-triiodoethoxy, 2,2,2-tribromoethoxy, 2,2,2-trichloroethoxy, 2,2,2-trifluoroethoxy, and hexafluoro-2-propoxy, cyclic halogen atom- or hetero atom-containing alkoxy groups such as 2-iodocyclohexyloxy, 2-bromocyclohexyloxy, 2-chlorocyclohexyloxy, and 2-fluorocyclohexyloxy, halogen atom- or hetero atom-containing aryl groups such as 2-iodophenoxy, 2-bromophenoxy, 2-chlorophenoxy, 2-fluorophenoxy, 3-iodophenoxy, 3-bromophenoxy, 3-chlorophenoxy, 3-fluorophenoxy, 4-iodophenoxy, 4-bromophenoxy, 4-chlorophenoxy, 4-fluorophenoxy, 2,6-diiodophenoxy, 2,6-dibromophenoxy, 2,6-dichlorophenoxy, 2,6-difluorophenoxy, 3,5-diiodophenoxy, 3,5-dibromophenoxy, 3,5-dichlorophenoxy, 3,5-difluorophenoxy, pentaiodophenoxy, pentabromophenoxy, pentachlorophenoxy, and pentafluorophenoxy, and hetero atom-containing aryl groups such as 2-nitrophenoxy, 4-nitrophenoxy, 2,4-dinitrophenoxy, 2,6-dinitrophenoxy, and 3-amino-2-naphthyloxy.

[0068] as X 1 and X 2Specific examples of the alkoxy group having an unsaturated bond having 1 to 10 carbon atoms include, for example, linear alkenyloxy groups such as vinyl oxy, 1-propenyloxy, 2-propenyloxy, isopropenyloxy, 2-methyl-2-propenyloxy, 2-butenyloxy, 3-butenyloxy, 3-methyl-2-butenyloxy, 1-pentenyloxy, 2-pentenyloxy, 3-pentenyloxy, 4-pentenyloxy, pent-1,4-dienyloxy, pent-2,4-dienyloxy, 1-hexenyloxy, 2-hexenyloxy, 3-hexenyloxy, 4-hexenyloxy, 5-hexenyloxy, hex-1,3-dienyloxy, hex-1,5-dienyloxy, hex-2,4-dienyloxy, hex-2,5-dienyloxy, hex-3,5-dienyloxy, and 3-methyl-hex-2,4-dienyloxy; cyclic alkenyloxy groups such as 1-cyclopentenyloxy, 2-cyclopentenyloxy, 2,4-cyclopentadienyloxy, 1-cyclohexenyloxy, 2-cyclohexenyloxy, and 3-cyclohexenyloxy; aryloxy groups such as phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,6-dimethylphenoxy, 3,5-dimethylphenoxy, 2,4,6-trimethylphenoxy, 1-naphthyloxy, and 2-naphthyloxy; and acetylenyloxy groups such as ethynoxy, 2-propynoxy, butynoxy, 2-butynoxy, 3-butynoxy, pentynoxy, 2-pentynoxy, 3-pentynoxy, and 4-pentynoxy.

[0069] X above 1 and X above 2 may be the same or different from each other. In addition, as X above 1 and X above 2 , the above-listed functional groups are merely simple examples, and the present embodiment is not limited to these.

[0070] X above 3 to X above 5 each independently represent 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. In addition, at least one of X above 3 to X above 5 is any one of the above hydrocarbon group having 1 to 10 carbon atoms or the above alkoxy group having 1 to 10 carbon atoms.

[0071] The above hydrocarbon group having 1 to 10 carbon atoms, the above alkoxy group having 1 to 10 carbon atoms, the above hydrocarbon group having a halogen atom or the like, and the above alkoxy group having a halogen atom or the like are the same as described above in X above 1 and X above 2 . Therefore, the details thereof are omitted.

[0072] X above3 ~ X 5 may be the same or different from each other. In addition, as the above X 3 ~ X 5 The above-mentioned functional groups are merely simple examples, and the present embodiment is not limited to these.

[0073] Specific examples of the phosphate esters represented by the above chemical formula (A) include, for example, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, 2-ethylhexyl diphenyl phosphate, triallyl phosphate, triargyl phosphate, tri(2-butoxyethyl) phosphate, tri(2-chloroethyl) phosphate, ethylbis(2,2,2-trifluoroethyl) phosphate, diethyl 2,2,2-trifluoroethyl phosphate, tri(2,2,2-trifluoroethyl) phosphate, tri(1,1,1,3,3,3-hexafluoro-2-propyl) phosphate, dimethyl fluorophosphate, diethyl fluorophosphate, dipropyl fluorophosphate, dibutyl fluorophosphate, dipentyl fluorophosphate, dihexyl fluorophosphate, and 2-ethylhexylphenyl fluorophosphate. Diallyl fluorophosphate, diacetylacetyl 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, dimethyltrimethylsilyl phosphate, diethyltrimethylsilyl phosphate, trimethylsilyl dipropyl phosphate, dibutyltrimethylsilyl phosphate, trimethyl Silyl dipentyl phosphate, dihexyltrimethylsilyl phosphate, trimethylsilyl diphenyl phosphate, diallyl trimethylsilyl phosphate, trimethylsilyl diargynyl 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, methyltrimethylsilyl fluorophosphate, ethyltrimethylsilyl fluorophosphate, trimethylsilyl(propyl) fluorophosphate, butyltrimethylsilyl fluorophosphate, trimethylsilyl(pentyl) fluorophosphate, hexyltrimethylsilyl Alkyl fluorophosphates, trimethylsilyl(phenyl) fluorophosphates, allyltrimethylsilyl fluorophosphates, trimethylsilyl(propynyl) fluorophosphates, 2-butoxyethyltrimethylsilyl fluorophosphates, 2-chloroethyltrimethylsilyl fluorophosphates, 2,2,2-trifluoroethyltrimethylsilyl fluorophosphates, 1,1,1,3,3,3-hexafluoro-2-propyltrimethylsilyl fluorophosphates, trimethylsilyl difluorophosphates, dimethylvinylsilyl difluorophosphates, dimethylphenylsilyl difluorophosphates, triethylsilyl difluorophosphates, cyclohexyldimethylsilyl difluorophosphates, triisopropylsilyl difluorophosphates, methyldiphenylsilyl difluorophosphates, etc.However, the phosphoric acid ester represented by the above formula (A) is not limited to these compound groups.

[0074] <raw material salt>

[0075] The above raw material salt is represented by the following formula (B).

[0076] [Chemical Formula 9]

[0077] MX 6 n (B)

[0078] In the above formula (B), the above M represents an alkali metal, an alkaline earth metal, aluminum, a transition metal, or onium.

[0079] As the above alkali metal, there is no particular limitation, and Li, Na, K, Rb, Cs can be given. Among these alkali metals, from the viewpoint of easiness of obtaining, Li, Na, and K are preferred, and from the viewpoint of versatility of the phosphate compound, Li and Na are more preferred.

[0080] As the above alkaline earth metal, there is no particular limitation, and Be, Mg, Ca, Sr, Ba can be given. Among these alkaline earth metals, from the viewpoints of easiness of obtaining and safety, Mg, Ca, and Ba are preferred, and from the viewpoint of versatility of the phosphate compound, Mg is more preferred.

[0081] As the above transition metal, there is no particular limitation, and Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn can be given. Among these transition metals, from the viewpoint of easiness of obtaining, Ti, Mn, Fe, Co, Ni, and Cu are preferred.

[0082] As the above onium, there is no particular limitation, and primary ammonium, secondary ammonium, tertiary ammonium, quaternary ammonium, quaternary phosphonium, sulfonium, and the like can be given.

[0083] As the above primary ammonium, there is no particular limitation, and for example, methylammonium, ethylammonium, propylammonium, isopropylammonium, and the like can be given. These can be used singly or in combination of two or more.

[0084] As the above secondary ammonium, there is no particular limitation, and for example, dimethylammonium, diethylammonium, dipropylammonium, dibutylammonium, ethylmethylammonium, methylpropylammonium, butylmethylammonium, butylpropylammonium, diisopropylammonium, and the like can be given.

[0085] As the above tertiary amine, there is no particular limitation, and examples thereof include trimethylamine, triethylamine, tripropylamine, tributylamine, ethyldimethylamine, diethylmethylamine, triisopropylamine, dimethylisopropylamine, diethylisopropylamine, dimethylpropylamine, butyldimethylamine, 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, pyridinium, and the like.

[0086] As the above quaternary amine, there is no particular limitation, and examples thereof include aliphatic quaternary amines, imidazoliums, pyridiniums, pyrazoliums, pyridaziniums, and the like.

[0087] Further, as the above aliphatic quaternary amines, there is no particular limitation, and examples thereof include tetraethylammonium, tetrapropylammonium, tetraisopropylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, trimethylpropylammonium, trimethylisopropylammonium, tetrabutylammonium, butyltrimethylammonium, trimethylamylammonium, hexyltrimethylammonium, 1-methyl-1-propylpyrrolidinium, 1-ethyl-1-methyl-pyrrolidinium, 1-butyl-1-methylpyrrolidinium, 1-ethyl-1-methyl-piperidinium, 1-butyl-1-methylpiperidinium, and the like.

[0088] As the above imidazoliums, there is no particular limitation, and examples thereof include 1,3-dimethyl-imidazolium, 1-ethyl-3-methylimidazolium, 1-n-propyl-3-methylimidazolium, 1-n-butyl-3-methylimidazolium, 1-n-hexyl-3-methylimidazolium, and the like.

[0089] As the above pyridiniums, there is no particular limitation, and examples thereof include 1-methylpyridinium, 1-ethylpyridinium, 1-n-propylpyridinium, and the like.

[0090] As the above pyrazoliums, there is no particular limitation, 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, 3-trifluoromethylpyrazolium, and the like.

[0091] As the above pyridaziniums, there is no particular limitation, 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, 3-chloro-6-methoxypyridazinium, and the like.

[0092] Among the oniums, from the viewpoints of easiness of obtaining and versatility, tetraethylammonium, triethylmethylammonium, 1-methyl-l-propylpyrrolidinium, and 1-ethyl-3-methylimidazolium, and the like are preferred.

[0093] As the halogen atom in the above X 6 , atoms of fluorine, chlorine, bromine, and iodine can be given. Among these halogen atoms, from the viewpoints of the height of the dissociation ability and the reuse of the by-product, atoms of chlorine, bromine, and iodine are preferred.

[0094] As the alkoxy group having 1 to 10 carbon atoms in the above X 6 , there is no particular limitation, and chain alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexyloxy, cyclic alkoxy groups such as cyclopentoxy and cyclohexyloxy, phenoxy, 3-methylphenoxy, 4-methylphenoxy, 3,5-dimethylphenoxy, and the like can be given. As the alkoxy group having 1 to 10 carbon atoms in the above X 6 , alkoxy groups having 1, 2, 3, 4, 5, and 6 carbon atoms are preferred, and alkoxy groups having 1, 2, and 3 carbon atoms are more preferred.

[0095] As the halogenated acyloxy group in the above X 6 , there is no particular limitation, and a functional group in which any one of the carbon atoms having 1 to 7 carbon atoms is substituted with a halogen atom or one or more hydrogen atoms is preferred. Specifically, for example, iodoacetyl, bromoacetyl, chloroacetyl, fluoroacetyl, diiodoacetyl, dibromoacetyl, dichloroacetyl, difluoroacetyl, triiodoacetyl, tribromoacetyl, trichloroacetyl, trifluoroacetyl, 3,3,3-triiodopropionyl, 3,3,3-tribromopropionyl, 3,3,3-trichloropropionyl, 3,3,3-trifluoropropionyl, pentaiodopropionyl, pentabromopropionyl, pentachloropropionyl, pentafluoropropionyl, 4,4,4-triiodobutyryl, 4,4,4-tribromobutyryl, 4,4,4-trichlorobutyryl, 4,4,4-trifluorobutyryl, 3,3,4,4,4-pentaiodobutyryl, 3,3,4,4,4-pentabromobutyryl, 3,3,4,4,4-pentachlorobutyryl, 3,3,4,4,4-pentafluorobutyryl, heptaiodobutyryl, heptabromobutyryl, heptachlorobutyryl, heptafluorobutyryl, pentaiodobenzoyl, pentabromobenzoyl, pentachlorobenzoyl, and pentafluorobenzoyl, and the like can be given. The above halogen atom indicates fluorine, chlorine, bromine, and iodine.

[0096] The sulfonyloxy group in the above X 6 is represented by -SO3Y. Here, 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 any one selected from a halogen atom, a heteroatom, or an unsaturated bond.

[0097] As the halogen atom in the above Y, atoms of fluorine, chlorine, bromine and iodine can be given.

[0098] As the hydrocarbon group having 1 to 10 carbon atoms in the above Y, there are no particular limitations, and for example, chain alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl and octyl, cyclic alkyl groups such as cyclopentyl and cyclohexyl, and the like can be given. As the hydrocarbon group having 1 to 10 carbon atoms in the above Y, hydrocarbon groups having 1, 2, 3, 4, 5 and 6 carbon atoms are preferred, and hydrocarbon groups having 1, 2 and 3 carbon atoms are more preferred.

[0099] The hydrocarbon group having 1 to 10 carbon atoms having a halogen atom in the above Y means a functional group in which part or all of the hydrogens in the hydrocarbon group are substituted with halogen atoms. The above halogen atom means atoms of fluorine, chlorine, bromine and iodine. As the hydrocarbon group having 1 to 10 carbon atoms having a halogen atom in the above Y, hydrocarbon groups having 1, 2, 3, 4, 5 and 6 carbon atoms having a halogen atom are preferred, and hydrocarbon groups having 1, 2 and 3 carbon atoms having a halogen atom are more preferred.

[0100] The hydrocarbon group having 1 to 10 carbon atoms having a hetero atom in the above Y means a functional group in which part or all of the hydrogens and carbons in the hydrocarbon group are substituted with hetero atoms. The above hetero atom means atoms such as oxygen, nitrogen and sulfur. As the hydrocarbon group having 1 to 10 carbon atoms having a hetero atom in the above Y, hydrocarbon groups having 1, 2, 3, 4, 5 and 6 carbon atoms having a hetero atom are preferred, and hydrocarbon groups having 1, 2 and 3 carbon atoms having a hetero atom are more preferred.

[0101] As specific examples of the hydrocarbon group having 1 to 10 carbon atoms and having a halogen atom or a hetero atom in the above-mentioned Y, for example, chain halogen-containing alkyl groups such as iodomethyl, bromomethyl, chloromethyl, fluoromethyl, diiodomethyl, dibromomethyl, dichloromethyl, difluoromethyl, triiodomethyl, tribromomethyl, trichloromethyl, trifluoromethyl, 2-iodoethyl, 2-bromoethyl, 2-chloroethyl, 2-fluoroethyl, 1,2-diiodoethyl, 1,2-dibromoethyl, 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, cyclic halogen-containing alkyl groups such as 2-iodocyclohexyl, 2-bromocyclohexyl, 2-chlorocyclohexyl, and 2-fluorocyclohexyl, halogen-containing aryl groups such as 2-iodophenyl, 2-bromophenyl, 2-chlorophenyl, 2-fluorophenyl, 3-iodophenyl, 3-bromophenyl, 3-chlorophenyl, 3-fluorophenyl, 4-iodophenyl, 4-bromophenyl, 4-chlorophenyl, 4-fluorophenyl, 2,6-diiodophenyl, 2,6-dibromophenyl, 2,6-dichlorophenyl, 2,6-difluorophenyl, 3,5-diiodophenyl, 3,5-dibromophenyl, 3,5-dichlorophenyl, 3,5-difluorophenyl, penta-iodophenyl, penta-bromophenyl, penta-chlorophenyl, and penta-fluorophenyl, and hetero-containing aryl groups such as 2-nitrophenyl, 4-nitrophenyl, 2,4-dinitrophenyl, 2,6-dinitrophenyl, and 3-amino-2-naphthyl, and the like.

[0102] The hydrocarbon group having 1 to 10 carbon atoms and having an unsaturated bond in the above-mentioned Y refers to, for example, a hydrocarbon group having 1 to 10 carbon atoms and having a double bond or a triple bond between carbon-carbon. Further, as the hydrocarbon group having an unsaturated bond, a hydrocarbon group having 1, 2, 3, 4, and 5 unsaturated bonds is preferable, and a hydrocarbon group having 1, 2, and 3 unsaturated bonds is more preferable.

[0103] As specific examples of the hydrocarbon group having 1 to 10 range of carbon atoms and having unsaturated bond in the above-mentioned Y, for example, chain alkenyl groups such as ethenyl, 1- propenyl, 2-propenyl, isopropenyl, 2-methyl-2-propenyl, 2-butenyl, 3-butenyl, 3-methyl-2-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, pent-1,4-dienyl, pent-2,4-dienyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, hex-1,3-dienyl, hex-1,5-dienyl, hex-2,4-dienyl, hex-2,5-dienyl, hex-3,5-dienyl, and 3-methyl-hex-2,4-dienyl, cyclic alkenyl groups such as 1-cyclopentenyl, 2-cyclopentenyl, 2,4-cyclopentadienyl, 1-cyclohexenyl, 2-cyclohexenyl, and 3-cyclohexenyl, aryl groups such as phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,6-dimethylphenyl, 3,5-dimethylphenyl, 2,4,6-trimethylphenyl, 1-naphthyl, and 2-naphthyl, chain alkynyl groups such as ethynyl, 2-propynyl, butynyl, 2-butynyl, 3-butynyl, pentynyl, 2-pentynyl, 3-pentynyl, and 4-pentynyl, and the like can be given.

[0104] As specific examples of the raw material salt represented by the above-mentioned formula (B), 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 (II) chloride, manganese (II) bromide, manganese (II) iodide, nickel (II) chloride, nickel (II) bromide, nickel (II) iodide, cobalt (II) chloride, cobalt (II) bromide, cobalt (II) iodide, 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, and the like can be given. Among them, the raw material salt represented by the above-mentioned formula (B) is not limited to these compound groups.

[0105] The above-mentioned n is a valence number, and represents a natural number of 1 to 4.

[0106] <Phosphate compound>

[0107] The above phosphate compound is represented by the following Chemical Formula (C).

[0108] [Chemical Formula 10]

[0109]

[0110] In the above Chemical Formula (C), the above M represents the same cation species as the above Chemical Formula (A). In addition, the above X 1 and X 2 represent the same functional group as the above Chemical Formula (A). Therefore, detailed explanation thereof is omitted.

[0111] As specific examples of the phosphoric acid salt compound represented by the above formula (C), for example, lithium diethylphosphate, sodium diethylphosphate, potassium diethylphosphate, magnesium diethylphosphate, calcium diethylphosphate, aluminum diethylphosphate, manganese (II) diethylphosphate, nickel (II) diethylphosphate, cobalt (II) diethylphosphate, copper (II) diethylphosphate, tetraethylammonium diethylphosphate, triethylmethylammonium diethylphosphate, 1-propyl-l-methylpyrrolidinium diethylphosphate, 1-ethyl-3-methylimidazolium diethylphosphate, lithium dipropylphosphate, sodium dipropylphosphate, potassium dipropylphosphate, magnesium dipropylphosphate, calcium dipropylphosphate, aluminum dipropylphosphate, manganese (II) dipropylphosphate, nickel (II) dipropylphosphate, cobalt (II) dipropylphosphate, copper (II) dipropylphosphate, tetraethylammonium dipropylphosphate, triethylmethylammonium dipropylphosphate, 1-propyl-l-methylpyrrolidinium dipropylphosphate, 1-ethyl-3-methylimidazolium dipropylphosphate, lithium dibutylphosphate, sodium dibutylphosphate, potassium dibutylphosphate, magnesium dibutylphosphate, calcium dibutylphosphate, aluminum dibutylphosphate, manganese (II) dibutylphosphate, nickel (II) dibutylphosphate, cobalt (II) dibutylphosphate, copper (II) dibutylphosphate, tetraethylammonium dibutylphosphate, triethylmethylammonium dibutylphosphate, 1-propyl-l-methylpyrrolidinium dibutylphosphate, 1-ethyl-3-methylimidazolium dibutylphosphate, 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, nickel (II) bis(2,2,2-trifluoroethyl)phosphate, cobalt (II) bis(2,2,2-trifluoroethyl)phosphate, copper (II) bis(2,2,2-trifluoroethyl)phosphate, tetraethylammonium bis(2,2,2-trifluoroethyl)phosphate, triethylmethylammonium bis(2,2,2-trifluoroethyl)phosphate, 1-propyl-l-methylpyrrolidinium bis(2,2,2-trifluoroethyl)phosphate, 1-ethyl-3-methylimidazolium bis(2,2,2-trifluoroethyl)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)phosphate, cobalt (II) ethyl(2,2,2-trifluoroethyl)phosphate, copper (II) ethyl(2,2,2-trifluoroethyl)phosphate, tetraethylammonium ethyl(2,2,2-trifluoroethyl)phosphate, triethylmethylammonium ethyl(2,2,2-trifluoroethyl)phosphate, 1-propyl-l-methylpyrrolidinium ethyl(2,2,2-trifluoroethyl)phosphate, 1-ethyl-3-methylimidazolium ethyl(2,2,2-trifluoroethyl)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, nickel (II) bis(2,2,2-trifluoroethyl)phosphate, cobalt (II) bis(2,2,2-trifluoroethyl)phosphate, copper (II) bis(2,2,2-trifluoroethyl)phosphate, tetraethylammonium bis(2,2,2-trifluoroethyl)phosphate, triethylmethylammonium bis(2,2,2-trifluoroethyl)phosphate, 1-propyl-l-methylpyrrolidinium bis(2,2,2-trifluoroethyl)phosphate, 1-ethyl-3-methylimidazolium bis(2,2,2-trifluoroethyl)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)phosphate, cobalt (II) ethyl(2,2,2-trifluoroethyl)phosphate, copper (II) ethyl(2,2,2-trifluoroethyl)phosphate, tetraethylammonium ethyl(2,2,2-trifluoroethyl)phosphate, triethylmethylammonium ethyl(2,2,2-trifluoroethyl)phosphate, 1-propyl-l-methylpyrrolidinium ethyl(2,2,2-trifluoroethyl)phosphate, 1-ethyl-3-methylimidazolium ethyl(2,2,2-trifluoroethyl)phosphate,2,2,2-trifluoroethyl)phosphonium, 1-propyl-1-methylpyrrolidinium ethyl (2,2,2- trifluoroethyl)phosphonium, 1-ethyl-3-methylimidazolium ethyl (2,2,2-trifluoroethyl)phosphonium, lithium 2,2,2-trifluoroethyl fluorophosphate, 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 difluorophosphate, 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, and the like. Among them, the phosphate compound represented by the above formula (C) is not limited to these compound groups.

[0112] <Reaction conditions of the step (I)>

[0113] The reaction molar ratio of the above-mentioned step (I) is not particularly limited, and can be appropriately set according to the reaction kind. In the reaction molar ratio of the phosphoric acid ester to the raw material salt, the lower limit value of the phosphoric acid ester is usually 1 mole or more per 1 mole of the raw material salt. In addition, the upper limit value of the phosphoric acid ester is usually 2.5 moles or less, and from the viewpoint of industrial production, 1.5 moles or less is preferred.

[0114] The reaction starting temperature of the above-mentioned step (I) is not particularly limited as long as the reaction proceeds, and can be appropriately set according to the reaction kind. The lower limit value of the reaction starting temperature is usually 0°C or higher, and from the viewpoint of reactivity, 20°C or higher, and more preferably 60°C or higher is preferred. In addition, the upper limit value of the reaction starting temperature is usually 150°C or lower, and from the viewpoint of reactivity, 120°C or lower, and more preferably 100°C or lower is preferred. Note that by setting the lower limit value of the reaction starting 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 value of the reaction starting temperature to 150°C or lower, it is possible to suppress the excess energy used in the reaction.

[0115] The method of adjusting the reaction start temperature is not particularly limited. For example, in the case where the reaction start temperature is cooled and controlled within the above-mentioned temperature range, the reaction vessel into which the phosphoric acid ester and the raw material salt are charged can be subjected to ice cooling or the like. In the case where the reaction start temperature is heated and controlled within the above-mentioned temperature range, the reaction vessel can be subjected to oil bath heating or the like set to an arbitrary temperature.

[0116] The reaction time of the above-mentioned step (I) is not particularly limited and can be appropriately set according to the reaction type. 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, 6 hours or less, more preferably 4 hours or less, is preferred.

[0117] The reaction of the above-mentioned step (I) can be carried out in the absence of a solvent or in a non-aqueous solvent. In the case where the reaction of step (I) is carried out in the absence of a solvent, the phosphoric acid ester also functions as a reaction solvent.

[0118] The non-aqueous solvent is not particularly limited as long as it does not cause an obstacle to the reaction with other reactants or products, and a non-protic organic solvent is preferably used.

[0119] The non-protic organic solvent is not particularly limited, and for example, alcohols, nitriles, esters, ketones, ethers, halogenated hydrocarbons, and the like can be mentioned. One of these can be used alone, or two or more kinds thereof can be used in combination.

[0120] The alcohol is not particularly limited, and for example, 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, and the like can be mentioned. One of these can be used alone, or two or more kinds thereof can be used in combination.

[0121] The nitrile is not particularly limited, and for example, acetonitrile, propionitrile, and the like can be mentioned. One of these can be used alone, or two or more kinds thereof can be used in combination.

[0122] The ester is not particularly limited, and for example, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and the like can be mentioned. One of these can be used alone, or two or more kinds thereof can be used in combination.

[0123] As the ketones, there are no particular limitations, and examples include acetone, methyl ethyl ketone, isobutyl methyl ketone, cyclohexanone, and the like. One of these can be used alone, or two or more of these can be used in combination.

[0124] As the ethers, there are no particular limitations, and examples include diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane, and the like. One of these can be used alone, or two or more of these can be used in combination.

[0125] As the halogenated hydrocarbons, there are no particular limitations, and examples include dichloromethane, chloroform, 1,1,2,2-tetrachloroethane, chlorobenzene, and the like. One of these can be used alone, or two or more of these can be used in combination.

[0126] In addition, other examples of the non-aqueous solvent include toluene, N,N-dimethylformamide, dimethyl sulfoxide, nitromethane, nitroethane, and the like.

[0127] Among the non-aqueous solvents exemplified above, in the present application, from the viewpoints of solubility of the reaction substrate and ease of obtaining, nitriles, esters, ketones, ethers, and halogenated hydrocarbons are preferred.

[0128] As for the amount of use of the non-aqueous solvent, the lower limit value with respect to 1 mole of the phosphoric acid ester is preferably 1 mole or more, and more preferably 10 moles or more. The upper limit value of the amount of use of the non-aqueous solvent with respect to 1 mole of the phosphoric acid ester is preferably 10,000 moles or less, more preferably 1,000 moles or less, and further preferably 100 moles or less. By setting the lower limit value of the amount of use of the non-aqueous solvent to 1 mole or more, it is possible to prevent a decrease in reactivity of the phosphoric acid ester with the raw material salt, and to suppress a decrease in yield and purity of the phosphoric acid salt compound. On the other hand, by setting the upper limit value of the amount of use of the non-aqueous solvent to 10,000 moles or less, it is possible to suppress the energy at the time of distilling it off, and to prevent becoming disadvantageous in industrial production.

[0129] The phosphoric acid salt compound obtained in the above-described process (I) can be isolated and purified according to its purity. The method is not particularly limited, and a publicly known method can be employed. Specifically, examples include methods such as atmospheric distillation, reduced pressure distillation, filtration, filtration, recrystallization, sublimation purification, silica gel column chromatography, preparative thin layer chromatography (PTLC), high speed liquid chromatography (HPLC), ion chromatography (IC), and the like.

[0130] (Method for producing phosphoric acid ester)

[0131] In the case where Z is a silicon atom, the phosphoric acid ester can be obtained by a publicly known production method using an acid anhydride or the like as a raw material. Among them, in the present embodiment, as shown in the chemical reaction formula below, 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 silyl phosphoric acid ester represented by Chemical Formula (F) is preferably included. By this, the phosphoric acid ester can be efficiently obtained.

[0132] [Chemical Formula 11]

[0133]

[0134] If the reaction is the step (II), as the silicon compound represented by Chemical Formula (E) above, the silicon compound that is by-produced in the step (I) can be reused. By this, the production efficiency is extremely high, and the manufacturing cost can be reduced to produce the phosphoric acid compound.

[0135] <Phosphoric acid compound>

[0136] The phosphoric acid compound is represented by the following Chemical Formula (D).

[0137] [Chemical Formula 12]

[0138]

[0139] In Chemical Formula (D) above, X 1 and X 2 represent the same functional groups as those of Chemical Formula (A) above. Therefore, detailed description thereof is omitted.

[0140] In Chemical Formula (D) above, 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 any one selected from a halogen atom, a hetero atom, or an unsaturated bond (hereinafter referred to as "primary hydrocarbon group having a halogen atom or the like"), or a secondary hydrocarbon group having 1 to 10 carbon atoms and having at least any one selected from a halogen atom, a hetero atom, or an unsaturated bond (hereinafter referred to as "secondary hydrocarbon group having a halogen atom or the like").

[0141] As the alkali metal in M', Li, Na, K, Rb, and Cs can be given. Among these alkali metals, from the viewpoint of easiness of obtaining, Li, Na, and K are preferable.

[0142] As the alkaline earth metal in M', there is no particular limitation, and Be, Mg, Ca, Sr, and Ba can be given. Among these alkaline earth metals, from the viewpoint of easiness of obtaining and safety, Mg, Ca, and Ba are preferable.

[0143] As the primary hydrocarbon group having 1 to 10 carbon atoms in the above M', there are no particular limitations, and examples include primary alkyl groups and the like. As the secondary hydrocarbon group having 1 to 10 carbon atoms in the above M', there are no particular limitations, and examples include secondary alkyl groups and the like. As the primary alkyl group having 1 to 10 carbon atoms and the secondary alkyl group having 1 to 10 carbon atoms, there are no particular limitations, and examples include chain alkyl groups such as methyl, ethyl, propyl, butyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, and octyl groups; cyclic alkyl groups such as cyclopentyl and cyclohexyl groups; and the like. As the primary hydrocarbon group having 1 to 10 carbon atoms in the above M', primary hydrocarbon groups having 1, 2, 3, 4, 5, and 6 carbon atoms are preferable, and primary hydrocarbon groups having 1, 2, and 3 carbon atoms are more preferable. As the secondary hydrocarbon group having 1 to 10 carbon atoms in the above M', secondary hydrocarbon groups having 1, 2, 3, 4, 5, and 6 carbon atoms are preferable, and secondary hydrocarbon groups having 1, 2, and 3 carbon atoms are more preferable.

[0144] As the primary hydrocarbon group having 1 to 10 carbon atoms and having a halogen atom or the like in the above M', and the secondary hydrocarbon group having 1 to 10 carbon atoms and having a halogen atom or the like, there are no particular limitations, and examples include chain halogenated alkyl groups such as 2-iodoethyl, 2-bromoethyl, 2-chloroethyl, 2-fluoroethyl, 1,2-diiodoethyl, 1,2-dibromoethyl, 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; cyclic halogenated alkyl groups such as 2-iodocyclohexyl, 2-bromocyclohexyl, 2-chlorocyclohexyl, and 2-fluorocyclohexyl; chain alkenyl groups such as 2-propenyl, 2-butenyl, and 3-butenyl; cyclic alkenyl groups such as 2-cyclopentenyl, 2-cyclohexenyl, and 3-cyclohexenyl; chain alkynyl groups such as 2-propynyl, 2-butynyl, 3-butynyl, 2-pentynyl, 3-pentynyl, and 4-pentynyl; and the like. As the primary hydrocarbon group having 1 to 10 carbon atoms in the above M', primary hydrocarbon groups having 1, 2, 3, 4, 5, and 6 carbon atoms having a halogen atom or the like are preferable, and primary hydrocarbon groups having 1, 2, and 3 carbon atoms having a halogen atom or the like are more preferable. As the secondary hydrocarbon group having 1 to 10 carbon atoms in the above M', secondary hydrocarbon groups having 1, 2, 3, 4, 5, and 6 carbon atoms having a halogen atom or the like are preferable, and secondary hydrocarbon groups having 1, 2, and 3 carbon atoms having a halogen atom or the like are more preferable.

[0145] The unsaturated bond in the above M' refers to, for example, a carbon-carbon double bond or a carbon-carbon triple bond.

[0146] More specifically, the phosphoric acid compound represented by the above formula (D) is preferably a phosphoric acid compound represented by the above formula (D) in which X 1 and X 2phosphoric acid diester in which each of R1to R4is independently an alkoxy group having 1 to 10 carbon atoms, and M' is a hydrogen atom, and X 1 and X 2 fluorophosphoric acid ester in which either of R1to R4is a fluorine atom and the other is an alkoxy group having 1 to 10 carbon atoms, and M' is a hydrogen atom, and X 1 and X 2 difluorophosphoric acid in which M' is a hydrogen atom.

[0147] As specific examples of the phosphoric acid compound represented by the above Chemical Formula (D), for example, dimethylphosphoric acid, diethylphosphoric acid, dipropylphosphoric acid, dibutylphosphoric acid, dipentylphosphoric acid, dihexylphosphoric acid, diphenylphosphoric acid, diallylphosphoric acid, dipropargylphosphoric acid, bis(2-butoxyethyl)phosphoric acid, bis(2-chloroethyl)phosphoric acid, bis(2,2,2-trifluoroethyl)phosphoric acid, bis(l, 1, 1,3,3,3-hexafluoro-2-propyl)phosphoric acid, methyl fluorophosphoric acid, ethyl fluorophosphoric acid, propyl fluorophosphoric acid, butyl fluorophosphoric acid, pentyl fluorophosphoric acid, hexyl fluorophosphoric acid, phenyl fluorophosphoric acid, allyl fluorophosphoric acid, propargyl fluorophosphoric acid, 2-butoxyethyl fluorophosphoric acid, 2-chloroethyl fluorophosphoric acid, 2,2,2-trifluoroethyl fluorophosphoric acid, 1, 1, 1,3,3,3-hexafluoro-2-propyl fluorophosphoric acid, difluorophosphoric acid, and the like can be given. Among them, the phosphoric acid compound represented by the above Chemical Formula (D) is not limited to these compound groups.

[0148] <Silicon compound>

[0149] The above silicon compound is represented by the following Chemical Formula (E).

[0150] [Chemical Formula 13]

[0151]

[0152] In the above Chemical Formula (E), X 3 to X 5 represent the same functional groups as those of the above Chemical Formula (A). Therefore, detailed explanation thereof is omitted.

[0153] X 7 is a leaving group, and represents a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a halogenated acyloxy group, or a sulfonyloxy group.

[0154] The halogen atom in the above X 7 may be given as an atom of fluorine, chlorine, bromine, and iodine. Among these halogen atoms, from the viewpoint of the height of the dissociation ability, and the reuse of the by-product, a chlorine atom, a bromine atom, and an iodine atom are preferred.

[0155] The halogen atom in the above X 7The alkyl group having 1 to 10 carbon atoms in the above-mentioned X is not particularly limited, and examples thereof include a linear alkyl group such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, and octyl; a cyclic alkyl group such as cyclopentyl and cyclohexyl; and the like. The alkyl group having 1 to 10 carbon atoms in the above-mentioned X is preferably an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, and more preferably an alkyl group having 1, 2, or 3 carbon atoms. 7 The alkyl group having 1 to 10 carbon atoms in the above-mentioned X is not particularly limited, and examples thereof include a linear alkyl group such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, and octyl; a cyclic alkyl group such as cyclopentyl and cyclohexyl; and the like. The alkyl group having 1 to 10 carbon atoms in the above-mentioned X is preferably an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, and more preferably an alkyl group having 1, 2, or 3 carbon atoms.

[0156] The alkyl group having 1 to 10 carbon atoms in the above-mentioned X is not particularly limited, and examples thereof include a linear alkyl group such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, and octyl; a cyclic alkyl group such as cyclopentyl and cyclohexyl; and the like. The alkyl group having 1 to 10 carbon atoms in the above-mentioned X is preferably an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, and more preferably an alkyl group having 1, 2, or 3 carbon atoms. 7 The haloacyloxy group in the above-mentioned X is not particularly limited, and is preferably a functional group in which 1 to 7 carbon atoms are replaced with a halogen atom. Specifically, examples thereof include iodoacetyl, bromoacetyl, chloroacetyl, fluoroacetyl, diiodoacetyl, dibromoacetyl, dichloroacetyl, difluoroacetyl, triiodoacetyl, tribromoacetyl, trichloroacetyl, trifluoroacetyl, 3,3,3-triiodopropionyl, 3,3,3-tribromopropionyl, 3,3,3-trichloropropionyl, 3,3,3-trifluoropropionyl, pentaiodopropionyl, pentabromopropionyl, pentachloropropionyl, pentafluoropropionyl, 4,4,4-triiodobutyryl, 4,4,4-tribromobutyryl, 4,4,4-trichlorobutyryl, 4,4,4-trifluorobutyryl, 3,3,4,4,4-pentaiodobutyryl, 3,3,4,4,4-pentabromobutyryl, 3,3,4,4,4-pentachlorobutyryl, 3,3,4,4,4-pentafluorobutyryl, heptaiodobutyryl, heptabromobutyryl, heptachlorobutyryl, heptafluorobutyryl, pentaiodobenzoyl, pentabromobenzoyl, pentachlorobenzoyl, pentafluorobenzoyl, and the like. The halogen atom in the above-mentioned haloacyloxy group represents fluorine, chlorine, bromine, and iodine.

[0157] The alkyl group having 1 to 10 carbon atoms in the above-mentioned X is not particularly limited, and examples thereof include a linear alkyl group such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, and octyl; a cyclic alkyl group such as cyclopentyl and cyclohexyl; and the like. The alkyl group having 1 to 10 carbon atoms in the above-mentioned X is preferably an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, and more preferably an alkyl group having 1, 2, or 3 carbon atoms. 7 The sulfoxy group in the above-mentioned X is represented by -SO3Y. Here, the above-mentioned 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 any one selected from a halogen atom, a hetero atom, or an unsaturated bond.

[0158] The halogen atom in the above-mentioned Y includes fluorine, chlorine, bromine, and iodine.

[0159] The hydrocarbon group having 1 to 10 carbon atoms in the above-mentioned Y is not particularly limited, and examples thereof include a linear alkyl group such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, and octyl; a cyclic alkyl group such as cyclopentyl and cyclohexyl; and the like. The hydrocarbon group having 1 to 10 carbon atoms in the above-mentioned 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.

[0160] The hydrocarbon group having a halogen atom having 1 to 10 carbon atoms in Y above means a functional group in which part or all of the hydrogens in the hydrocarbon group are substituted with halogen atoms. The halogen atom above means a fluorine, chlorine, bromine, and iodine atom. The hydrocarbon group having a halogen atom having 1 to 10 carbon atoms in Y above is preferably a hydrocarbon group having a halogen atom having 1, 2, 3, 4, 5, and 6 carbon atoms, and more preferably a hydrocarbon group having a halogen atom having 1, 2, and 3 carbon atoms.

[0161] The hydrocarbon group having a hetero atom having 1 to 10 carbon atoms in Y above means a functional group in which part or all of the hydrogens and carbons in the hydrocarbon group are substituted with hetero atoms. The hetero atom above means an oxygen, nitrogen, sulfur, and the like. The hydrocarbon group having a hetero atom having 1 to 10 carbon atoms in Y above is preferably a hydrocarbon group having a hetero atom having 1, 2, 3, 4, 5, and 6 carbon atoms, and more preferably a hydrocarbon group having a hetero atom having 1, 2, and 3 carbon atoms.

[0162] The hydrocarbon group having 1 to 10 carbon atoms and having an unsaturated bond in Y above means, for example, a hydrocarbon group having 1 to 10 carbon atoms and having a double bond or a triple bond between carbon-carbon. Further, as the hydrocarbon group having an unsaturated bond, a hydrocarbon group having 1, 2, 3, 4, and 5 unsaturated bonds is preferred, and a hydrocarbon group having 1, 2, and 3 unsaturated bonds is more preferred.

[0163] As specific examples of the hydrocarbon group having 1 to 10 carbon atoms in the range of the above-mentioned Y and having a halogen atom, a hetero atom, or an unsaturated bond, there are, for example, chain halogen-containing alkyl groups such as iodomethyl, bromomethyl, chloromethyl, fluoromethyl, diiodomethyl, dibromomethyl, dichloromethyl, difluoromethyl, triiodomethyl, tribromomethyl, trichloromethyl, trifluoromethyl, 2-iodoethyl, 2-bromoethyl, 2-chloroethyl, 2-fluoroethyl, 1,2-diiodoethyl, 1,2-dibromoethyl, 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; cyclic halogen-containing alkyl groups such as 2-iodocyclohexyl, 2-bromocyclohexyl, 2-chlorocyclohexyl, and 2-fluorocyclohexyl; chain alkenyl groups such as ethenyl, 2-propenyl, isopropenyl, 2-butenyl, and 3-butenyl; cyclic alkenyl groups such as 2-cyclopentenyl, 2-cyclohexenyl, and 3-cyclohexenyl; chain alkynyl groups such as ethynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, and 4-pentynyl; aryl groups such as phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,6-dimethylphenyl, 3,5-dimethylphenyl, 2,4,6-trimethylphenyl, 2-nitrophenyl, 4-nitrophenyl, 2,4-dinitrophenyl, and 2,6-dinitrophenyl; halogenated aryl groups such as 2-iodophenyl, 2-bromophenyl, 2-chlorophenyl, 2-fluorophenyl, 3-iodophenyl, 3-bromophenyl, 3-chlorophenyl, 3-fluorophenyl, 4-iodophenyl, 4-bromophenyl, 4-chlorophenyl, 4-fluorophenyl, 2,6-diiodophenyl, 2,6-dibromophenyl, 2,6-dichlorophenyl, 2,6-difluorophenyl, 3,5-diiodophenyl, 3,5-dibromophenyl, 3,5-dichlorophenyl, 3,5-difluorophenyl, pentaiodophenyl, pentabromophenyl, pentachlorophenyl, and pentafluorophenyl; and naphthyl groups such as 1-naphthyl and 2-naphthyl.

[0164] More specifically, the silicon compound represented by the above-mentioned formula (E) is preferably a silicon compound represented by the above-mentioned formula (E) wherein X 3 ~ X 5 each independently is a hydrocarbon group having 1 to 6 carbon atoms, and the above-mentioned X 7 is a trialkylsilyl halide when X is a halogen atom.

[0165] As specific examples of the silicon compound represented by the above formula (E), for example, 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, and the like can be given. Among them, the silicon compound represented by the above formula (E) is not limited to these compound groups.

[0166] <Reaction conditions of the step (II)>

[0167] The reaction molar ratio of the above step (II) is not particularly limited, and can be appropriately set depending on the kind of the reaction. In the reaction molar ratio of the phosphoric acid compound to the silicon compound, generally, the lower limit value of the silicon compound is 1 mole or more per 1 mole of the phosphoric acid compound. In addition, the upper limit value 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, and more preferably 1.5 moles or less.

[0168] The reaction start temperature of the above step (II) is not particularly limited as long as the reaction proceeds, and can be appropriately set depending on the kind of the reaction. The lower limit value of the reaction start temperature is generally 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 value of the reaction start temperature is generally 150°C or lower, and from the viewpoint of reactivity, it is preferably 120°C or lower, and more preferably 100°C or lower. Note that by making the lower limit value of the reaction start temperature 0°C or higher, it is possible to prevent the reaction rate from significantly decreasing. On the other hand, by making the upper limit value of the reaction start temperature 150°C or lower, it is possible to suppress the excess energy used in the reaction.

[0169] The adjustment method of the reaction start temperature is not particularly limited. For example, in the case where the reaction start temperature is cooled and controlled within the above temperature range, the reaction vessel into which the phosphoric acid compound and the silicon compound are charged can be performed by ice cooling or the like. In addition, in the case where the reaction start temperature is heated and controlled within the above temperature range, it can be performed by an oil bath or the like set to an arbitrary temperature.

[0170] The reaction time of the above step (II) is not particularly limited, and can be appropriately set depending on the kind of the reaction. The lower limit value of the reaction time is generally 1 hour or more. In addition, the upper limit value of the reaction time is generally 12 hours or less, and from the viewpoint of industrial production, it is preferably 6 hours or less, and more preferably 3 hours or less.

[0171] The reaction in step (II) described above can be carried out in a solvent-free environment or in a non-aqueous solvent. When the reaction in step (II) is carried out in a solvent-free environment, the silicon compound also functions as a reaction solvent.

[0172] As the aforementioned non-aqueous solvent, the same non-aqueous solvent as described in step (I) above can be used. Therefore, its details are omitted.

[0173] Regarding the amount of the aforementioned non-aqueous solvent used, the lower limit is preferably 1 mole or more, more preferably 10 moles or more, relative to 1 mole of the aforementioned phosphate compound. The upper limit 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 aforementioned phosphate 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 a decrease in the reactivity of the phosphate compound with the silicon compound, and to suppress a decrease in the yield and purity of the silyl phosphate. On the other hand, by setting the upper limit of the amount of the aforementioned non-aqueous solvent used to 10,000 moles or less, it is possible to suppress the energy required for its distillation, preventing it from becoming detrimental in industrial production.

[0174] The phosphate ester obtained in step (II) above can be purified by separation according to its purity. There are no particular limitations on the method; known methods can be used. Specifically, methods such as atmospheric distillation, vacuum distillation, filtration, filtration, recrystallization, sublimation purification, silica gel column chromatography, preparative thin-layer chromatography (PTLC), high-performance liquid chromatography (HPLC), and ion chromatography (IC) can be used.

[0175] Example

[0176] Hereinafter, preferred embodiments of the present invention will be described in detail by way of example. However, unless otherwise specified, the materials, proportions, etc., described in these embodiments are not intended to limit the scope of the present invention.

[0177] It should be noted that, in the following embodiments, the determination of purity and the measurement of physicochemical properties are performed using the following apparatus.

[0178] (purity)

[0179] The purity of the phosphate compounds was calculated based on anion analysis using ion chromatography. The analytical apparatus and determination conditions are as follows.

[0180] Device: 850 Professional IC Anion (made by Metrohm)

[0181] Column: Dionex IonPac AS23 2x250mm

[0182] (Thermo Fisher Scientific)

[0183] Test sample: 100 ppm of test sample aqueous solution

[0184] Flow rate: 1 mL / min

[0185] Eluent: 4.5 mM of Na2CO3 in a H2O-acetonitrile (7:3) mixed solution

[0186] (NMR measurement)

[0187] Tabletop nuclear magnetic resonance device: Spinsolve 60 ULTRA Phosphorus

[0188] (Magritek)

[0189] (Example 1)

[0190] <ethyl (2,2,2-trifluoroethyl) sodium phosphate (without solvent)>

[0191] To a 50 mL flask of a tomato type into which a stirrer was put, sodium iodide (630 mg, 4.20 mmol, manufactured by FUJIFILM and LIGHTNING PHARMACEUTICALS) as a raw material salt was added, and then, at room temperature, diethyl 2,2,2-trifluoroethylphosphonate (1.18 g, 5.00 mmol) as a phosphonate was added. The mixed solution was heated at 120°C for 4 hours under a nitrogen stream. After the reaction mixture was cooled to room temperature, the reaction mixture was filtered, and the residue was dried at 120°C under a nitrogen stream overnight, whereby ethyl (2,2,2-trifluoroethyl) sodium phosphate as a phosphonate compound was obtained as a white solid (930 mg, 96.1%). The purity of ethyl (2,2,2-trifluoroethyl) sodium phosphate was 99.6%.

[0192] (Example 2)

[0193] <di(2,2,2-trifluoroethyl) copper (II) phosphate (without solvent)>

[0194] To a 100 mL eggplant flask into which a stirrer bar was placed was added copper (II) chloride (980 mg, 7.29 mmol, manufactured by Wako Pure Chemical Industries, Ltd.) as a starting salt, followed by the addition of tris(2,2,2-trifluoroethyl) phosphate (50.0 g, 145 mmol) as a phosphoric acid ester at room temperature. The mixed solution was heated under reflux at a temperature of 155°C in a hot water bath for 6 hours under a stream of nitrogen. After the reaction mixture was allowed to cool to room temperature, the reaction mixture was filtered, and the residue was dried at 120°C under a stream of nitrogen overnight, thereby obtaining copper (II) bis(2,2,2-trifluoroethyl) phosphate as a phosphonate compound as a light blue solid (4.06 g, 96.1%). The purity of copper (II) bis(2,2,2-trifluoroethyl) phosphate was 98.4%.

[0195] (Example 3)

[0196] <1-ethyl-3-methylimidazolium bis(2,2,2-trifluoroethyl) phosphate>

[0197] To a 50 mL eggplant flask into which a stirrer bar was placed was added 1-ethyl-3-methylimidazolium bromide (760 mg, 3.11 mmol, manufactured by TCI) as a starting salt, followed by the addition of bis(2,2,2-trifluoroethyl) ethyl phosphate (905 mg, 3.12 mmol) as a phosphoric acid ester at room temperature. The mixed solution was heated at 120°C for 4 hours under a stream of nitrogen. After the reaction mixture was allowed to cool to room temperature, the reaction mixture was concentrated using an evaporator, followed by drying the liquid at 60°C for 1 hour, thereby obtaining 1-ethyl-3-methylimidazolium bis(2,2,2-trifluoroethyl) phosphate as a phosphonate compound as a colorless liquid (1.49 g, quantitative). The purity of 1-ethyl-3-methylimidazolium bis(2,2,2-trifluoroethyl) phosphate was 99.1%.

[0198] (Example 4)

[0199] <synthesis of lithium bis(2,2,2-trifluoroethyl) phosphate (using a nonaqueous solvent)>

[0200] To a 50 mL tomato flask put in a stirrer, lithium chloride (0.634 g, 15.0 mmol) as a starting salt and acetonitrile (40.0 g, 974 mmol, manufactured by Kishida Chemical Co.) as an aprotic organic solvent were added, and then, bis(2,2,2-trifluoroethyl)trimethylsilyl phosphate (5.00 g, 15.0 mmol) as a phosphoric acid ester was added at room temperature. The mixed solution was heated under a stream of nitrogen at 82°C to be refluxed for 2 hours. After the reaction mixture was cooled to room temperature, it was further cooled at 0°C, and the precipitate at that time 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, whereby lithium bis(2,2,2-trifluoroethyl)phosphate (2.28 g, 56.9%) as a phosphated compound was obtained as a white solid. The purity of lithium bis(2,2,2-trifluoroethyl)phosphate was 99.9%.

[0201] (Example 5)

[0202] <Synthesis 1 of lithium difluorophosphate (without solvent)>

[0203] To a 50 mL tomato flask put in a stirrer, trimethylsilyl difluorophosphate (3.50 g, 20.1 mmol) as a phosphoric acid ester was added, and then, lithium chloride (568 mg, 13.4 mmol) as a starting salt was added at room temperature. The mixture was heated under a stream of nitrogen at 80°C for 1 hour. After being cooled 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 drying machine, whereby lithium difluorophosphate (920 mg, 63.6%) as a phosphated compound was obtained as a white solid. The purity of lithium difluorophosphate was 99.5%.

[0204] (Example 6)

[0205] <Synthesis 2 of lithium difluorophosphate (using a non-aqueous solvent)>

[0206] After adding trimethylsilyl difluorophosphate (50.0 g, 287 mmol) as a phosphoric acid ester to a 500 mL tomato flask equipped with a stirrer under nitrogen protection, it was diluted with acetonitrile (150 g, 3.65 mol, manufactured by Kishida Chemical Co., Ltd.) as an aprotic organic solvent. In addition, lithium chloride (11.8 g, 278 mmol) as a raw material salt was added at room temperature. The mixture was heated under reflux at 82°C for 5 hours under a nitrogen stream. After being cooled to room temperature, the reaction mixture was concentrated using an evaporator, and the obtained 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 drying machine, whereby lithium difluorophosphate (27.4 g, 91.4%) as a phosphoric acid salt compound was obtained as a white solid. The purity of lithium difluorophosphate was 99.4%.

[0207] (Example 7)

[0208] (Synthesis of bis(2,2,2-trifluoroethyl)trimethylsilyl phosphate (without solvent))

[0209] After adding chlorotrimethylsilane (16.6 g, 153 mmol, manufactured by TCI Co., Ltd.) as a silicon compound to a 50 mL tomato flask equipped with a stirrer, bis(2,2,2-trifluoroethyl) phosphate (20.0 g, 76.3 mmol) as a phosphoric acid compound was added at room temperature. The mixed solution was heated under reflux at 80°C for 6 hours under a nitrogen stream. The excess chlorotrimethylsilane was removed from the reaction mixture using an evaporator, whereby bis(2,2,2-trifluoroethyl)trimethylsilyl phosphate (21.2 g, 83.1%) as a phosphoric acid ester was obtained as a colorless liquid. The purity of bis(2,2,2-trifluoroethyl)trimethylsilyl phosphate was 99.7%.

[0210] The physical and chemical properties of the obtained bis(2,2,2-trifluoroethyl)trimethylsilyl phosphate were as follows.

[0211] 1 H-NMR (CDC13, δ ppm): -0.06 (s, 9H), 4.02 (dq, 4H, J H-F = 8.3 Hz); H-P = 8.3 Hz);

[0212] 19 F-NMR (CDC13, δ ppm): -74.8 (t, 6F, J H-F = 8.3 Hz).

[0213] 31 P-NMR (CDC13, δ ppm): -10.1 (tt, IP, J H-P = 8.3 Hz).

[0214] (Example 8)

[0215] Synthesis 1 of trimethylsilyl difluorophosphate (without solvent)

[0216] To a 200 mL flask of a gage type equipped with a stirrer was added chlorotrimethylsilane (48.7 g, 448 mmol, manufactured by TCI Corporation) as a silicon compound, and then, at room temperature, difluorophosphoric acid (45.7 g, 448 mmol) as a phosphoric acid compound was added dropwise. The mixed solution was stirred at 50°C for 6 hours under a stream of nitrogen. By normal pressure distillation of the reaction mixture, trimethylsilyl difluorophosphate (49.0 g, 62.7%) was obtained as a phosphoric acid ester in the form of a colorless liquid. The purity of trimethylsilyl difluorophosphate was 95.6%.

[0217] (Example 9)

[0218] Synthesis 2 of trimethylsilyl difluorophosphate (reuse of chlorotrimethylsilane as a by-product, without solvent)

[0219] To a 50 mL flask of a gage type equipped with a stirrer was added chlorotrimethylsilane {7.16 g, 65.9 mmol} as a silicon compound, and then, at room temperature, difluorophosphoric acid (6.71 g, 65.8 mmol) as a phosphoric acid compound was added dropwise. The mixed solution was stirred at 50°C for 3 hours under a stream of nitrogen. By normal pressure distillation of the reaction mixture, trimethylsilyl difluorophosphate (7.12 g, 62.2%) was obtained as a phosphoric acid ester in the form of a colorless liquid. The purity of trimethylsilyl difluorophosphate was 96.1%. Note that, as chlorotrimethylsilane, the by-product (by-product (E')) of Step (I) of the synthesis of lithium difluorophosphate of Example 5 was used.

[0220] The physical and chemical properties of the obtained trimethylsilyl difluorophosphate were as follows.

[0221] 1 H-NMR (CDC13, δ ppm): 0.33 (s, 9H);

[0222] 19 F-NMR (CDC13, δ ppm): -80.4 (d, 2F, J = 985.9 Hz);

[0223] 31 P-NMR (CDC13, δ ppm): -29.1 (dd, IP, J = 985.9 Hz).

[0224] (Example 10)

[0225] Synthesis of dimethylvinylsilyl difluorophosphate (without solvent)

[0226] To a 100 mL flask equipped with a stirrer, dimethylvinylsilyl chloride (10.1 g, 83.7 mmol, manufactured by TCI) as a silicon compound was added, and then, at room temperature, difluorophosphoric acid (8.14 g, 79.8 mmol) as a phosphoric acid compound was added by dropwise addition. The mixed solution was stirred at 60°C for 3 hours under a stream of nitrogen. Dimethylvinylsilyl difluorophosphate as a phosphoric acid ester was obtained as a colorless liquid by distillation of the reaction mixture under reduced pressure (2.33 g, 15.7%). The purity of dimethylvinylsilyl difluorophosphate was 97.9%.

[0227] The physical and chemical properties of the obtained dimethylvinylsilyl difluorophosphate were as follows.

[0228] 1 H-NMR (CDC13, δ ppm): 0.44 (s, 7H), 6.02-6.13 (m, 2H);

[0229] 19 F-NMR (CDC13, δ ppm): -80.0 (d, 2F, J = 990.3 Hz);

[0230] 31 P-NMR (CDC13, δ ppm): -28.4 (dd, IP, J = 990.3 Hz).

[0231] (Example 11)

[0232] Synthesis of dimethylphenylsilyl difluorophosphate (without solvent)

[0233] To a 100 mL flask equipped with a stirrer, dimethylphenylsilyl chloride (16.8 g, 98.4 mmol, manufactured by TCI) as a silicon compound was added, and then, at room temperature, difluorophosphoric acid (10.1 g, 99.0 mmol) as a phosphoric acid compound was added by dropwise addition. The mixed solution was stirred at 60°C for 3 hours under a stream of nitrogen. Dimethylphenylsilyl difluorophosphate as a phosphoric acid ester was obtained as a colorless liquid by distillation of the reaction mixture under reduced pressure (10.6 g, 45.6%). The purity of dimethylphenylsilyl difluorophosphate was 97.5%.

[0234] The physical and chemical properties of the obtained dimethylphenylsilyl difluorophosphate were as follows.

[0235] 1 H-NMR (CDC13, δ ppm): 0.44 (s, 7H), 6.02-6.13 (m, 2H);

[0236] 19 F-NMR (CDC13, δ ppm): -79.7 (d, 2F, J = 991.4 Hz);

[0237] 31 P-NMR (CDC13, δ ppm): -30.0 (dd, IP, J = 991.4 Hz).

[0238] (Example 12)

[0239] Synthesis of triethylsilyl difluorophosphate (without solvent)

[0240] To a 50 mL tomato flask put with a stirrer was added chlorotriethylsilane (10.0 g, 66.3 mmol, manufactured by TCI Corporation) as a silicon compound, and then, at room temperature, difluorophosphoric acid (6.69 g, 65.6 mmol) as a phosphoric acid compound was added by dropwise addition. The mixed solution was stirred at 60°C for 4 hours under a nitrogen stream. By distillation of the reaction mixture under reduced pressure, triethylsilyl difluorophosphate (7.29 g, 51.4%) as a phosphoric acid ester was obtained as a colorless liquid. The purity of triethylsilyl difluorophosphate was 98.3%.

[0241] The physical and chemical properties of the obtained triethylsilyl difluorophosphate were as follows.

[0242] 1 H-NMR (CDC13, δ ppm): 0.40-1.11 (m, 15H);

[0243] 19 F-NMR (CDC13, δ ppm): -80.9 (d, 2F, J = 986.4 Hz);

[0244] 31 P-NMR (CDC13, δ ppm): -29.5 (dd, IP, J = 986.4 Hz).

[0245] (Example 13)

[0246] Synthesis of cyclohexyldimethylsilyl difluorophosphate (without solvent)

[0247] To a 50 mL flask equipped with a stirrer, chloro(cyclohexyldimethyl)silane (12.0 g, 67.9 mmol, manufactured by TCI Corporation) as a silicon compound was added, and then, at room temperature, by dropwise addition, difluorophosphoric acid (6.83 g, 67.0 mmol) as a phosphorus acid compound was added. The mixed solution was stirred at 60°C for 4 hours under a stream of nitrogen. By distilling the reaction mixture under reduced pressure, cyclohexyldimethylsilyl difluorophosphate as a phosphoric ester was obtained as a colorless liquid (9.92 g, 61.0%). The purity of cyclohexyldimethylsilyl difluorophosphate was 93.6%.

[0248] The physical and chemical properties of the obtained cyclohexyldimethylsilyl difluorophosphate were as follows.

[0249] 1 H-NMR (CDC13, δ ppm): 0.29 (s, 6H), 0.92-1.67 (br m, 11H);

[0250] 19 F-NMR (CDC13, δ ppm): -79.8 (d, 2F, J=989.0 Hz);

[0251] 31 P-NMR (CDC13, δ ppm): -29.5 (dd, IP, J=989.0 Hz).

[0252] (Example 14)

[0253] Synthesis of dimethylphenylsilyl difluorophosphate (using a non-aqueous solvent)

[0254] To a 50 mL screw vial equipped with a stirrer, sodium difluorophosphate (5.01 g, 40.4 mmol) as a phosphorus acid compound and acetonitrile (20.0 g, 487 mmol, manufactured by Kishida Chemical Corporation) as an aprotic organic solvent were added under nitrogen protection, and then, at room temperature, by dropwise addition, chlorodimethylphenylsilane (6.82 g, 40.0 mmol, manufactured by TCI Corporation) as a silicon compound was added. The mixed solution was stirred at 60°C for 2 hours under a nitrogen atmosphere. After cooling to room temperature, the reaction mixture was filtered using a 0.45 μm membrane filter. The filtrate was bubbled with nitrogen for 12 hours to remove acetonitrile. By filtering the residue using a 0.45 μm membrane filter, dimethylphenylsilyl difluorophosphate as a phosphoric ester was obtained as a colorless liquid (7.79 g, 82.5%). The purity of dimethylphenylsilyl difluorophosphate was 95.4%.

[0255] (Example 15)

[0256] Synthesis of triisopropylsilyl difluorophosphate (using a nonaqueous solvent)

[0257] After adding a phosphorus acid compound as sodium difluorophosphate (2.02 g, 16.3 mmol) and an aprotic organic solvent as acetonitrile (9.13 g, 222 mmol, manufactured by Kishida Chemical Co., Ltd.) to a 50 mL screw tube with a stirrer under nitrogen protection, a silicon compound as chlorotriisopropylsilane (3.14 g, 16.3 mmol, manufactured by TCI Co., Ltd.) was added dropwise at room temperature. The mixed solution was stirred at 60°C for 2 hours under a nitrogen atmosphere. After cooling to room temperature, the reaction mixture was filtered using a 0.45 μm membrane filter. The filtrate was bubbled with nitrogen for 12 hours to remove acetonitrile. The residue was filtered using a 0.45 μm membrane filter to obtain triisopropylsilyl difluorophosphate as a colorless liquid phosphonate (1.00 g, 23.7 %). The purity of triisopropylsilyl difluorophosphate was 97.4 %.

[0258] The physical and chemical properties of the obtained triisopropylsilyl difluorophosphate were as follows.

[0259] 1 H-NMR (CDC13, δ ppm): 0.98-1.27 (m, 21H);

[0260] 19 F-NMR (CDC13, δ ppm): -80.4 (d, 2F, J=983.5 Hz);

[0261] 31 P-NMR (CDC13, δ ppm): -29.5 (dd, IP, J=989.0 Hz).

[0262] (Example 16)

[0263] Synthesis of methyldiphenylsilyl difluorophosphate (using a nonaqueous solvent)

[0264] To a 50 mL screw vial equipped with a stirrer under nitrogen protection was added sodium difluorophosphate (3.01 g, 24.3 mmol) as a phosphorus compound and acetonitrile (10.0 g, 244 mmol, manufactured by Kishida Chemical Co., Ltd.) as an aprotic organic solvent, and then chloro(methyl)diphenylsilane (5.36 g, 23.0 mmol, manufactured by TCI Co., Ltd.) as a silicon compound was added dropwise at room temperature. The mixed solution was stirred at 60°C for 11 hours under a nitrogen atmosphere. After cooling to room temperature, the reaction mixture was filtered using a 0.45 μm membrane filter. The filtrate was bubbled with nitrogen for 12 hours to remove acetonitrile. The residue was filtered using a 0.45 μm membrane filter to obtain methyl diphenylsilyl difluorophosphate as a colorless liquid (5.22 g, 76.1 %). The purity of methyl diphenylsilyl difluorophosphate was 88.0 %.

[0265] The physical and chemical properties of the obtained methyl diphenylsilyl difluorophosphate were as follows.

[0266] 1 H-NMR (CDC13, δ ppm): 0.92 (s, 3H), 7.29-7.73 (m, 10H);

[0267] 19 F-NMR (CDC13, δ ppm): -78.8 (d, 2F, J = 995.6 Hz);

[0268] 31 P-NMR (CDC13, δ ppm): -30.3 (dd, IP, J = 995.6 Hz).

Claims

1. A method for manufacturing a phosphate compound, comprising at least: In step (I), a phosphate ester represented by chemical formula (A) is reacted with a raw material salt represented by chemical formula (B) to generate a phosphate compound represented by chemical formula (C). ； In chemical formula (A), Z represents a silicon atom; X 1 and X 2 Either of these represents a halogen atom, and the other 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 or a heteroatom, or an alkoxy group having 1 to 10 carbon atoms and having at least one of a halogen atom, a heteroatom, or an unsaturated bond; X 3 ~X 5 Each of the following 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 or a heteroatom, or an alkoxy group having 1 to 10 carbon atoms and having at least one of a halogen atom, a heteroatom, or an unsaturated bond, and X 3 ~X 5 At least one of the groups is a hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. ； In the chemical formula (B), M represents an alkali metal, or copper; X 6 Represents a halogen atom; n represents a natural number from 1 to 2. ； In chemical formula (C), M represents the same type of cation as in chemical formula (B); X 1 and X 2 represents the same functional group as in chemical formula (A); n represents the same valence as in chemical formula (B).

2. The method for manufacturing the phosphate compound according to claim 1, wherein, The method for manufacturing the phosphate compound includes: step (II), wherein a phosphate compound represented by chemical formula (D) is reacted with a silicon compound represented by chemical formula (E) to generate a silyl phosphate ester represented by chemical formula (F). ； In the chemical formula (D), M' represents a hydrogen atom or an alkali metal; X 1 and X 2 represents the same functional group as in chemical formula (A); n represents the same valence as in chemical formula (B). ； In the chemical formula (E), X 3 ~X 5 X represents the same functional group as in the chemical formula (A); 7 The leaving group represents a halogen atom. ； In the chemical formula (F), X 1 ~X 5 It represents the same functional group as in the chemical formula (A).

3. The method for manufacturing the phosphate compound according to claim 2, wherein, The silicon compound represented by chemical formula (E) is a byproduct generated during process (I).

4. The method for manufacturing the phosphate compound according to claim 2 or 3, wherein, The phosphoric acid compound is X in the chemical formula (D). 1 and X 2 Fluorophosphates in which one of the atoms is a fluorine atom, the other is an alkoxy group with 1 to 10 carbon atoms, and M' is a hydrogen atom.

5. The method for manufacturing the phosphate compound according to claim 2 or 3, wherein, The phosphoric acid compound is X in the chemical formula (D). 1 and X 2 Difluorophosphoric acid when M' is a fluorine atom and M' is a hydrogen atom.

6. The method for producing the phosphate compound according to claim 2 or 3, wherein, The silicon compound is X in the chemical formula (E). 3 ~X 5 Each is independently a hydrocarbon group having 1 to 6 carbon atoms, and the X 7 Trialkylsilyl halides when the halogen atom is a halogen atom.

7. The method for producing the phosphate compound according to any one of claims 1 to 3, wherein, The M in the chemical formula (B) is a lithium atom or a sodium atom.

8. The method for producing the phosphate compound according to claim 2 or 3, wherein, At least one of the steps (I) and (II) shall be carried out in a solvent-free environment.

9. The method for manufacturing the phosphate compound according to claim 2 or 3, wherein, At least one of the steps (I) and (II) shall be carried out in a non-aqueous solvent.

10. The method for producing the phosphate compound according to claim 9, wherein, The non-aqueous solvent is an aprotic organic solvent.

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