Heteropolyoxotungstate compound, solvate thereof, or mixture of compound and solvate thereof, and method for producing compound, solvate thereof, or mixture of compound and solvate thereof

Abstract

Provided are: a heteropolyoxytungstate compound represented by a general formula (I), a solvate thereof, or a mixture of the compound and the solvate thereof; and a method for producing this compound, the solvate thereof, or the mixture of the compound and the solvate thereof. General formula (I): (Am+)x / m(Bn+)y / n(C-(x+y)).

Description

Heteropolyoxotungstate compound or solvate thereof or mixture thereof, and method for producing the same

[0001] The present invention relates to a heteropolyoxotungstate compound, a solvate thereof, or a mixture thereof, and a method for producing the same.

[0002] Polyoxometalates (POMs) are anionic metal oxide clusters, ０ or d １ POM has an oxygen-bridged structure in which an early transition metal (e.g., Mo (hexavalent or pentavalent), W (hexavalent or pentavalent), V (pentavalent), Nb (pentavalent), Ta (pentavalent), etc.) with the electron configuration is incorporated. A variety of structures can be adopted by incorporating various elements into the anionic metal oxide cluster of POM. Furthermore, the physicochemical properties such as redox ability, light absorption ability, and acidity can be changed depending on the combination of constituent elements of POM and its structure.

[0003] For example, Patent Document 1 describes that a POM containing polyoxomolybdic acid and a compound having a pyridinium skeleton has a high photoluminescence quantum yield.

[0004] Polyoxotungstic acid (POT), a type of POM, includes isopolyoxotungstic acid, which is composed of an oxygen acid containing tungsten, and heteropolyoxotungstic acid, which is composed of an oxygen acid containing tungsten and one or more other heteroatoms. The heteroatoms that make up heteropolyoxotungstic acid can be selected from many elements in Groups I-VIII, including Si, Ge, and P, and by changing the combination and composition ratio, POMs with different physicochemical properties can be formed.

[0005] US Patent No. 5,949,999 discloses a photochromic article comprising a complex of a polyoxometalate anion, such as phosphotungstic acid, and a countercation, such as an ammonium cation.

[0006] U.S. Patent No. 1,119,2908 U.S. Patent No. 10,711,182

[0007] In view of the above circumstances, an object of the present invention is to provide a novel heteropolyoxotungstate compound, a solvate thereof, or a mixture thereof, and a method for producing the same.

[0008] As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have succeeded in synthesizing a heteropolyoxotungstate compound represented by general formula (I), a solvate thereof, or a mixture thereof, and have also discovered a method for efficiently synthesizing a heteropolyoxotungstate compound represented by general formula (I), a solvate thereof, or a mixture thereof, thereby completing the present invention.

[0009] That is, the present invention relates to the following inventions: <1> A heteropolyoxotungstate compound represented by general formula (I) or a solvate thereof. (A ｍ＋ ) ｘ／ｍ (B ｎ＋ ) ｙ／ｎ (C －（ｘ＋ｙ） ) (I) [wherein, A ｍ＋ are each independently H ＋ , a metal ion, or an ammonium ion; B ｎ＋ each independently represents an iodonium cation; －（ｘ＋ｙ） represents heteropolyoxotungstic acid; m is an integer of 1 to 5, n is an integer of 1 or 2, x and x / m are integers, and y and y / n are natural numbers.

[0010] <2> The heteropolyoxotungstate compound or solvate thereof according to <1>, wherein the heteropolyoxotungstic acid is a heteropolyoxotungstic acid represented by general formula (II-1) or (II-2), or a heteropolyoxotungstic acid represented by a defective species thereof. [XW １２ O ４０ ] －ｚ１ (II-1) [X ２ W １８ O ６２ ] －ｚ２ (II-2) [wherein, X each independently represents B, Al, Si ＩＶ , Ge ＩＶ , PＶ , As Ｖ , V Ｖ , Cr ＩＩＩ , Fe ＩＩＩ , Co ＩＩＩ , Co ＩＩ , Cu ＩＩ , Cu Ｉ , Zn, Se ＶＩ , or S ＶＩ and z1 and z2 are natural numbers.

[0011] <3> The heteropolyoxotungstic acid represented by (II-1) is １２ O ４０ ] ３－ , [SiW １２ O ４０ ] ４－ , [B.W. １２ O ４０ ] ５－ or [SW １２ O ４０ ] ２－ The heteropolyoxotungstate compound or a solvate thereof according to <2>,

[0012] <4> The heteropolyoxotungstic acid represented by (II-2) is ２ W １８ O ６２ ] ６－ , [Si ２ W １８ O ６２ ] ８－ or [S ２ W １８ O ６２ ] ４－ The heteropolyoxotungstate compound or a solvate thereof according to <2>,

[0013] <5> A heteropolyoxotungstate mixture containing two or more different heteropolyoxotungstate compounds or solvates thereof according to <1>.

[0014] <6> A heteropolyoxotungstate mixture comprising two or more different heteropolyoxotungstate compounds or solvates thereof according to <1>, wherein the heteropolyoxotungstate is a Keggin type or a Dawson type, or a silicotungstic acid which is a defect species thereof, and wherein the molar ratio of I to W in XRF analysis or XPS analysis is I:W=0.5 to 10:9 to 18.

[0015] <7> A heteropolyoxotungstate mixture comprising two or more different heteropolyoxotungstate compounds or solvates thereof according to <1>, wherein the heteropolyoxotungstate is a Keggin type or a Dawson type, or a phosphotungstic acid, which is a defect species thereof, and wherein the molar ratio of I to W in XRF analysis or XPS analysis is I:W=0.5 to 6:9 to 18.

[0016] <8> The heteropolyoxotungstate compound or solvate thereof according to <1>, wherein the iodonium cation is an iodonium cation represented by general formula (III): [In the formula, R ３Ａ and R ３Ｂ each independently represents a C １－１８ R represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group which may have a substituent, or a 5- to 18-membered aromatic heterocyclic group which may have a substituent; ３Ａ and R ３Ｂ are directly connected to each other by a single bond, or are connected to each other by a divalent linking group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring together with the iodine atom in formula (III).

[0017] <9> The heteropolyoxotungstate compound or solvate thereof according to <1>, wherein the iodonium cation is an iodonium cation represented by general formula (IV-1) or (IV-2): [In the formula, Ar ４Ａ and Ar ４Ｂ each independently represents a C６－１８ C represents an aryl group or a 5- to 18-membered heterocyclic group, which may have the above-mentioned substituents. ６－１８ The aryl group or the 5- to 18-membered heterocyclic group may be a C group in which at least a portion of the hydrogen atoms are optionally substituted with a halogen atom, a hydroxy group, a thiol group, a nitro group, a cyano group, a carboxy group, an amino group, or a sulfo group, or a C group in which at least a portion of the hydrogen atoms are optionally substituted with a halogen atom, a hydroxy group, a thiol group, a nitro group, a cyano group, a carboxy group, an amino group, or a sulfo group. １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbyloxycarbonyloxy group, C １－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ Hydrocarbyloxycarbonylamino group, C １－１８ Hydrocarbylthio group, C １－１８ a hydrocarbylsulfinyl group, or C １－１８ and the divalent carbon atom at any position of the substituent except for the terminal may be substituted with -O-, -C(=O)-, -COO-, -OCO-, -CONH-, -NHCO-, -S-, or SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), Ar ４Ａ and Ar ４Ｂare directly connected to each other by a single bond, or are connected to each other by a divalent linking group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring together with the iodine atom in formula (IV-1). [In the formula, R ４Ｃ and R ４Ｄ are each independently a halogen atom, a hydroxy group, a thiol group, a nitro group, a cyano group, a carboxy group, an amino group, a sulfo group, or a C in which at least a portion of the hydrogen atoms may be substituted with a halogen atom, a hydroxy group, a thiol group, a nitro group, a cyano group, a carboxy group, an amino group, or a sulfo group. １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbyloxycarbonyloxy group, C １－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ Hydrocarbyloxycarbonylamino group, C １－１８ Hydrocarbylthio group, C １－１８ a hydrocarbylsulfinyl group, or C １－１８ a hydrocarbylsulfonyl group, and a divalent carbon atom at any position excluding the terminal is -O-, -C(=O)-, -COO-, -OCO-, -CONH-, -NHCO-, -S-, or SO ２- (provided that adjacent divalent carbon atoms are not simultaneously replaced); v and w are each an integer of 0 to 5, and when the values ​​of v and w are an integer of 2 or more, R ４Ｃ and R ４Ｄ may be the same or different from each other.

[0018] <10> In the iodonium cation represented by the general formula (IV-1), Ar ４Ｂ The heteropolyoxotungstate compound or a solvate thereof according to <9>, wherein the compound (I) is an iodonium cation represented by general formula (IV-3): [In the formula, R ４Ｅ represents a halogen atom, a nitro group, C １－４ a haloalkyl group or a branched C ３－１０ Alkyl group, C １－１２ Hydrocarbyloxy group, C １－１２ Hydrocarbyl carbonyl group, C １－１２ Hydrocarbylcarbonyloxy group, C １－１２ Hydrocarbyloxycarbonyl group or C １－１２ represents a hydrocarbyloxycarbonyloxy group; R ４Ｅ is a halogen atom, a nitro group, C １－４ When Ar is a haloalkyl group, ４Ａ and Ar ４Ｂ are different from each other.]

[0019] <11> In the iodonium cation represented by the general formula (IV-1), Ar ４Ｂ The heteropolyoxotungstate compound or a solvate thereof according to <9>, wherein the compound (I) is an iodonium cation represented by general formula (IV-4): [In the formula, R ４Ｆ each independently represents a C １－１２ Hydrocarbyl group, C １－１２ Hydrocarbyloxy group, C １－１２ Hydrocarbyl carbonyl group, C １－１２ Hydrocarbylcarbonyloxy group, C１－１２ Hydrocarbyloxycarbonyl group or C １－１２ represents a hydrocarbyloxycarbonyloxy group.]

[0020] <12> A method for producing a heteropolyoxotungstate compound represented by general formula (I) or a solvate thereof, the method comprising a step of reacting a compound represented by general formula (V-1) with a compound represented by general formula (V-2) to carry out salt exchange. (A ｍ＋ ) ｘ／ｍ (B ｎ＋ ) ｙ／ｎ (C －（ｘ＋ｙ） ) (I) (A ｍ＋ ) ｘ／ｍ (A' ｍ’＋ ) ｙ／ｍ’ (C －（ｘ＋ｙ） ) (V-1) (B ｎ＋ ) ｙ／ｎ (Y － ) ｙ (V-2) [wherein, A ｍ＋ are each independently H ＋ A' represents a metal ion or an ammonium ion; ｍ’＋ each independently represents a metal ion or an ammonium ion; B ｎ＋ each independently represents an iodonium cation; －（ｘ＋ｙ） represents heteropolyoxotungstic acid; Y － represents a monovalent counter anion; m and m' are integers of 1 to 5, n is an integer of 1 or 2, x and x / m are integers, and y / m', y and y / n are natural numbers.

[0021] <13> A method for producing a heteropolyoxotungstate compound represented by general formula (I) or a solvate thereof, the method comprising: a step of reacting a compound represented by general formula (V-1) with a compound represented by general formula (V-2) to perform salt exchange; and a step of removing the compound represented by general formula (V-3) from the produced compounds represented by general formulas (I) and (V-3). (A ｍ＋ ) ｘ／ｍ (B ｎ＋ )ｙ／ｎ (C －（ｘ＋ｙ） ) (I) (A ｍ＋ ) ｘ／ｍ (A' ｍ’＋ ) ｙ／ｍ’ (C －（ｘ＋ｙ） ) (V-1) (B ｎ＋ ) ｙ／ｎ (Y － ) ｙ (V-2) (A' ｍ’＋ ) ｙ／ｍ’ (Y － ) ｙ (V-3) [wherein, A ｍ＋ are each independently H ＋ A' represents a metal ion or an ammonium ion; ｍ’＋ each independently represents a metal ion or an ammonium ion; B ｎ＋ each independently represents an iodonium cation; －（ｘ＋ｙ） represents heteropolyoxotungstic acid; Y － represents a monovalent counter anion; m and m' are integers of 1 to 5, n is an integer of 1 or 2, x and x / m are integers, and y / m', y and y / n are natural numbers.

[0022] <14> A method for producing a heteropolyoxotungstate compound represented by general formula (I) or a solvate thereof, comprising: ｍ’＋ H ＋ and reacting the compound represented by general formula (V-4) produced by the above step with a compound represented by general formula (V-2). ｍ＋ ) ｘ／ｍ (B ｎ＋ ) ｙ／ｎ (C －（ｘ＋ｙ） ) (I) (A ｍ＋ ) ｘ／ｍ (A' ｍ’＋ ) ｙ／ｍ’ (C －（ｘ＋ｙ） ) (V-1) (A ｍ＋ ) ｘ／ｍ (H ＋ ) ｙ (C－（ｘ＋ｙ） ) (V-4) (B ｎ＋ ) ｙ／ｎ (Y － ) ｙ (V-2) [wherein, A ｍ＋ are each independently H ＋ A' represents a metal ion or an ammonium ion; ｍ’＋ each independently represents a metal ion or an ammonium ion; B ｎ＋ each independently represents an iodonium cation; －（ｘ＋ｙ） represents heteropolyoxotungstic acid; Y － represents a monovalent counter anion; m and m' are integers of 1 to 5, n is an integer of 1 or 2, x and x / m are integers, and y / m', y and y / n are natural numbers.

[0023] According to the present invention, it is possible to provide a novel heteropolyoxotungstate compound, a solvate thereof, or a mixture thereof, and a method for producing the same.

[0024] Preferred embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments.

[0025] [1. Heteropolyoxotungstate compound or solvate thereof, or mixture thereof] A heteropolyoxotungstate compound according to one embodiment of the present invention is represented by the following general formula (I): (A ｍ＋ ) ｘ／ｍ (B ｎ＋ ) ｙ／ｎ (C －（ｘ＋ｙ） ) (I) [wherein, A ｍ＋ are each independently H ＋ , a metal ion, or an ammonium ion; B ｎ＋ each independently represents an iodonium cation; －（ｘ＋ｙ） represents heteropolyoxotungstic acid; m is an integer of 1 to 5, n is an integer of 1 or 2, x and x / m are integers, and y and y / n are natural numbers.] In the following, A ｍ＋are also called "other countercations."

[0026] The "heteropolyoxotungstic acid," "iodonium cation," "other counter cation," "compound or solvate, or mixture thereof," and "solvate" will be explained in this order below.

[0027] [1-1. Heteropolyoxotungstate] The heteropolyoxotungstate compound according to this embodiment is represented by the following general formula (I): (A ｍ＋ ) ｘ／ｍ (B ｎ＋ ) ｙ／ｎ (C －（ｘ＋ｙ） ) (I) C －（ｘ＋ｙ） represents a heteropolyoxotungstic acid; x is an integer and y is a natural number.

[0028] The heteropolyoxotungstic acid according to this embodiment is not particularly limited, and known and commonly used compounds can be used. Examples of known heteropolyoxotungstic acids include Keggin type, Dawson type, or defective species thereof, as well as Anderson type, Lacuna-Keggin type, substituted Keggin type, and Strandberg type. Any of these may be used. The heteropolyoxotungstic acid may include all structurally existing isomers, such as geometric isomers, optical isomers, rotational isomers, stereoisomers, and tautomers, as well as mixtures of isomers, and is not limited to the chemical formulas described for convenience.

[0029] Keggin-type heteropolyoxotungstic acid ([XW １２ O ４０ ] －ｚ１ X's are each independently B, Al, or Si. ＩＶ , Ge ＩＶ , P Ｖ , As Ｖ , V Ｖ , Cr ＩＩＩ , Fe ＩＩＩ , Co ＩＩＩ , Co ＩＩ , Cu ＩＩ , Cu Ｉ , Zn, Se ＶＩ , or S ＶＩwhere z1 is a natural number.) is known to exist in α-Keggin type, β-Keggin type, γ-Keggin type, etc. １２ O ４０ ] －ｚ１ The above isomers and mixtures of these isomers are included. Similarly, Dawson-type heteropolyoxotungstic acid ([X ２ M １８ O ６２ ] －ｚ２ X's are each independently B, Al, or Si. ＩＶ , Ge ＩＶ , P Ｖ , As Ｖ , V Ｖ , Cr ＩＩＩ , Fe ＩＩＩ , Co ＩＩＩ , Co ＩＩ , Cu ＩＩ , Cu Ｉ , Zn, Se ＶＩ , or S ＶＩ where z2 is a natural number.) is known to exist in α-Dawson type, β-Dawson type, γ-Dawson type, etc. ２ M １８ O ６２ ] －ｚ２ The term "isomer" includes the above isomers or mixtures of these isomers.

[0030] As the heteropolyoxotungstic acid according to this embodiment, it is preferable to use a Keggin type or a Dawson type, or a defect species thereof, from the viewpoint of excellent thermal stability and stability under an oxidizing atmosphere. As the Keggin type heteropolyoxotungstic acid, for example, [PW １２ O ４０ ] ３－ , [SiW １２ O ４０ ] ４－ , [B.W. １２ O ４０ ] ５－ , [SW １２ O ４０ ] ２－ Examples of the Dawson type heteropolyoxotungstic acid include [P ２ W １８ O ６２ ]６－ , [Si ２ W １８ O ６２ ] ８－ , [S ２ W １８ O ６２ ] ４－ Examples of Keggin type or Dawson type defect heteropolyoxotungstic acids include [PW ９ O ３４ ] ９－ , [P.W. １０ O ３６ ] ７－ , [P.W. １１ O ３９ ] ７－ , [SiW ９ O ３４ ] １０－ , [SiW １０ O ３６ ] ８－ , [SiW １１ O ３９ ] ８－ , [P ２ W １７ O ６１ ] １０－ Among these, the heteropolyoxotungstic acid according to this embodiment is [PW １２ O ４０ ] ３－ , [SiW １２ O ４０ ] ４－ , [B.W. １２ O ４０ ] ５－ , [SW １２ O ４０ ] ２－ , [P ２ W １８ O ６２ ] ６－ , [Si ２ W １８ O ６２ ] ８－ , [S ２ W １８ O ６２ ] ４－ is preferred, １２ O ４０ ] ３－ , [SiW １２ O ４０ ] ４－, [B.W. １２ O ４０ ] ５－ , [SW １２ O ４０ ] ２－ is more preferred.

[0031] [1-2. Iodonium Cation] The heteropolyoxotungstate compound according to this embodiment is represented by the following general formula (I): (A ｍ＋ ) ｘ／ｍ (B ｎ＋ ) ｙ／ｎ (C －（ｘ＋ｙ） ) (I) B ｎ＋ each independently represents an iodonium cation; n is an integer of 1 or 2, and y and y / n are natural numbers.

[0032] The meanings of terms, symbols, etc. used in this specification will be explained below, and embodiments of the present invention will be described in more detail.

[0033] As used herein, the term "halogen atom" refers to a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0034] In this specification, for example, "C １－６ " and other terms refer to the number of carbon atoms in the core group.

[0035] As used herein, "C １－１８ The term "hydrocarbylene group" refers to a divalent hydrocarbon group generated by removing two hydrogen atoms from a hydrocarbon having 1 to 18 carbon atoms. The hydrocarbylene group may be linear or branched, or may be partially or entirely cyclic. The hydrocarbylene group includes alkylene groups, arylene groups, etc. Also, "C １－１８ The divalent carbon atom at any position of the "hydrocarbylene group" may be -O-, -S-, -C(=O)-, -COO-, -OCO-, -CONH-, -NHCO-, -S-, -SO-, or -SO ２ - may be substituted (however, adjacent divalent carbon atoms may not be substituted at the same time). １－１８The "hydrocarbylene group" is not particularly limited, and examples thereof include "C" such as methylene group, ethylene group, n-propylene group, i-propylene group, cyclopentadiyl group, cyclohexanediyl group, oxyethane-1,1-diyl group, oxyethane-1,2-diyl group, oxypropane-1,3-diyl group, oxypropane-1,2-diyl group, 2-methylpropane-1,3-diyl group, and oxyethyleneoxyethane-1,1-diyl group. １－１８ alkylene group"; 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 1,8-naphthylene group, 4,4'-biphenylene group, anthracenediyl group, phenanthrenediyl group, naphthacenediyl group, pyrenediyl group, perylenediyl group, chrysenediyl group, etc. ６－１８ arylene group" and the like.

[0036] As used herein, "C １－１８ The term "alkyl group" means a linear or branched alkyl group having 1 to 18 carbon atoms. １－１８ The divalent carbon atom at any position excluding the terminal contained in the "alkyl group" is -O-, -C(=O)-, -COO-, -OCO-, -CONH-, -NHCO-, -S- or -SO ２ However, adjacent divalent carbon atoms may not be replaced at the same time. １－１８The "alkyl group" is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, an i-pentyl group, a sec-pentyl group, a t-pentyl group, a neopentyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 1,1-dimethylpropyl group, a 1,2-dimethylpropyl group, an n-hexyl group, an i-hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 1 , 1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, 1-ethyl-2-methylpropyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, and the like. １－１８ The alkyl group may have a divalent carbon atom at any position excluding the terminal, and the divalent carbon atom may be -O-, -C(=O)-, -COO-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ The group substituted with - is not particularly limited, and examples thereof include a 2-methoxyethoxymethyl group, an ethoxycarbonylmethyl group, and the like.

[0037] As used herein, "C １－１８ The term "haloalkyl group" refers to "C １－１８ "C" means a group in which one or more hydrogen atoms of an "alkyl group" are substituted with halogen atoms. １－１８ The "haloalkyl group" is not particularly limited, and examples thereof include a dichloromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, and a 3,3,3-trifluoropropyl group.

[0038] As used herein, "C ２－１８ The term "alkenyl group" refers to a group having two or more carbon atoms. １－１８ "C" means an alkenyl group having one or more double bonds, and includes alkadienyl groups, alkatrienyl groups, etc.２－１８ The "alkenyl group" is not particularly limited, and examples thereof include a vinyl group (ethenyl group), an allyl group (2-propenyl group), a 1-propenyl group, an isopropenyl group (1-methylvinyl group), a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, and a dodecenyl group.

[0039] As used herein, "C ２－１８ The term "alkynyl group" refers to a group having two or more carbon atoms. １－１８ "C" means an alkynyl group having one or more triple bonds in the "alkyl group." ２－１８ The "alkynyl group" is not particularly limited, and examples thereof include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, a decynyl group, an undecynyl group, and a dodecynyl group.

[0040] As used herein, "C ３－１８ The term "alicyclic group" refers to a hydrocarbon group having, in whole or in part, a monocyclic or polycyclic structure having 3 to 18 carbon atoms. Alicyclic groups also include cycloalkyl groups, cycloalkenyl groups, cycloalkynyl groups, monocycloalkyl groups, polycycloalkyl groups, etc. ３－１８ The divalent carbon atom at any position excluding the terminals contained in the "alicyclic group" may be -O-, -C(=O)-, -COO-, -OCO-, -CONH-, -NHCO-, -S- or -SO ２ - may be substituted (however, adjacent divalent carbon atoms may not be substituted at the same time). ３－１８The "cycloalkyl group" is not particularly limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 1-i-propylcyclopentan-1-yl group, a cyclohexyl group, a t-butylcyclohexyl group, a tricyclodecanyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a 2-methyladamantan-2-yl group, a 2-i-propyladamantan-2-yl group, a bornyl group, a norbornyl group, a fenchyl group, a pinanyl group, an adamantyl group, a tricyclodecyl group, a tetracyclododecyl group, a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a bornylmethyl group, a norbornylmethyl group, an adamantylmethyl group, a 1-methylcyclopentyloxycarbonylmethyl group, a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group.

[0041] As used herein, the term "3- to 18-membered non-aromatic heterocyclic group" refers to a 3- to 18-membered non-aromatic heterocyclic group containing one or more heteroatoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms, and may be a monocyclic, polycyclic, or fused ring, and may be saturated or partially unsaturated. The "3- to 18-membered non-aromatic heterocyclic group" is not particularly limited, and examples thereof include an aziridinyl group, an azetidyl group, a pyrrolidinyl group, a pyrrolyl group, a piperidinyl group, a piperazinyl group, a morpholinyl group, a thiomorpholinyl group, a tetrahydrofuryl group, a tetrahydropyranyl group, an oxetanyl group, a tetrahydrofuryl group, a tetrahydropyranyl group, an imidazolinyl group, an oxazolinyl group, a 2,5-diazabicyclo[2.2.1]heptyl group, a 2,5-diazabicyclo[2.2.2]octyl group, a 3,8-diazabicyclo[3.2.1]octyl group, a 1,4-diazabicyclo[4.3.0]nonyl group, a 1-azaadamantyl group, and a 2-azaadamantyl group.

[0042] As used herein, "C ６－１８ The term "aryl group" means an aromatic hydrocarbon cyclic group having 6 to 18 carbon atoms, and may be a monocyclic, polycyclic, or fused ring. ６－１８The "aryl group" is not particularly limited, and examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an azulenyl group, a pentalenyl group, a heptalenyl group, an indacenyl group, an acenaphthyl group, a phenanthrenyl group, an anthracenyl group, and the like.

[0043] As used herein, "C ７－１８ An aralkyl group is defined as "C １－１２ The substitutable portion of the "C alkyl group" is ６－１２ "C" means a group substituted with an "aryl group." ７－１８ The "aralkyl group" is not particularly limited, and examples thereof include a benzyl group, a phenethyl group, a 3-phenylpropyl group, a 4-phenylbutyl group, a 1-naphthylmethyl group, and a 2-naphthylmethyl group.

[0044] As used herein, the term "5- to 18-membered aromatic heterocyclic group" refers to a monocyclic, polycyclic, or fused 5- to 18-membered aromatic heterocyclic group containing one or more heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom. The "5- to 18-membered aromatic heterocyclic group" is not particularly limited, and examples thereof include a pyrrolyl group, a furyl group, a thienyl group, an imidazolyl group, a triazolyl group, a tetrazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a furazanyl group, a thiadiazolyl group, an oxadiazolyl group, a pyridyl group, a pyrazinyl group, a pyridazinyl group, a pyrimidinyl group, a triazinyl group, a purinyl group, a pteridinyl group, a quinolyl group, an isoquinolyl group, a naphthyridinyl group, a Examples of such groups include an aryl group, a quinoxalinyl group, a cinnolinyl group, a quinazolinyl group, a phthalazinyl group, an imidazopyridyl group, an imidazothiazolyl group, an imidazooxazolyl group, a benzothiazolyl group, a benzoxazolyl group, a benzimidazolyl group, an indolyl group, an isoindolyl group, an indazolyl group, a pyrrolopyridyl group, a thienopyridyl group, a furopyridyl group, a benzothiadiazolyl group, a benzoxadiazolyl group, a pyridopyrimidinyl group, a benzofuryl group, and a benzothienyl group.

[0045] As used herein, "C １－１８The term "hydrocarbyl group" refers to a monovalent group formed by removing one hydrogen atom from a hydrocarbon having 1 to 18 carbon atoms. Hydrocarbyl groups include alkyl groups, alkenyl groups, alkynyl groups, alicyclic groups, aryl groups, aralkyl groups, and the like. １－１８ A divalent carbon atom at any position excluding the terminals contained in the "hydrocarbyl group" may be -O-, -C(=O)-, -COO-, -OCO-, -CONH-, -NHCO-, -S- or -SO ２ - may be substituted (however, adjacent divalent carbon atoms may not be substituted at the same time). １－１８ The "hydrocarbyl group" is not particularly limited, and examples thereof include "C １－１８ alkyl group," "C ２－１８ alkenyl group," "C ２－１８ alkynyl group," "C ３－１８ “Alicyclic group”, “C ６－１８ aryl group," "C ７－１８ aralkyl groups, etc.

[0046] As used herein, "C １－１８ The term "hydrocarbyloxy group" refers to a group consisting of "C １－１８ "C" means a group in which an oxygen atom (-O-) is bonded to a "hydrocarbyl group." １－１８ The "hydrocarbyloxy group" is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, a sec-butoxy group, a t-butoxy group, an n-pentoxy group, an i-pentoxy group, a sec-pentoxy group, an n-hexoxy group, an i-hexoxy group, a 1,1-dimethylpropyloxy group, a 1,2-dimethylpropyloxy group, a 2,2-dimethylpropyloxy group, a 1-methyl- "C" groups such as 2-ethylpropyloxy group, 1-ethyl-2-methylpropyloxy group, 1,1,2-trimethylpropyloxy group, 1,2,2-trimethylpropyloxy group, 1,1-dimethylbutyloxy group, 1,2-dimethylbutyloxy group, 2,2-dimethylbutyloxy group, 2,3-dimethylbutyloxy group, 1,3-dimethylbutyloxy group, 2-ethylbutyloxy group, 2-methylpentyloxy group, and 3-methylpentyloxy group １－１８alkoxy group"; cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, 1-methylcyclopentyloxycarbonylmethoxy group, 1-ethylcyclohexyloxycarbonylmethoxy group, 1-methyladamantyloxycarbonylmethoxy group, etc. ３－１８ alicyclic oxy group"; phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, azulenyloxy group, pentalenyloxy group, heptalenyloxy group, indacenyloxy group, acenaphthyloxy group, phenanthrenyloxy group, anthracenyloxy group, etc. ６－１８ aryloxy group" and the like.

[0047] As used herein, "C １－１８ The term "hydrocarbyl carbonyl group" refers to a group consisting of "C １－１８ It means a group in which a carbonyl group (—C(═O)—) is bonded to a “hydrocarbyl group.” １－１８ The "hydrocarbyl carbonyl group" is not particularly limited, and examples thereof include "C" such as an acetyl group, a propionyl group, an isopropionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, a pentanoyl group, a 3-methylbutanoyl group, a pivaloyl group, a hexanoyl group, and a heptanoyl group. １－１８ alkylcarbonyl group"; cyclopropylcarbonyl group, cyclobutylcarbonyl group, cyclopentylcarbonyl group, 2-methylcyclopentylcarbonyl group, 3-methylcyclopentylcarbonyl group, cyclohexylcarbonyl group, 2-methylcyclohexylcarbonyl group, 3-methylcyclohexylcarbonyl group, 4-methylcyclohexylcarbonyl group, adamantylcarbonyl group, etc. ３－１８ alicyclic carbonyl group"; "C" such as benzoyl group, 1-naphthoyl group, 2-naphthoyl group, etc. ６－１８ arylcarbonyl group" and the like.

[0048] As used herein, "C １－１８ The term "hydrocarbylcarbonyloxy group" refers to a group consisting of "C １－１８ "C" means a group in which an oxygen atom (-O-) is bonded to a "hydrocarbyl carbonyl group."１－１８ The "hydrocarbylcarbonyloxy group" is not particularly limited, and examples thereof include "C" such as a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, an isobutylcarbonyloxy group, a t-butylcarbonyloxy group, an n-pentylcarbonyloxy group, an isopentylcarbonyloxy group, and a hexylcarbonyloxy group. １－１８ alkylcarbonyloxy group"; cyclopropylcarbonyloxy group, cyclobutylcarbonyloxy group, cyclopentylcarbonyloxy group, cyclohexylcarbonyloxy group, etc. ３－１８ alicyclic carbonyloxy group"; "C" such as a phenylcarbonyloxy group, a naphthylcarbonyloxy group, an acenaphthylcarbonyloxy group, a phenanthrenylcarbonyloxy group, an anthracenylcarbonyloxy group, etc. ６－１８ arylcarbonyloxy group" and the like.

[0049] As used herein, "C １－１８ The term "hydrocarbyloxycarbonyl group" refers to a group consisting of "C １－１８ It means a group in which a carbonyl group (—C(═O)—) is bonded to a “hydrocarbyloxy group.” １－１８ The "hydrocarbyloxycarbonyl group" is not particularly limited, and examples thereof include "C" such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, an i-butoxycarbonyl group, a sec-butoxycarbonyl group, a t-butoxycarbonyl group, an n-pentoxycarbonyl group, and a neopentyloxycarbonyl group. １－１８ alkoxycarbonyl group"; "C" such as a cyclopropyloxycarbonyl group, a cyclobutyloxycarbonyl group, a cyclopentyloxycarbonyl group, a cyclohexyloxycarbonyl group, a 2-methylcyclopentyloxycarbonyl group, a 3-methylcyclopentyloxycarbonyl group, a 2-methylcyclohexyloxycarbonyl group, a 3-methylcyclohexyloxycarbonyl group, and a 4-methylcyclohexyloxycarbonyl group; ３－１８alicyclic oxycarbonyl group"; "C" such as a phenoxycarbonyl group, a naphthoxycarbonyl group, an acenaphthyloxycarbonyl group, a phenanthrenyloxycarbonyl group, an anthracenyloxycarbonyl group, etc. ６－１８ aryloxycarbonyl group" and the like.

[0050] As used herein, "C １－１８ The term "hydrocarbyloxycarbonyloxy group" refers to a group consisting of "C １－１８ "C" means a group in which an oxygen atom (-O-) is bonded to a "hydrocarbyloxycarbonyl group." １－１８ The "hydrocarbyloxycarbonyloxy group" is not particularly limited, and examples thereof include "C" such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propyloxycarbonyloxy group, an i-propyloxycarbonyloxy group, an n-butoxycarbonyloxy group, an i-butoxycarbonyloxy group, a sec-butoxycarbonyloxy group, a t-butoxycarbonyloxy group, an n-pentyloxycarbonyloxy group, an i-pentyloxycarbonyloxy group, and an n-hexyloxycarbonyloxy group. １－１８ alkoxycarbonyloxy group"; "C" such as cyclopropyloxycarbonyloxy group, cyclobutyloxycarbonyloxy group, cyclopentyloxycarbonyloxy group, cyclohexyloxycarbonyloxy group, etc. ３－１８ alicyclic oxycarbonyloxy group"; "C" such as a phenoxycarbonyloxy group, a naphthoxycarbonyloxy group, an acenaphthyloxycarbonyloxy group, a phenanthrenyloxycarbonyloxy group, an anthracenyloxycarbonyloxy group, etc. ６－１８ aryloxycarbonyloxy group" and the like.

[0051] As used herein, "C １－１８ The term "hydrocarbylamino group" refers to a group consisting of one "C １－１８ "C" means a group bonded to an amino group. １－１８The "hydrocarbylamino group" is not particularly limited, and examples thereof include a "C hydrocarbylamino group" such as a methylamino group, an ethylamino group, an n-propylamino group, an i-propylamino group, an n-butylamino group, an i-butylamino group, a sec-butylamino group, a t-butylamino group, an n-pentylamino group, an i-pentylamino group, a neopentylamino group, and an n-hexylamino group. １－１８ alkylamino group"; cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, 2-methylcyclopentylamino group, 3-methylcyclopentylamino group, cyclohexylamino group, 2-methylcyclohexylamino group, 3-methylcyclohexylamino group, 4-methylcyclohexylamino group, etc. ３－１８ alicyclic amino group"; phenylamino group, 1-naphthylamino group, 2-naphthylamino group, etc. ６－１８ arylamino group" and the like.

[0052] As used herein, "diC １－１８ The term "hydrocarbylamino group" refers to two identical or different "C １－１８ "DiC" means a group in which a "hydrocarbyl group" is bonded to an amino group. １－１８ The "hydrocarbylamino group" is not particularly limited, and examples thereof include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a diisobutylamino group, a di-t-butylamino group, a di-n-pentylamino group, a di-n-hexylamino group, an N-ethyl-N-methylamino group, an N-methyl-N-n-propylamino group, an N-isopropyl-N-methylamino group, an N-n-butyl-N-methylamino group, an N N-isobutyl-N-methylamino group, N-t-butyl-N-methylamino group, N-methyl-N-n-pentylamino group, N-n-hexyl-N-methylamino group, N-ethyl-N-n-propylamino group, N-ethyl-N-isopropylamino group, N-n-butyl-N-ethylamino group, N-ethyl-N-isobutylamino group, N-t-butyl-N-ethylamino group, N-ethyl-N-n-pentylamino group, N-ethyl-N-n-hexylamino group, and other "di-C １－１８alkylamino group"; "di-C" such as dicyclopropylamino group, dicyclobutylamino group, dicyclopentylamino group, dicyclohexylamino group, etc. ３－１８ alicyclic amino group"; "di-C" such as diphenylamino group, phenylnaphthylamino group, etc. ６－１８ "N-C arylamino group" such as N-methylcyclopentanamino group, N-methylcyclohexylamino group, etc. １－１８ Alkyl-N—C ３－１８ cycloalkylamino group"; "N-C cycloalkylamino group" such as N-methyl-2-phenylethylamino group, N-ethyl-N-(4-methylphenyl)amino group, etc. １－１８ Alkyl-N—C ６－１８ arylamino group" and the like.

[0053] As used herein, "C １－１８ The term "hydrocarbylaminocarbonyl group" refers to a group consisting of "C １－１８ It means a group in which a carbonyl group (—C(═O)—) is bonded to a “hydrocarbylamino group.” １－１８ The "hydrocarbylaminocarbonyl group" is not particularly limited, and examples thereof include "C" such as a methylaminocarbonyl group, an ethylaminocarbonyl group, an n-propylaminocarbonyl group, an i-propylaminocarbonyl group, an n-butylaminocarbonyl group, a sec-butylaminocarbonyl group, a t-butylaminocarbonyl group, an n-pentylaminocarbonyl group, a 2-pentylaminocarbonyl group, a neopentylaminocarbonyl group, a 4-methyl-2-pentylaminocarbonyl group, an n-hexylaminocarbonyl group, and a 3-methyl-n-pentylaminocarbonyl group. １－１８ alkylaminocarbonyl group"; cyclopropylaminocarbonyl group, cyclobutylaminocarbonyl group, cyclopentylaminocarbonyl group, cyclohexylaminocarbonyl group, 2-methylcyclopentylaminocarbonyl group, 3-methylcyclopentylaminocarbonyl group, 2-methylcyclohexylaminocarbonyl group, 3-methylcyclohexylaminocarbonyl group, 4-methylcyclohexylaminocarbonyl group, etc. ３－１８ alicyclic aminocarbonyl group"; phenylaminocarbonyl group, 1-naphthylaminocarbonyl group, 2-naphthylaminocarbonyl group, etc.６－１８ arylaminocarbonyl group.

[0054] As used herein, "diC １－１８ The term "hydrocarbylaminocarbonyl group" refers to a "diC １－１８ "DiC" means a group in which a carbonyl group (-C(=O)-) is bonded to a "hydrocarbylamino group." １－１８ The "hydrocarbylaminocarbonyl group" is not particularly limited, and examples thereof include a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a di-n-propylaminocarbonyl group, a diisopropylaminocarbonyl group, a di-n-butylaminocarbonyl group, a diisobutylaminocarbonyl group, a di-t-butylaminocarbonyl group, a di-n-pentylaminocarbonyl group, a di-n-hexylaminocarbonyl group, an N-ethyl-N-methylaminocarbonyl group, an N-methyl-N-n-propylaminocarbonyl group, an N-isopropyl-N-methylaminocarbonyl group, an N-n-butyl-N-methylaminocarbonyl group, an N-isobutyl-N-methylaminocarbonyl group, an N-t-butyl-N-methylaminocarbonyl group, an N-methyl-N-n-pentylaminocarbonyl group, an N-n-hexyl-N-methylaminocarbonyl group, "diC" groups such as an N-ethyl-N-n-propylaminocarbonyl group, an N-ethyl-N-isopropylaminocarbonyl group, an N-n-butyl-N-ethylaminocarbonyl group, an N-ethyl-N-isobutylaminocarbonyl group, an N-t-butyl-N-ethylaminocarbonyl group, an N-ethyl-N-n-pentylaminocarbonyl group, and an N-ethyl-N-n-hexylaminocarbonyl group １－１８ alkylamino group"; "di-C" such as dicyclopropylaminocarbonyl group, dicyclobutylaminocarbonyl group, dicyclopentylaminocarbonyl group, dicyclohexylaminocarbonyl group, etc. ３－１８ alicyclic aminocarbonyl group"; "di-C" such as diphenylaminocarbonyl group, phenylnaphthylaminocarbonyl group, etc. ６－１８ arylaminocarbonyl group" and the like.

[0055] As used herein, "C １－１８ The term "hydrocarbylcarbonylamino group" refers to a group consisting of "C １－１８"C" means a group in which an amino group is bonded to a "hydrocarbyl carbonyl group." １－１８ The "hydrocarbylcarbonylamino group" is not particularly limited, and examples thereof include "C" such as methylcarbonylamino group, ethylcarbonylamino group, n-propylcarbonylamino group, i-propylcarbonylamino group, n-butylcarbonylamino group, i-butylcarbonylamino group, sec-butylcarbonylamino group, t-butylcarbonylamino group, n-pentylcarbonylamino group, i-pentylcarbonylamino group, and n-hexylcarbonylamino group. １－１８ alkylcarbonylamino group; cyclopropylcarbonylamino group, cyclobutylcarbonylamino group, cyclopentylcarbonylamino group, cyclohexylcarbonylamino group, etc. ３－１８ alicyclic carbonylamino group"; "C" such as phenylcarbonylamino group, naphthylcarbonylamino group, acenaphthylcarbonylamino group, phenanthrenylcarbonylamino group, anthracenylcarbonylamino group, etc. ６－１８ arylcarbonylamino group" and the like.

[0056] As used herein, "C １－１８ The term "hydrocarbylaminocarbonyloxy group" refers to a group consisting of "C １－１８ "C" means a group in which an oxygen atom (-O-) is bonded to a "hydrocarbylaminocarbonyl group." １－１８ The "hydrocarbylaminocarbonyloxy group" is not particularly limited, and examples thereof include "C" such as a methylaminocarbonyloxy group, an ethylaminocarbonyloxy group, and an n-propylaminocarbonyloxy group. １－１８ alkylaminocarbonyloxy group"; cyclopropylaminocarbonyloxy group, cyclohexylaminocarbonyloxy group, etc. ３－１８ alicyclic aminocarbonyloxy group"; phenylaminocarbonyloxy group, 1-naphthylaminocarbonyloxy group, etc. ６－１８ arylaminocarbonyloxy group" and the like.

[0057] As used herein, "diC １－１８ The term "hydrocarbylaminocarbonyloxy group" refers to a "diC １－１８"DiC" means a group in which an oxygen atom (—O—) is bonded to a "hydrocarbylaminocarbonyl group." １－１８ The "hydrocarbylaminocarbonyloxy group" is not particularly limited, and examples thereof include "diC" such as dimethylaminocarbonyloxy group, diethylaminocarbonyloxy group, and di-n-propylaminocarbonyloxy group. １－１８ alkylaminocarbonyloxy group, etc.

[0058] As used herein, "C １－１８ The term "hydrocarbylaminocarbonylamino group" refers to a group consisting of "C １－１８ "Hydrocarbylaminocarbonyl group" means a group bonded to an amino group. １－１８ The "hydrocarbylaminocarbonylamino group" is not particularly limited, and examples thereof include "C" such as methylaminocarbonylamino group, ethylaminocarbonyloxy group, and n-propylaminocarbonylamino group. １－１８ alkylaminocarbonylamino group"; cyclopropylaminocarbonylamino group, cyclohexylaminocarbonylamino group, etc. ３－１８ alicyclic aminocarbonylamino group"; phenylaminocarbonylamino group, 1-naphthylaminocarbonylamino group, etc. ６－１８ arylaminocarbonylamino group" and the like.

[0059] As used herein, "diC １－１８ The term "hydrocarbylaminocarbonylamino group" refers to a "diC １－１８ "Hydrocarbylaminocarbonyl group" means a group bonded to an amino group. １－１８ The "hydrocarbylaminocarbonylamino group" is not particularly limited, and examples thereof include "diC" such as dimethylaminocarbonylamino group, diethylaminocarbonylamino group, and di-n-propylaminocarbonylamino group. １－１８ alkylaminocarbonylamino group, etc.

[0060] As used herein, "C １－１８ The term "hydrocarbyloxycarbonylamino group" refers to a group consisting of "C １－１８"C" means a group in which a "hydrocarbyloxycarbonyl group" is bonded to an amino group. １－１８ The "hydrocarbyloxycarbonylamino group" is not particularly limited, and examples thereof include "C" such as a methoxycarbonylamino group, an ethoxycarbonylamino group, an n-propoxycarbonylamino group, an i-propoxycarbonylamino group, an n-butoxycarbonylamino group, and a t-butoxycarbonylamino group. １－１８ alkoxycarbonylamino group"; cyclopropyloxycarbonylamino group, cyclohexyloxycarbonylamino group, etc. ３－１８ alicyclic oxycarbonylamino group"; phenyloxycarbonylamino group, 1-naphthyloxycarbonylamino group, etc. ６－１８ aryloxycarbonylamino group" and the like.

[0061] As used herein, "C １－１８ The term "hydrocarbylthio group" refers to a group consisting of "C １－１８ "C" means a group in which a sulfur atom (-S-) is bonded to a "hydrocarbyl group." １－１８ The "hydrocarbylthio group" is not particularly limited, and examples thereof include a "C methylthio group, an ethylthio group, an n-propylthio group, an i-propylthio group, an n-butylthio group, an i-butylthio group, a t-butylthio group, an n-pentylthio group, an n-hexylthio group, etc. １－１８ alkylthio group"; cyclopropylthio group, cyclobutylthio group, cyclopentylthio group, cyclohexylthio group, 2-methylcyclopentylthio group, 3-methylcyclopentylthio group, 2-methylcyclohexylthio group, 3-methylcyclohexylthio group, 4-methylcyclohexylthio group, etc. ３－１８ alicyclic thio group"; "C" such as a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, an acenaphthylthio group, a phenanthrenylthio group, an anthracenylthio group, etc. ６－１８ arylthio group" and the like.

[0062] As used herein, "C １－１８ The term "hydrocarbylsulfinyl group" refers to a group consisting of "C １－１８ "C" means a group in which a sulfinyl group (-S(=O)-) is bonded to a "hydrocarbyl group."１－１８ The "hydrocarbylsulfinyl group" is not particularly limited, and examples thereof include "C" such as methylsulfinyl group, ethylsulfinyl group, n-propylsulfinyl group, i-propylsulfinyl group, n-butylsulfinyl group, t-butylsulfinyl group, pentylsulfinyl group, and hexylsulfinyl group. １－１８ alkylsulfinyl group"; cyclopropylsulfinyl group, cyclobutylsulfinyl group, cyclopentylsulfinyl group, cyclohexylsulfinyl group, 2-methylcyclopentylsulfinyl group, 3-methylcyclopentylsulfinyl group, 2-methylcyclohexylsulfinyl group, 3-methylcyclohexylsulfinyl group, 4-methylcyclohexylsulfinyl group, etc. ３－１８ alicyclic sulfinyl group"; "C" such as a phenylsulfinyl group, a naphthylsulfinyl group, an acenaphthylsulfinyl group, a phenanthrenylsulfinyl group, an anthracenylsulfinyl group, etc. ６－１８ arylsulfinyl group" and the like.

[0063] As used herein, "C １－１８ The term "hydrocarbylsulfonyl group" refers to a group consisting of "C １－１８ The hydrocarbyl group may be a sulfonyl group (-SO ２ -) is bonded to the group. １－１８ The "hydrocarbylsulfonyl group" is not particularly limited, and examples thereof include "C" such as a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, an i-propylsulfonyl group, an n-butylsulfonyl group, a t-butylsulfonyl group, and a pentylsulfonyl group. １－１８ alkylsulfonyl group"; "C" such as cyclopropylsulfonyl group, cyclobutylsulfonyl group, cyclopentylsulfonyl group, cyclohexylsulfonyl group, 2-methylcyclopentylsulfonyl group, 3-methylcyclopentylsulfonyl group, 2-methylcyclohexylsulfonyl group, 3-methylcyclohexylsulfonyl group, and 4-methylcyclohexyl group; ３－１８ alicyclic sulfonyl group"; "C" such as a phenylsulfonyl group, a naphthylsulfonyl group, an acenaphthylsulfonyl group, a phenanthrenylsulfonyl group, an anthracenylsulfonyl group, etc. ６－１８arylsulfonyl group" and the like.

[0064] In this specification, the term "optionally having a substituent" is not particularly limited as long as it is chemically permissible and has the effect of the present invention. Examples of the "substituent" include (1) a halogen atom, (2) a hydroxy group, (3) a thiol group, (4) a nitro group, (5) a cyano group, (6) a carboxy group, (7) an amino group, (8) a sulfo group, or (9) a C group in which at least a portion of the hydrogen atoms may be substituted with the above (1) to (8). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbyloxycarbonyloxy group, C １－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ Hydrocarbyloxycarbonylamino group, C １－１８ Hydrocarbylthio group, C １－１８ Hydrocarbylsulfinyl group, C １－１８ A hydrocarbylsulfonyl group, wherein a divalent carbon atom at any position except the terminal of the substituent is —O—, —C(═O)—, —COO—, —OCO—, —CONH—, —NHCO—, —S—, or SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not simultaneously substituted), etc.

[0065] [1-2-1. Iodonium Cation (III)] As the iodonium cation according to this embodiment, an iodonium cation represented by the following general formula (III) can be used.

[0066]

[0067] In the iodonium cation represented by general formula (III), R ３Ａ and R ３Ｂ each independently represents a C １－１８ R represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group which may have a substituent, or a 5- to 18-membered aromatic heterocyclic group which may have a substituent; ３Ａ and R ３Ｂ are directly connected to each other by a single bond, or are connected to each other by a divalent linking group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring together with the iodine atom in formula (V-1).

[0068] In the iodonium cation represented by the general formula (III), for example, R ３Ａ and R ３Ｂ wherein any one of C １－１８ Among the hydrocarbyl groups, C which may have a substituent ２－１８ It may be an alkynyl group. ３Ａ and R ３Ｂ wherein any one of C １－１８ In the case of an alkynyl group, for example, the following iodonium cations can be exemplified.

[0069]

[0070] Also R ３Ａ and R ３Ｂ C which may have a substituent ６－１８ In the case where they are aryl groups, they are directly connected to each other via a single bond or via a divalent linking group such as -O-, -S-, -C(=O)-, -S(=O)-, or -S(=O) ２ -, -C(=O)O-, or C１－３ They may be linked via an alkylene group to form a ring together with the iodine atom in formula (III). Examples of the ring include the following iodonium cations.

[0071]

[0072] [1-2-2. Iodonium Cation (IV)] The iodonium cation according to this embodiment may be an iodonium cation represented by (IV-1) or (IV-2).

[0073]

[0074] [1-2-2-1. Iodonium cation (IV-1)] In the iodonium cation represented by general formula (IV-1), Ar ４Ａ and Ar ４Ｂ each independently represents a C ６－１８ C represents an aryl group or a 5- to 18-membered heterocyclic group, which may have the above-mentioned substituents. ６－１８ The aryl group or the 5- to 18-membered heterocyclic group may be a C group in which at least a portion of the hydrogen atoms are optionally substituted with a halogen atom, a hydroxy group, a thiol group, a nitro group, a cyano group, a carboxy group, an amino group, or a sulfo group, or a C group in which at least a portion of the hydrogen atoms are optionally substituted with a halogen atom, a hydroxy group, a thiol group, a nitro group, a cyano group, a carboxy group, an amino group, or a sulfo group. １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbyloxycarbonyloxy group, C １－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C１－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ Hydrocarbyloxycarbonylamino group, C １－１８ Hydrocarbylthio group, C １－１８ a hydrocarbylsulfinyl group, or C １－１８ The divalent carbon atom at any position of the substituent except for the terminal may be substituted with a hydrocarbylsulfonyl group, and may be —O—, —C(═O)—, —COO—, —OCO—, —CONH—, —NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), Ar ４Ａ and Ar ４Ｂ are directly connected to each other by a single bond, or are connected to each other by a divalent linking group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring together with the iodine atom in formula (IV-1).

[0075] In the iodonium cation represented by the general formula (IV-1), for example, Ar ４Ａ and Ar ４Ｂ At least one of the following may be an optionally substituted 5- to 18-membered heterocyclic group. Examples of the iodonium cation include the following iodonium cations:

[0076]

[0077] In the iodonium cation represented by the general formula (IV-1), Ar ４Ａ and Ar ４Ｂ may be the same as or different from each other. ４Ａ and Ar ４ＢBy making them different from each other, the iodonium cation represented by general formula (IV-1) can be made asymmetric, which is preferable because it makes it possible to reduce the crystallinity of the iodonium cation and improve its solubility.

[0078] [1-2-2-2. Iodonium cation (IV-2)] In the iodonium cation represented by general formula (IV-2), R ４Ｃ and R ４Ｄ are each independently a halogen atom, a hydroxy group, a thiol group, a nitro group, a cyano group, a carboxy group, an amino group, a sulfo group, or a C in which at least a portion of the hydrogen atoms may be substituted with a halogen atom, a hydroxy group, a thiol group, a nitro group, a cyano group, a carboxy group, an amino group, or a sulfo group. １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbyloxycarbonyloxy group, C １－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ Hydrocarbyloxycarbonylamino group, C １－１８ Hydrocarbylthio group, C １－１８ a hydrocarbylsulfinyl group, or C １－１８a hydrocarbylsulfonyl group, and a divalent carbon atom at any position excluding the terminal is -O-, -C(=O)-, -COO-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); v and w are each an integer of 0 to 5, and when the values ​​of v and w are an integer of 2 or more, R ４Ｃ and R ４Ｄ may be the same or different from each other. In the iodonium cation represented by general formula (IV-2), (R ４Ｃ ) ｖ and (R ４Ｄ ) ｗ may be the same or different. ４Ｃ ) ｖ and (R ４Ｄ ) ｗ By making them different from each other, the iodonium cation represented by general formula (IV-2) can be made asymmetric, which is preferable because it makes it possible to reduce the crystallinity of the iodonium cation and improve its solubility.

[0079] In the iodonium cation represented by general formula (IV-2), for example, R ４Ｃ and R ４Ｄ is a C which may have a halogen atom, a hydroxy group, a nitro group, a cyano group, or a substituent as an electron donating group or an electron withdrawing group, etc. １－４ Haloalkyl group, optionally substituted C １－１８ Hydrocarbyloxy group, optionally substituted C １－１８ Hydrocarbyloxycarbonyl group, optionally substituted C １－１８ Hydrocarbylcarbonyloxy group, optionally substituted C １－１８ It may be a hydrocarbylthio group, etc. Examples of the iodonium cation include the following iodonium cations.

[0080]

[0081] [1-2-2-3. Iodonium cation (IV-3)] In another embodiment, in the iodonium cation represented by the following general formula (IV-1), Ar ４Ｂ may be an iodonium cation represented by the following general formula (IV-3).

[0082]

[0083] In general formula (IV-3), R ４Ｅ represents a halogen atom, a nitro group, C １－４ a haloalkyl group or a branched C ３－１０ alkyl groups (e.g., i-propyl, i-butyl, sec-butyl, t-butyl, sec-pentyl, t-pentyl, neopentyl, 1-methylbutyl, 2-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, etc.), C １－１２ Hydrocarbyloxy group, C １－１２ Hydrocarbyl carbonyl group, C １－１２ Hydrocarbylcarbonyloxy group, C １－１２ Hydrocarbyloxycarbonyl group or C １－１２ represents a hydrocarbyloxycarbonyloxy group; R ４Ｅ is a halogen atom, a nitro group, C １－４ When Ar is a haloalkyl group, ４Ａ and Ar ４Ｂ are assumed to be different from each other.

[0084] In general formula (IV-3), from the viewpoint of reducing the crystallinity of the iodonium cation and improving the solubility, R ４Ｅ is a halogen atom, a nitro group, C １－４ a haloalkyl group or a C group which may have a substituent １－８ Alkoxy group, branched C ３－８ is an alkyl group, and R ４Ｅ is a halogen atom, a nitro group, C １－４ When Ar is a haloalkyl group, ４Ａ and Ar ４Ｂ are preferably different asymmetric iodonium cations, and R４Ｅ is a fluorine atom, a chlorine atom, a nitro group, C １－４ is a haloalkyl group, and Ar ４Ａ and Ar ４Ｂ are more preferably different asymmetric iodonium cations.

[0085] [1-2-2-4. Iodonium cation (IV-4)] In another embodiment, in the iodonium cation represented by the following general formula (IV-1), Ar ４Ｂ may be an iodonium cation represented by the following general formula (IV-4).

[0086]

[0087] In general formula (IV-4), R ４Ｆ each independently represents a C １－１２ Hydrocarbyl group, C １－１２ Hydrocarbyloxy group, C １－１２ Hydrocarbyl carbonyl group, C １－１２ Hydrocarbylcarbonyloxy group, C １－１２ Hydrocarbyloxycarbonyl group or C １－１２ represents a hydrocarbyloxycarbonyloxy group.

[0088] In general formula (IV-4), from the viewpoint of improving the stability and solubility of the iodonium cation, R ４Ｆ each independently represents a C １－１０ Alkyl group, C １－１０ An alkoxy group is preferred, and C １－８ Alkyl group, C １－８ More preferably, it is an alkoxy group, and C １－４ Alkyl group, C １－４ An alkoxy group is more preferred.

[0089] [1-2-3. Specific examples of iodonium cations] Specific examples of iodonium cations represented by general formulas (III) to (IV-2) include ethynyl(phenyl)iodonium cation, bis(pyridine)iodonium cation, bis(2,4,6-trimethylpyridine)iodonium cation, diphenyliodonium cation, bis(4-(t-butyl)phenyl)iodonium cation, (2-carboxyphenyl)(phenyl)iodonium cation, (4-nitrophenyl)(phenyl)iodonium cation, (3-(trifluoromethyl)phenyl)(2,4,6-trimethylphenyl)iodonium cation, bis(4-fluorophenyl)iodonium cation, (4-(bromomethyl)phenyl)(2,4,6-trimethoxyphenyl)iodonium cation, 4-biphenylyl(2,4,6-trimethoxyphenyl)iodonium cation, bis(2,4,6-trimethylphenyl)iodonium cation, 4-isopropyl-4'-methyl Examples of iodonium cations include phenyl diphenyliodonium cation, (4-(trifluoromethyl)phenyl)(2,4,6-trimethylphenyl)iodonium cation, ((4-trifluoromethyl)phenyl)(2,4,6-trimethoxyphenyl)iodonium cation, (5-fluoro-2-nitrophenyl)(2,4,6-trimethoxyphenyl)iodonium cation, (3-bromophenyl)(mesityl)iodonium cation, bis(4-bromophenyl)iodonium cation, (3,5-dichlorophenyl)(2,4,6-trimethoxyphenyl)iodonium cation, (4-methylphenyl)(2,4,6-trimethylphenyl)iodonium cation, (3-methylphenyl)(2,4,6-trimethylphenyl)iodonium cation, (2-methylphenyl)(2,4,6-trimethylphenyl)iodonium cation, and phenyl(2,4,6-trimethoxyphenyl)iodonium cation.

[0090] [1-3. Other Counter Cations] The heteropolyoxotungstate compound according to this embodiment is represented by the following general formula (I): (A ｍ＋ ) ｘ／ｍ (B ｎ＋ ) ｙ／ｎ (C－（ｘ＋ｙ） ) (I) A ｍ＋ are each independently H ＋ , a metal ion, or an ammonium ion; m is an integer of 1 to 5, and x and x / m are integers.

[0091] A ｍ＋ The metal ions that can be used as the metal ion are not particularly limited, and examples thereof include Li ＋ , Na ＋ , K. ＋ , Rb ＋ , Cs ＋ , Be ２＋ , Mg ２＋ , Ca ２＋ , Sr ２＋ , Ba ２＋ , Co ３＋ , Bi ３＋ , Zr ４＋ , Hf ４＋ , Bi ５＋ These metal ions may be used alone or in combination of two or more.

[0092] A ｍ＋ The ammonium cation that can be used as the cation is not particularly limited, and examples thereof include NH ４＋ , quaternary ammonium cations, etc. The quaternary ammonium cations include (R) ４ N ＋ R is independent of each other and may be the same or different. R is not particularly limited, and examples thereof include C １－１８ Examples of R include a C １－１２ C is preferably a hydrocarbyl group, and may have a substituent. １－８ It is more preferably a hydrocarbyl group.

[0093] A ｍ＋ From the viewpoint of the stability and reactivity of the heteropolyoxotungstate, ＋ , Na ＋ , K. ＋ , Rb ＋ , Cs ＋ , Mg ２＋ , Ca２＋ , Sr ２＋ , Ba ２＋ , Co ３＋ , N.H. ４＋ , or a quaternary ammonium cation is preferred, Na ＋ , K. ＋ , Rb ＋ , Cs ＋ , Co ３＋ , N.H. ４＋ , or a quaternary ammonium cation is more preferred, NH ４＋ or quaternary ammonium cations are more preferred.

[0094] In the heteropolyoxotungstate compound or compounds represented by the following formula (I), the ratios of x / m and y / n are not particularly limited and can be appropriately set depending on the stability, reactivity, application, etc. of the heteropolyoxotungstate compound. (A ｍ＋ ) ｘ／ｍ (B ｎ＋ ) ｙ／ｎ (C －（ｘ＋ｙ） ) (I)

[0095] For example, when the value of x+y is 3 and m and n are 1, from the viewpoint of achieving both reactivity and stability of the heteropolyoxotungstate compound, x:y=0-2:1-3 is preferable, 0-2:2-3 is more preferable, and 0-1:2-3 is even more preferable. In the above case, x is preferably an integer of 0-2 and y is an integer of 1-3, preferably x is an integer of 0-2 and y is an integer of 2-3, and more preferably x is an integer of 0-1 and y is an integer of 2-3.

[0096] Furthermore, for example, when the value of x+y is 4 and m and n are 1, from the viewpoint of achieving both reactivity and stability of the heteropolyoxotungstate compound, x:y=0-3:1-4 is preferable, 0-2:1-4 is more preferable, and 0-2:2-4 is even more preferable. In the above case, x is preferably an integer of 0-3 and y is an integer of 1-4, more preferably x is an integer of 0-2 and y is an integer of 1-4, and even more preferably x is an integer of 0-2 and y is an integer of 2-4.

[0097] [1-4. Compound, Solvate, or Mixture of These] The heteropolyoxotungstate mixture according to this embodiment may contain two or more different heteropolyoxotungstate compounds represented by the following general formula (I) or solvates thereof. (A ｍ＋ ) ｘ／ｍ (B ｎ＋ ) ｙ／ｎ (C －（ｘ＋ｙ） ) (I) A ｍ＋ are each independently H ＋ , a metal ion, or an ammonium ion; B ｎ＋ each independently represents an iodonium cation; －（ｘ＋ｙ） represents heteropolyoxotungstic acid; m is an integer of 1 to 5, n is an integer of 1 or 2, x and x / m are integers of 0 or more, and y and y / n are natural numbers.

[0098] In the heteropolyoxotungstate mixture, C －（ｘ＋ｙ） The heteropolyoxotungstic acid represented by the formula (I) is not particularly limited, and examples thereof include [PW １２ O ４０ ] ３－ , [SiW １２ O ４０ ] ４－ , [B.W. １２ O ４０ ] ５－ , [SW １２ O ４０ ] ２－ , [P ２ W １８ O ６２] ６－ , [Si ２ W １８ O ６２ ] ８－ , [S ２ W １８ O ６２ ] ４－ , [P.W. ９ O ３４ ] ９－ , [P.W. １０ O ３６ ] ７－ , [P.W. １１ O ３９ ] ７－ , [SiW ９ O ３４ ] １０－ , [SiW １０ O ３６ ] ８－ , [SiW １１ O ３９ ] ８－ , [P ２ W １７ O ６１ ] １０－ etc. can be used.

[0099] In the heteropolyoxotungstate salt mixture, B bonded to one of the heteropolyoxotungstates is ｎ＋ The number of (iodonium cations) is not particularly limited, and for example, two or more iodonium cations B selected from integers of 1 to 10 are used per one heteropolyoxotungstic acid. ｎ＋ The heteropolyoxotungstate compound may contain two or more different heteropolyoxotungstate compounds to which B is bonded. ｎ＋ The group may include those in which one, two, and three are bonded.

[0100] In addition, in the two or more different heteropolyoxotungstate compounds represented by the above general formula (I) or solvates thereof, each of them is C －（ｘ＋ｙ） When the heteropolyoxotungstic acid represented by ｍ＋ and B ｎ＋In this case, the heteropolyoxotungstate mixture contains a plurality of heteropolyoxotungstate compounds or solvates thereof having different numbers of . In this case, the heteropolyoxotungstate mixture is represented by the following general formula (I'): (A ｍ＋ ) ｘ’／ｍ (B ｎ＋ ) ｙ’／ｎ (C －（ｘ’＋ｙ’） ) (I') [wherein, A ｍ＋ are each independently H ＋ , a metal ion, or an ammonium ion; B ｎ＋ each independently represents an iodonium cation; －（ｘ’＋ｙ’） represents heteropolyoxotungstic acid; m is an integer of 1 to 5, n is an integer of 1 or 2, x' and x' / m are real numbers of 0 or more, y' and y' / n are real numbers of more than 0, and x'+y' is a natural number.

[0101] B bound to one heteropolyoxotungstic acid ｎ＋ The number of (iodonium cations) can be changed by appropriately adjusting the blending ratio of the raw materials of heteropolyoxotungstic acid and iodonium cations used in producing the heteropolyoxotungstate compound or solvate, or a mixture thereof.

[0102] In the heteropolyoxotungstate compound or mixture, B ｎ＋ When an iodonium cation is used as the I3d or W4f, the elemental composition of I and W contained in the heteropolyoxotungstate compound or mixture can be determined by XRF or XPS analysis. A known, conventional method can be used for XRF analysis; for example, the molar ratio of S to W in the heteropolyoxotungstate compound or mixture can be determined by SQX analysis using a calibration curve method or a fundamental parameter (FP) method. A known, conventional method can be used for XPS analysis; for example, the molar ratio of S to W in the heteropolyoxotungstate compound or mixture can be determined by determining the atomic percentage of each element based on the peak areas of I3d and W4f.

[0103] In the heteropolyoxotungstate salt mixture, a Keggin type or a Dawson type or a silicotungstic acid which is a defective species thereof is used as the heteropolyoxotungstic acid, and B ｎ＋ When an iodonium cation is used as the I (iodine) and W (tungsten), the molar ratio of I (iodine) to W (tungsten) in the heteropolyoxotungstate mixture determined by XRF or XPS analysis is preferably I:W=0.5-10:9-18, more preferably I:W=1-10:9-18, and even more preferably I:W=2-8:10-18.

[0104] In the heteropolyoxotungstate salt mixture, Keggin-type or Dawson-type silicotungstic acid is used as the heteropolyoxotungstic acid, and B ｎ＋ When an iodonium cation is used as the I (iodine) and W (tungsten), the molar ratio of I (iodine) to W (tungsten) in the heteropolyoxotungstate mixture determined by XRF or XPS analysis is preferably I:W=0.5-8:12-18, more preferably I:W=1-8:12-18, and even more preferably I:W=2-8:12-18.

[0105] In the heteropolyoxotungstate salt mixture, Keggin-type silicotungstic acid is used as the heteropolyoxotungstic acid, and B ｎ＋ When an iodonium cation is used as the heteropolyoxotungstate, the molar ratio of I (iodine) to W (tungsten) in the heteropolyoxotungstate mixture determined by XRF or XPS analysis is preferably I:W=0.5 to 4:12, more preferably I:W=1 to 4:12, and even more preferably I:W=2.5 to 4:12. In the heteropolyoxotungstate mixture, a Dawson-type silicotungstic acid is used as the heteropolyoxotungstic acid, and B ｎ＋When an iodonium cation is used as the I (iodine) and W (tungsten), the molar ratio of I (iodine) to W (tungsten) in the heteropolyoxotungstate mixture determined by XRF or XPS analysis is preferably I:W=0.5 to 8:18, more preferably I:W=1 to 8:18, and even more preferably I:W=2 to 8:18.

[0106] In the heteropolyoxotungstate salt mixture, a Keggin type or a Dawson type or a phosphotungstic acid, which is a defective species thereof, is used as the heteropolyoxotungstic acid. ｎ＋ When an iodonium cation is used as the I (iodine) and W (tungsten), the molar ratio of I (iodine) to W (tungsten) in the heteropolyoxotungstate mixture determined by XRF or XPS analysis is preferably I:W=0.5-6:9-18, more preferably I:W=1-6:9-18, and even more preferably I:W=2-6:10-18.

[0107] In the heteropolyoxotungstate salt mixture, Keggin-type or Dawson-type phosphotungstic acid is used as the heteropolyoxotungstic acid, and B ｎ＋ When an iodonium cation is used as the I (iodine) and W (tungsten), the molar ratio of I (iodine) to W (tungsten) in the heteropolyoxotungstate mixture determined by XRF or XPS analysis is preferably I:W=0.5-6:12-18, more preferably I:W=1-6:12-18, and even more preferably I:W=2-6:12-18.

[0108] In the heteropolyoxotungstate salt mixture, Keggin-type phosphotungstic acid is used as the heteropolyoxotungstic acid, and B ｎ＋When an iodonium cation is used as the heteropolyoxotungstate, the molar ratio of I (iodine) to W (tungsten) in the heteropolyoxotungstate mixture determined by XRF or XPS analysis is preferably I:W=0.5 to 3:12, more preferably I:W=1 to 3:12, and even more preferably I:W=1.5 to 3:12. In the heteropolyoxotungstate mixture, Dawson-type phosphotungstic acid is used as the heteropolyoxotungstic acid, and B ｎ＋ When an iodonium cation is used as the I (iodine) and W (tungsten), the molar ratio of I (iodine) to W (tungsten) in the heteropolyoxotungstate mixture determined by XRF or XPS analysis is preferably I:W=0.5 to 6:18, more preferably I:W=1 to 6:18, and even more preferably I:W=2 to 6:18.

[0109] [1-5. Solvates] It is generally known that heteropolyoxotungstates, when crystallized, incorporate the solvent used for crystallization to form a solvate. The solvate of the heteropolyoxotungstate compound or mixture according to this embodiment is not particularly limited, and examples thereof include alcohol solvates such as methanol solvates, ethanol solvates, and isopropanol solvates; and hydrates such as monohydrates, dihydrates, trihydrates, and tetrahydrates.

[0110] [2. Method for Producing Heteropolyoxotungstate Compound or Solvate Thereof] The method for producing the heteropolyoxotungstate compound or solvate thereof according to another embodiment of the present invention is not particularly limited, and for example, a salt exchange method, an ion exchange method, or the like can be used.

[0111] [2-1. Salt Exchange Method] A method for producing a heteropolyoxotungstate compound represented by general formula (I) or a solvate thereof is characterized by having a step of reacting a compound represented by general formula (V-1) with a compound represented by general formula (V-2) to carry out salt exchange. (A ｍ＋ ) ｘ／ｍ (B ｎ＋ ) ｙ／ｎ (C －（ｘ＋ｙ）) (I) (A ｍ＋ ) ｘ／ｍ (A' ｍ’＋ ) ｙ／ｍ’ (C －（ｘ＋ｙ） ) (V-1) (B ｎ＋ ) ｙ／ｎ (Y － ) ｙ (V-2) [wherein, A ｍ＋ are each independently H ＋ A' represents a metal ion or an ammonium ion; ｍ’＋ each independently represents a metal ion or an ammonium ion; B ｎ＋ each independently represents an iodonium cation; －（ｘ＋ｙ） represents heteropolyoxotungstic acid; Y － represents a monovalent counter anion; m and m' are integers of 1 to 5, n is an integer of 1 or 2, x and x / m are integers, and y / m', y and y / n are natural numbers.

[0112] In general formula (V-2), for example, when n is 1, (B ＋ ) ｙ (Y － ) ｙ This is expressed as y(B ＋ ・Y － ) shall mean

[0113] According to another embodiment, a method for producing a heteropolyoxotungstate compound represented by general formula (I) or a solvate thereof may include the steps of: reacting a compound represented by general formula (V-1) with a compound represented by general formula (V-2) to perform salt exchange; and removing the compound represented by general formula (V-3) from the resulting compounds represented by general formulas (I) and (V-3). ｍ＋ ) ｘ／ｍ (B ｎ＋ ) ｙ／ｎ (C －（ｘ＋ｙ） ) (I) (A ｍ＋ ) ｘ／ｍ (A' ｍ’＋ ) ｙ／ｍ’ (C －（ｘ＋ｙ） ) (V-1) (Bｎ＋ ) ｙ／ｎ (Y － ) ｙ (V-2) (A' ｍ’＋ ) ｙ／ｍ’ (Y － ) ｙ (V-3) [wherein, A ｍ＋ are each independently H ＋ A' represents a metal ion or an ammonium ion; ｍ’＋ each independently represents a metal ion or an ammonium ion; B ｎ＋ each independently represents an iodonium cation; －（ｘ＋ｙ） represents heteropolyoxotungstic acid; Y － represents a monovalent counter anion; m and m' are integers of 1 to 5, n is an integer of 1 or 2, x and x / m are integers, and y / m', y and y / n are natural numbers.

[0114] In general formula (V-3), for example, when m' is 1, (A' ＋ ) ｙ (Y － ) ｙ This is expressed as y(A' ＋ ・Y － ) shall mean

[0115] <Compound Represented by General Formula (V-1)> In the compound represented by general formula (V-1), which is one of the raw materials in the method for producing a heteropolyoxotungstate compound or a solvate thereof according to this embodiment, ｍ＋ ) ｘ／ｍ (A' ｍ’＋ ) ｙ／ｍ’ (C －（ｘ＋ｙ） ) (V-1) A ｍ＋ are each independently H ＋ , a metal ion, or an ammonium ion; ｍ’＋ each independently represents a metal ion or an ammonium ion.

[0116] A' ｍ’＋ From the viewpoint of promoting the salt exchange reaction, ＋, Li ＋ , Na ＋ , K. ＋ , Rb ＋ , Cs ＋ , Be ２＋ , Mg ２＋ , Ca ２＋ , Sr ２＋ , Ba ２＋ , Co ３＋ , Bi ３＋ , Zr ４＋ , Hf ４＋ , Bi ５＋ , N.H. ４＋ , quaternary ammonium cations, or a combination thereof, and ＋ , Na ＋ , K. ＋ , Mg ２＋ , Ca ２＋ , N.H. ４＋ , quaternary ammonium cations, or a combination thereof, and ＋ , Na ＋ , K. ＋ , N.H. ４＋ , quaternary ammonium cations, or combinations thereof are more preferred.

[0117] The compound represented by the general formula (V-1) can be synthesized by a known synthesis method. Commercially available products of the compound represented by the general formula (V-1) include, for example, phosphotungstic acid (H ３ [P.W. １２ O ４０ ]・nH ２ O), tungstosilicic acid (H ４ [SiW １２ O ４０ ]・26H ２ O) and the like.

[0118] <Compound Represented by General Formula (V-2)> In the compound represented by general formula (V-2), which is one of the raw materials in the method for producing a heteropolyoxotungstate compound or a solvate thereof according to this embodiment, ｎ＋ ) ｙ／ｎ (Y － )ｙ (V-2) Y － represents a monovalent counter anion.

[0119] Y － From the viewpoint of promoting the salt exchange reaction, Br － , Cl － , I － , O.H. － , C.F. ３ SO ３ － , C ２ F ５ SO ３ － , C ３ F ７ SO ３ － , C ４ F ９ SO ３ － , p-CH ３ (C ６ H ４ ) SO ３ － , ClSO ３ － , ClO ４ － , (C ６ F ５ ) ４ B-, BF ４ － , P.F. ６ － , SbF ６ － , AlCl ４ － , BiF ６ － , AsF ６ － Preferably, Br － , Cl － , I － , O.H. － , C.F. ３ SO ３ － , C ４ F ９ SO ３ － , B.F. ４ － , P.F. ６ － , SbF６ － More preferably, Br － , Cl － , C.F. ３ SO ３ － , B.F. ４ － , P.F. ６ － , SbF ６ － It is more preferable that:

[0120] Commercially available products of the compound represented by the general formula (V-2) include, for example, tributylsulfonium iodide, (thiodi-4,1-phenylene)bis(diphenylsulfonium)bis(hexafluorophosphate), 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate, (4-(bromomethyl)phenyl)(2,4,6-trimethoxyphenyl)iodonium p-toluenesulfonate, 4-biphenylyl(2,4,6-trimethoxyphenyl)iodonium trifluoromethanesulfonate, bis(4-t-butylphenyl)iodonium hexafluorophosphate, and bis(2,4,6-trimethylphenyl)iodonium trifluoromethanesulfonate, all of which are manufactured by Tokyo Chemical Industry Co., Ltd. iodonium trifluoromethanesulfonate, bis(2,4,6-trimethylpyridine)iodonium hexafluorophosphate, bis(4-fluorophenyl)iodonium trifluoromethanesulfonate, ethynyl(phenyl)iodonium tetrafluoroborate, (4-(trifluoromethyl)phenyl)(2,4,6-trimethoxyphenyl)iodonium p-toluenesulfonate, (4-(trifluoromethyl)phenyl)(2,4,6-trimethylphenyl)iodonium trifluoromethanesulfonate, diphenyliodonium chloride, diphenyliodonium bromide, diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, and the like.

[0121] <Mixing Molar Ratio of Compound Represented by General Formula (V-1) and Compound Represented by General Formula (V-2)> In the reaction of the compound represented by general formula (V-1) and the compound represented by general formula (V-2), the mixing molar ratio of the compound represented by general formula (V-1) and the compound represented by general formula (V-2) is not particularly limited, and may be any ratio as long as the molar ratio of A contained in the target heteropolyoxotungstate or solvate thereof is within the range of 0.01 to 0.01. ｍ＋ and B ｎ＋ The blending molar ratio of the compound represented by general formula (V-1) to the compound represented by general formula (V-2) is preferably 1-3:1-20, more preferably 1-3:1-18, and even more preferably 2:1-15.

[0122] <Reaction of Compound Represented by General Formula (V-1) with Compound Represented by General Formula (V-2)> The reaction conditions for the reaction between the compound represented by general formula (V-1) and the compound represented by general formula (V-2) are not particularly limited and can be carried out under known and commonly used reaction conditions, and the type of solvent, reaction temperature, reaction time, pressure, and the like can be appropriately set. The type of solvent is not particularly limited and examples thereof include water, methanol, ethanol, 1,4-dioxane, acetonitrile, 1-propanol, 2-propanol, ethyl acetate, acetonitrile, acetone, dichloromethane, chloroform, dimethylformamide, and diethyl ether. These solvents may be used alone or in combination. The reaction temperature is not particularly limited and may be, for example, room temperature or heated. The reaction time is not particularly limited and is preferably 1 minute to 24 hours, and more preferably 1 minute to 5 hours. The pressure is not particularly limited and may be normal pressure or increased pressure.

[0123] <Step of Removing the Compound Represented by General Formula (V-3)> The method for removing the compound represented by general formula (V-3) is not particularly limited, and examples thereof include a method of extracting the by-produced compound represented by general formula (V-3) into an aqueous layer and removing it, a method of precipitating it as an inorganic salt and filtering it off, and a method of crystallizing the target compound represented by general formula (I) or a solvate thereof and filtering it off. (A' ｍ’＋ ) ｙ／ｍ’ (Y － ) ｙ (V-3) (A ｍ＋ ) ｘ／ｍ (B ｎ＋ ) ｙ／ｎ (C －（ｘ＋ｙ） ) (I)

[0124] The method for crystallizing and filtering the target compound represented by general formula (I) or a solvate thereof is not particularly limited, and examples thereof include a method in which the target compound is heated to dissolve in a solvent and then slowly cooled to precipitate crystals, and a method in which a poor solvent and a good solvent are combined to cause crystallization. The poor solvent can be appropriately selected depending on the target compound, and for example, diethyl ether, dipropyl ether, ethyl acetate, butyl acetate, hexane, toluene, 2-propanol, ethanol, methanol, etc. may be used. The good solvent can also be appropriately selected depending on the target compound, and for example, water, methanol, ethanol, 1,4-dioxane, dimethylformamide, chloroform, dichloromethane, etc. may be used.

[0125] [2-2. Ion exchange method] In another embodiment, a method for producing a heteropolyoxotungstate compound represented by general formula (I) or a solvate thereof comprises the steps of: subjecting a compound represented by general formula (V-1) to an ion exchange resin; ｍ’＋ H ＋ and a step of reacting the compound represented by general formula (V-4) produced by the above step with a compound represented by general formula (V-2). ｍ＋ ) ｘ／ｍ (B ｎ＋ ) ｙ／ｎ (C －（ｘ＋ｙ） ) (I) (A ｍ＋) ｘ／ｍ (A' ｍ’＋ ) ｙ／ｍ’ (C －（ｘ＋ｙ） ) (V-1) (A ｍ＋ ) ｘ／ｍ (H ＋ ) ｙ (C －（ｘ＋ｙ） ) (V-4) (B ｎ＋ ) ｙ／ｎ (Y － ) ｙ (V-2) [wherein, A ｍ＋ are each independently H ＋ A' represents a metal ion or an ammonium ion; ｍ’＋ each independently represents a metal ion or an ammonium ion; B ｎ＋ each independently represents an iodonium cation; －（ｘ＋ｙ） represents heteropolyoxotungstic acid; Y － represents a monovalent counter anion; m and m' are integers of 1 to 5, n is an integer of 1 or 2, x and x / m are integers, and y / m', y and y / n are natural numbers.

[0126] <Ion Exchange Resin> The ion exchange resin is a compound represented by general formula (V-1) A' ｍ’＋ H ＋ There are no particular limitations on the ion exchange resin, and any known or commonly used resin can be used as long as it can exchange ions with the cation exchange resin. There are no particular limitations on the ion exchange resin, and examples of the ion exchange resin that can be used include a strong acid cation exchange resin and a weak acid cation exchange resin.

[0127] Commercially available ion exchange resins include Amberlite™ IR-200CT, HPR1200 H, HPR1024 H, HPR1006NNC H, and Dowex™ 50W, all manufactured by The Dow Chemical Company; and ORLITE™ DS-1 and DS-4, all manufactured by Organo Corporation.

[0128] A' of the compound represented by general formula (V-1) was extracted using an ion exchange resin. ｍ’＋ H ＋As a method for ion-exchanging the compound represented by general formula (V-1), a known, commonly used method can be used. The method is not particularly limited, and examples thereof include a method in which a column is filled with an ion-exchange resin, and then a solution of water, an organic solvent, or the like containing the compound represented by general formula (V-1) is passed through the column to bring the compound represented by general formula (V-1) into contact with the ion-exchange resin, and then the compound is eluted with an elution solvent, and a method in which an ion-exchange resin and the compound represented by general formula (V-1) are mixed in a beaker, and then the ion-exchange resin is removed by filtration.

[0129] The elution solvent that can be used when passing a solution containing the compound represented by general formula (V-1) through a column packed with an ion exchange resin is not particularly limited, and examples that can be used include Milli-Q water, pure water (ion-exchanged water, demineralized water), methanol, and ethanol.

[0130] In addition, when the compound represented by the general formula (V-1) is contacted using a column packed with an ion exchange resin, the SV (space velocity, h －１ ) is A' of the compound represented by formula (V-1). ｍ’＋ H ＋ There are no particular limitations on the SV, as long as it can be used to exchange ions. The SV is preferably 0.1 to 100, more preferably 0.5 to 50, and even more preferably 1 to 30. The SV is a unit that indicates how many times the resin volume the amount of liquid that passes through the resin per hour.

[0131] <Reaction with Compound Represented by General Formula (V-2)> A' of the compound represented by General Formula (V-1) ｍ’＋ H ＋ In the reaction of the compound represented by general formula (V-4) produced by ion-exchanging with the compound represented by general formula (V-2), the reaction conditions and the blending ratio of the two compounds can be appropriately set within the same ranges as those in the salt exchange method. ｍ＋ ) ｘ／ｍ (H ＋ ) ｙ (C －（ｘ＋ｙ） ) (V-4) (B ｎ＋ ) ｙ／ｎ (Y － )ｙ (V-2)

[0132] <Step of Removing By-Products> The compound represented by general formula (V-4) is reacted with the compound represented by general formula (V-2) to produce the heteropolyoxotungstate compound represented by general formula (I) and the by-product y(H ＋ ・Y － The by-product can be removed by the same method as that used to remove the compound represented by general formula (V-3) in the salt exchange method.

[0133] The present invention will be specifically explained below with reference to examples, but the present invention is not limited to these examples. In the following synthesis examples, if there is a discrepancy between the compound name and the chemical formula, the chemical formula shall prevail.

[0134] [Synthesis Example 1: Tetrakis(bis(4-tert-butylphenyl)iodonium)silicotungstate (M-1)]

[0135] <Salt exchange method> 36.76 g of bis(4-tert-butylphenyl)iodonium chloride was dissolved in 50 g of cyclohexanone to obtain tungstosilicic acid (H ４ [SiW １２ O ４０ ]・26H ２ 41.06 g of methylparaben (C10-10) was added, and the reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was filtered, and the resulting powder was dried under reduced pressure at room temperature for 18 hours. The dried powder was crystallized from dichloromethane and acetonitrile at room temperature to obtain the target compound. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 8.19 (d, 16H), 7.51 (d, 16H), 1.22 (s, 72H). １８３ W-NMR (20.84 MHz, DMSO-D6): δ (ppm) = -92.7 (s, 12 W). ESI-MS: NEGATIVE m / z 718.5 (median) ([SiW １２ O ４０ ] ４－ ) XPS analysis I:W (molar ratio of I to W) = 4:12

[0136] <Ion exchange method> 60.41 g of sodium silicate was dissolved in 240 g of ion-exchanged water to prepare an aqueous solution of sodium silicate. ３ The column was packed with a strongly acidic cation exchange resin, ORLITE™ DS-1 (manufactured by Organo Corporation). An aqueous sodium silicate solution was poured into the column to a depth of about 1 to 15 cm. ３ The solution was passed through the column at a rate of 1 / min, followed by ion-exchanged water at the same rate. The eluate with an acidic pH was collected. 23.00 g of bis(4-tert-butylphenyl)iodonium chloride was added to the collected eluate, and the reaction solution was stirred at room temperature for 30 minutes. The reaction solution was filtered, and the resulting white powder was dried under reduced pressure at room temperature for 18 hours. The dried powder was crystallized at room temperature using dichloromethane and acetonitrile to obtain the target compound.

[0137] [Synthesis Example 2: Tris(bis(4-tert-butylphenyl)iodonium)phosphotungstate (M-2)]

[0138] In the salt exchange method of Synthesis Example 1, the raw material compound was changed from 36.76 g of bis(4-tert-butylphenyl)iodonium chloride to 27.57 g, and phosphotungstic acid (H ３ [P.W. １２ O ４０ ]・30H ２ The target compound was obtained in the same manner as above, except that 41.97 g of methyl methylpropional (C10) was used. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 8.19 (d, 12H), 7.51 (d, 12H), 1.22 (s, 54H). １８３ W-NMR (20.84 MHz, DMSO-D6): δ (ppm) = -86.7 (s, 12 W). ESI-MS: NEGATIVE m / z 959 (median) ([PW １２ O ４０ ] ３－ ) XPS analysis I:W (molar ratio of I to W) = 3:12

[0139] [Synthesis Example 3: Tetrakis(dimesityliodonium)silicitungstate (M-3)]

[0140] The target compound was obtained in the same manner as in the salt exchange method of Synthesis Example 1, except that 34.36 g of dimesityliodonium chloride was used as the raw material compound instead of 36.76 g of bis(4-tert-butylphenyl)iodonium chloride. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 2.29 (s, 24H), 2.47 (s, 48H), 7.19 (s, 16H). １８３ W-NMR (20.84 MHz, DMSO-D6): δ (ppm) = -92.7 (s, 12 W). ESI-MS: NEGATIVE m / z 718.5 (median) ([SiW １２ O ４０ ] ４－ ) XPS analysis I:W (molar ratio of I to W) = 4:12

[0141] [Synthesis Example 4: Tetrakis((4-nitrophenyl)(phenyl)iodonium)silicitungstate (M-4)]

[0142] The target compound was obtained in the same manner as in the salt exchange method of Synthesis Example 1, except that 31.00 g of (4-nitrophenyl)(phenyl)iodonium chloride was used as the starting compound instead of 36.76 g of bis(4-tert-butylphenyl)iodonium chloride. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 7.30-7.51 (m, 28H), 8.20 (d, 8H). １８３ W-NMR (20.84 MHz, DMSO-D6): δ (ppm) = -92.7 (s, 12 W). ESI-MS: NEGATIVE m / z 718.5 (median) ([SiW １２ O ４０ ] ４－ ) XPS analysis I:W (molar ratio of I to W) = 4:12

[0143] [Synthesis Example 5: Tetrakis(mesityl(3-(trifluoromethyl)phenyl)iodonium)silicotungstate (M-5)]

[0144] The target compound was obtained in the same manner as in the salt exchange method of Synthesis Example 1, except that 36.57 g of mesityl(3-(trifluoromethyl)phenyl)iodonium chloride was used as the starting compound instead of 36.76 g of bis(4-tert-butylphenyl)iodonium chloride. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 2.31 (s, 12H), 2.61 (s, 24H), 7.25 (s, 8H), 7.73 (t, 4H), 8.01 (d, 4H), 8.15 (d, 4H), 8.43 (s, 4H). １８３ W-NMR (20.84 MHz, DMSO-D6): δ (ppm) = -92.7 (s, 12 W). ESI-MS: NEGATIVE m / z 718.5 (median) ([SiW １２ O ４０ ] ４－ ) XPS analysis I:W (molar ratio of I to W) = 4:12

[0145] [Synthesis Example 6: Tetrakis((5-fluoro-2-nitrophenyl)(2,4,6-trimethoxyphenyl)iodonium)silicotungstate (M-6)]

[0146] The target compound was obtained in the same manner as in the salt exchange method of Synthesis Example 1, except that 40.27 g of (5-fluoro-2-nitrophenyl)(2,4,6-trimethoxyphenyl)iodonium chloride was used as the starting compound instead of 36.76 g of bis(4-tert-butylphenyl)iodonium chloride. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 3.73 (s, 36H), 5.80 (s, 8H), 7.20 (m, 8H), 8.20 (d, 4H). １８３ W-NMR (20.84 MHz, DMSO-D6): δ (ppm) = -92.7 (s, 12 W). ESI-MS: NEGATIVE m / z 718.5 (median) ([SiW １２ O ４０ ] ４－ ) XPS analysis I:W (molar ratio of I to W) = 4:12

[0147] [Synthesis Example 7: Tetrakis((4-isobutylphenyl)(p-tolyl)iodonium)silicotungstate (M-7)]

[0148] The target compound was obtained in the same manner as in the salt exchange method of Synthesis Example 1, except that 33.15 g of (4-isobutylphenyl)(p-tolyl)iodonium chloride was used as the starting compound instead of 36.76 g of bis(4-tert-butylphenyl)iodonium chloride. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 1.01 (d, 24H), 2.22 (m, 4H), 2.35 (s, 12H), 2.51 (d, 8H), 7.10-7.20 (m, 32H). １８３ W-NMR (20.84 MHz, DMSO-D6): δ (ppm) = -92.7 (s, 12 W). ESI-MS: NEGATIVE m / z 718.5 (median) ([SiW １２ O ４０ ] ４－ ) XPS analysis I:W (molar ratio of I to W) = 4:12

[0149] [Synthesis Example 8: Tetrakis((4-((2-hydroxytetradecyl)oxy)phenyl)(phenyl)iodonium)silicotungstate (M-8)]

[0150] The target compound was obtained in the same manner as in the salt exchange method of Synthesis Example 1, except that 46.72 g of (4-((2-hydroxytetradecyl)oxy)phenyl)(phenyl)iodonium chloride was used as the starting compound instead of 36.76 g of bis(4-tert-butylphenyl)iodonium chloride. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 0.85 (t, 12H), 1.23-1.47 (m, 88H), 3.69-3.76 (m, 4H), 3.83 -3.91 (m, 8H), 4.84 (d, 4H), 7.07 (d, 8H), 7.52 (t, 8H), 7.62-7.66 (m, 4H), 8.16-8.22 (m, 16H). １８３W-NMR (20.84 MHz, DMSO-D6): δ (ppm) = -92.7 (s, 12 W). ESI-MS: NEGATIVE m / z 718.5 (median) ([SiW １２ O ４０ ] ４－ ) XPS analysis I:W (molar ratio of I to W) = 4:12

[0151] [Synthesis Example 9: Tetrakis(diphenyliodonium)silicitungstate (M-9)]

[0152] The target compound was obtained in the same manner as in the salt exchange method of Synthesis Example 1, except that 27.13 g of diphenyliodonium chloride was used as the raw material compound instead of 36.76 g of bis(4-tert-butylphenyl)iodonium chloride. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 8.02 (d, 16H), 7.59 (t, 8H), 7.41 (t, 16H). １８３ W-NMR (20.84 MHz, DMSO-D6): δ (ppm) = -92.7 (s, 12 W). ESI-MS: NEGATIVE m / z 718.5 (median) ([SiW １２ O ４０ ] ４－ ) XPS analysis I:W (molar ratio of I to W) = 4:12

[0153] [Synthesis Example 10: Tris(diphenyliodonium)phosphotungstate (M-10)]

[0154] In the salt exchange method of Synthesis Example 1, 20.36 g of diphenyliodonium chloride was used instead of 36.76 g of bis(4-tert-butylphenyl)iodonium chloride as a raw material compound, and phosphotungstic acid (H ３ [P.W. １２ O ４０ ]・30H ２ The target compound was obtained in the same manner as above, except that 41.97 g of methyl methylpropional (C10) was used. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 8.02 (d, 12H), 7.59 (t, 8H), 7.41 (t, 12H).１８３ W-NMR (20.84 MHz, DMSO-D6): δ (ppm) = -86.7 (s, 12 W). ESI-MS: NEGATIVE m / z 959 (median) ([PW １２ O ４０ ] ３－ ) XPS analysis I:W (molar ratio of I to W) = 3:12

[0155] Test Example: Evaluation of Solvent Solubility The heteropolyoxotungstate compounds M-1 to M-10 obtained in Synthesis Examples 1 to 10 above were tested for solubility in each solvent (methanol, acetonitrile, and dimethylformamide) by the following method. 1 g of powder of each of M-1 to M-10 was weighed into a beaker, and the solvent was added. The weight concentration (wt%) of M-1 to M-10 was calculated from the amount of solvent added when dissolution was confirmed visually, and the concentration was evaluated according to the following criteria. The results are shown in Table 1. ◎: Dissolved at 10 wt% or more ○: Dissolved at 5 wt% or more but less than 10 wt% △: Dissolved at 1 wt% or more but less than 5 wt% ×: Not dissolved at less than 1 wt%

[0156]

[0157] The results in Table 1 show that when the iodonium cation has a lipophilic substituent, such as a t-butyl group, on the benzene ring bonded to the iodine atom, as in M-1 and M-2, it tends to have good solubility in methanol and acetonitrile, and particularly good solubility in dimethylformamide. In contrast, when the iodonium cation has the two benzene rings bonded to the iodine atom or the substituents on the benzene rings are the same, i.e., symmetrical, and is unsubstituted, as in M-9 and M-10, it has slight solubility in dimethylformamide, indicating its potential use as a functional molecular block. On the other hand, M-9 and M-10 showed poor solubility in methanol and acetonitrile compared to M-1 and M-2.

[0158] When the iodonium cation had two mesityl groups bonded to the iodine atom, as in M-3, it dissolved in methanol, had good solubility in acetonitrile, and had very good solubility in dimethylformamide. When the iodonium cation had a nitro group, an electron-withdrawing group, on one of the benzene rings bonded to the iodine atom, as in M-4, it had poor solubility in methanol, possibly due to the orientation caused by the imbalance of electrons. On the other hand, it dissolved in acetonitrile and had good solubility in dimethylformamide. When the iodonium cation had a benzene ring substituted with a mesityl group on one side of the iodine atom and a trifluoromethyl group, an electron-withdrawing group, on the other side, as in M-5, it dissolved in methanol and acetonitrile, and had very good solubility in dimethylformamide, possibly due to the reduced electron imbalance compared to M-4. When the iodonium cation, like M-6, has a benzene ring with a methoxy group, which is an electron-donating group, on one side of the iodine atom and a benzene ring with a nitro group and a fluorine atom, which are electron-withdrawing groups, on the other side, it dissolves in methanol and acetonitrile, but has good solubility in dimethylformamide.

[0159] As in M-7 and M-8, when an isobutyl group is substituted on one benzene ring of the iodine atom of the iodonium cation, or when a long-chain alkyl group is substituted, the solubility in each solvent does not change significantly; they are soluble in methanol and acetonitrile, and have very good solubility in dimethylformamide.

[0160] The heteropolyoxotungstate compound having good solvent solubility can be dissolved in a solvent to form a uniform film or the like, and can be suitably used as a catalyst having oxidation-reduction ability, a magnetic material, or an actinic ray- or radiation-sensitive compound.

Claims

1. A heteropolyoxotungstate compound represented by general formula (I) or a solvate thereof: (A ｍ＋ ) ｘ／ｍ (B ｎ＋ ) ｙ／ｎ (C －（ｘ＋ｙ） ) (I) [In the formula, A ｍ＋ are each independently H ＋ , a metal ion, or an ammonium ion; B ｎ＋ each independently represents an iodonium cation; C －（ｘ＋ｙ） represents heteropolyoxotungstic acid; m is an integer of 1 to 5, n is an integer of 1 or 2, x and x / m are integers, and y and y / n are natural numbers.

2. The heteropolyoxotungstate compound or solvate thereof according to claim 1, wherein the heteropolyoxotungstic acid is a heteropolyoxotungstic acid represented by general formula (II-1) or (II-2), or a heteropolyoxotungstic acid represented by a defective species thereof: [XW] １２ Oh ４０ ] －ｚ１ (II-1) [X ２ W １８ O ６２ ] －ｚ２ (II-2) [In the formula, X is independently B, Al, or Si. ＩＶ , Ge ＩＶ , P Ｖ , As Ｖ , V Ｖ , Cr ＩＩＩ , Fe ＩＩＩ , Co ＩＩＩ , Co ＩＩ , Cu ＩＩ , Cu Ｉ , Zn, Se ＶＩ , or S ＶＩ represents; z1 and z2 are natural numbers.

3. The heteropolyoxotungstic acid represented by (II-1) is １２ O ４０ ] ３－ , [SiW １２ O ４０ ] ４－ , [B.W. １２ O ４０ ] ５－ or [SW １２ O ４０ ] ２－ The heteropolyoxotungstate compound or a solvate thereof according to claim 2,

4. The heteropolyoxotungstic acid represented by (II-2) is ２ W １８ O ６２ ] ６－ , [Si ２ W １８ O ６２ ] ８－ or [S ２ W １８ O ６２ ] ４－ The heteropolyoxotungstate compound or a solvate thereof according to claim 2,

5. A heteropolyoxotungstate mixture comprising two or more different heteropolyoxotungstate compounds or solvates thereof according to claim 1.

6. 10. A heteropolyoxotungstate mixture comprising two or more different heteropolyoxotungstate compounds or solvates thereof according to claim 1, wherein the heteropolyoxotungstate is a Keggin type or a Dawson type, or a silicotungstic acid which is a defect species thereof, and wherein the molar ratio of I to W in XRF analysis or XPS analysis is I:W=0.5 to 10:9 to 18.

7. 10. A heteropolyoxotungstate mixture comprising two or more different heteropolyoxotungstate compounds or solvates thereof according to claim 1, wherein the heteropolyoxotungstate is a Keggin type or a Dawson type, or a phosphotungstic acid which is a defect species thereof, and wherein the molar ratio of I to W in XRF analysis or XPS analysis is I:W=0.5 to 6:9 to 18.

8. 2. The heteropolyoxotungstate compound or solvate thereof according to claim 1, wherein the iodonium cation is an iodonium cation represented by general formula (III): 【Chemistry 1】 [In the formula, R ３Ａ and R ３Ｂ each independently represents a C １－１８ represents a hydrocarbyl group, an optionally substituted 3- to 18-membered non-aromatic heterocyclic group, or an optionally substituted 5- to 18-membered aromatic heterocyclic group, R ３Ａ and R ３Ｂ are directly connected to each other by a single bond, or are connected to each other by a divalent linking group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring together with the iodine atom in formula (III).

9. 2. The heteropolyoxotungstate compound or solvate thereof according to claim 1, wherein the iodonium cation is an iodonium cation represented by general formula (IV-1) or (IV-2): 【Chemistry 2】 [In the formula, Ar ４Ａ and Ar ４Ｂ each independently represents a C ６－１８ represents an aryl group or a 5- to 18-membered heterocyclic group; C which may have the above-mentioned substituent ６－１８ The aryl group or the 5- to 18-membered heterocyclic group may be a C group in which at least a portion of the hydrogen atoms are optionally substituted with a halogen atom, a hydroxy group, a thiol group, a nitro group, a cyano group, a carboxy group, an amino group, or a sulfo group, or a C group in which at least a portion of the hydrogen atoms are optionally substituted with a halogen atom, a hydroxy group, a thiol group, a nitro group, a cyano group, a carboxy group, an amino group, or a sulfo group. １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbyloxycarbonyloxy group, C １－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ Hydrocarbyloxycarbonylamino group, C １－１８ Hydrocarbylthio group, C １－１８ a hydrocarbylsulfinyl group, or C １－１８ optionally substituted with hydrocarbylsulfonyl groups, The divalent carbon atom at any position of the substituent except for the terminal may be selected from the group consisting of -O-, -C(=O)-, -COO-, -OCO-, -CONH-, -NHCO-, -S-, and SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time), Ar ４Ａ and Ar ４Ｂ are directly connected to each other by a single bond, or are connected to each other by a divalent linking group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring together with the iodine atom in formula (IV-1). 【Transformation 3】 [In the formula, R ４Ｃ and R ４Ｄ are each independently a halogen atom, a hydroxy group, a thiol group, a nitro group, a cyano group, a carboxy group, an amino group, a sulfo group, or a C in which at least a portion of the hydrogen atoms may be substituted with a halogen atom, a hydroxy group, a thiol group, a nitro group, a cyano group, a carboxy group, an amino group, or a sulfo group. １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbyloxycarbonyloxy group, C １－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ Hydrocarbyloxycarbonylamino group, C １－１８ Hydrocarbylthio group, C １－１８ a hydrocarbylsulfinyl group, or C １－１８ is a hydrocarbyl sulfonyl group, The divalent carbon atom at any position except for these terminals may be —O—, —C(═O)—, —COO—, —OCO—, —CONH—, —NHCO—, —S—, or SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time); v and w are each an integer of 0 to 5, and when the values ​​of v and w are an integer of 2 or more, R ４Ｃ and R ４Ｄ may be the same or different from each other.

10. In the iodonium cation represented by the general formula (IV-1), Ar ４Ｂ is an iodonium cation represented by general formula (IV-3): The heteropolyoxotungstate compound or a solvate thereof according to claim 9. 【Chemistry 4】 【Transformation 5】 [In the formula, R ４Ｅ represents a halogen atom, a nitro group, C １－４ a haloalkyl group or a branched C ３－１０ Alkyl group, C １－１２ Hydrocarbyloxy group, C １－１２ Hydrocarbyl carbonyl group, C １－１２ Hydrocarbylcarbonyloxy group, C １－１２ Hydrocarbyloxycarbonyl group or C １－１２ represents a hydrocarbyloxycarbonyloxy group; R ４Ｅ is a halogen atom, a nitro group, C １－４ When Ar is a haloalkyl group, ４Ａ and Ar ４Ｂ are different from each other.]

11. In the iodonium cation represented by the general formula (IV-1), Ar ４Ｂ is an iodonium cation represented by general formula (IV-4): The heteropolyoxotungstate compound or a solvate thereof according to claim 9. 【Transformation 6】 【Transformation 7】 [In the formula, R ４Ｆ each independently represents a C １－１２ Hydrocarbyl group, C １－１２ Hydrocarbyloxy group, C １－１２ Hydrocarbyl carbonyl group, C １－１２ Hydrocarbylcarbonyloxy group, C １－１２ Hydrocarbyloxycarbonyl group or C １－１２ represents a hydrocarbyloxycarbonyloxy group.]

12. A method for producing a heteropolyoxotungstate compound represented by general formula (I) or a solvate thereof, comprising: A production method comprising a step of reacting a compound represented by general formula (V-1) with a compound represented by general formula (V-2) to carry out salt exchange. (A ｍ＋ ) ｘ／ｍ (B ｎ＋ ) ｙ／ｎ (C －（ｘ＋ｙ） ) (I) (A) ｍ＋ ) ｘ／ｍ (A' ｍ’＋ ) ｙ／ｍ’ (C －（ｘ＋ｙ） ) (V-1) (B ｎ＋ ) ｙ／ｎ (Y － ) ｙ (V-2) [In the formula, A ｍ＋ are each independently H ＋ , a metal ion, or an ammonium ion; A' ｍ’＋ each independently represents a metal ion or an ammonium ion; B ｎ＋ each independently represents an iodonium cation; C －（ｘ＋ｙ） represents heteropolyoxotungstic acid; Y － represents a monovalent counter anion; m and m' are integers from 1 to 5, n is an integer of 1 or 2, x and x / m are integers, and y / m', y, and y / n are natural numbers.

13. A method for producing a heteropolyoxotungstate compound represented by general formula (I) or a solvate thereof, comprising: a step of reacting a compound represented by general formula (V-1) with a compound represented by general formula (V-2) to perform salt exchange; a step of removing the compound represented by general formula (V-3) from the produced compounds represented by general formulas (I) and (V-3); A manufacturing method comprising the steps of: (A ｍ＋ ) ｘ／ｍ (B ｎ＋ ) ｙ／ｎ (C －（ｘ＋ｙ） ) (I) (A) ｍ＋ ) ｘ／ｍ (A' ｍ’＋ ) ｙ／ｍ’ (C －（ｘ＋ｙ） ) (V-1) (B ｎ＋ ) ｙ／ｎ (Y － ) ｙ (V-2) (A' ｍ’＋ ( ｙ／ｍ’ (Y) － ( ｙ (V-3) [In the formula, A ｍ＋ are each independently H ＋ , a metal ion, or an ammonium ion; A' ｍ’＋ each independently represents a metal ion or an ammonium ion; B ｎ＋ each independently represents an iodonium cation; C －（ｘ＋ｙ） represents heteropolyoxotungstic acid; Y － represents a monovalent counter anion; m and m' are integers from 1 to 5, n is an integer of 1 or 2, x and x / m are integers, and y / m', y, and y / n are natural numbers.

14. A method for producing a heteropolyoxotungstate compound represented by general formula (I) or a solvate thereof, comprising: A' of the compound represented by general formula (V-1) is obtained by ion exchange resin. ｍ’＋ H ＋ and ion-exchanging the a step of reacting the compound represented by general formula (V-4) produced by the above step with a compound represented by general formula (V-2); A manufacturing method comprising the steps of: (A ｍ＋ ) ｘ／ｍ (B ｎ＋ ) ｙ／ｎ (C －（ｘ＋ｙ） ) (I) (A) ｍ＋ ) ｘ／ｍ (A' ｍ’＋ ) ｙ／ｍ’ (C －（ｘ＋ｙ） ) (V-1) (A ｍ＋ ) ｘ／ｍ (H ＋ ) ｙ (C －（ｘ＋ｙ） ) (V-4) (B ｎ＋ ) ｙ／ｎ (Y － ) ｙ (V-2) [In the formula, A ｍ＋ are each independently H ＋ , a metal ion, or an ammonium ion; A' ｍ’＋ each independently represents a metal ion or an ammonium ion; B ｎ＋ each independently represents an iodonium cation; C －（ｘ＋ｙ） represents heteropolyoxotungstic acid; Y － represents a monovalent counter anion; m and m' are integers from 1 to 5, n is an integer of 1 or 2, x and x / m are integers, and y / m', y, and y / n are natural numbers.

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