Method for producing heteropolyoxometalate having modified lacunary site, or mixture thereof

Abstract

The present invention provides a novel method for producing a heteropolyoxometalate having a modified lacunary site, or a mixture thereof, the method comprising: a step for using a Keggin-type or Dawson-type heteropolyoxometalate as a mono-lacunary Keggin-type or Dawson-type heteropolyoxometalate; and a step for obtaining a heteropolyoxometalate having a modifiect lacunary site by reacting the mono-lacunary Keggin-type or Dawson-type heteropolyoxometalate with a P, Si, Ge, or Sn compound having one or more hydro groups or an organic group and two or more leaving groups.

Description

Method for producing heteropolyacid salts or mixtures thereof with modified defect sites

[0001] The present invention relates to a method for producing a heteropolyacid salt or a mixture thereof in which defect sites have been modified.

[0002] Polyacids are those having the general formula [M ｘ O ｙ ] ｎ－ (wherein x, y, and n are all natural numbers). The metal atom M constituting the polyacid is called a polyatom, and examples thereof include Mo (hexavalent or pentavalent), W (hexavalent or pentavalent), V (pentavalent), Nb (pentavalent), and Ta (pentavalent). The polyacid is an isopolyacid composed of the polyatom M and an oxygen acid, or a polyacid containing a different type of heteroatom X (for example, P as the heteroatom X) in addition to the polyatom M and oxygen. ５＋ , Si ４＋ , Ge ４＋ , B ３＋ Heteropolyacids containing [X ｗ M ｘ O ｙ ] ｎ－ (wherein w, x, y, and n are all natural numbers)

[0003] It is also known that polyacids have multiple defect species in which a portion of the basic skeleton is missing. The terminal oxygen atoms at the defect sites, where a portion of the basic skeleton of a polyacid is missing, have a certain degree of negative charge density on the oxygen atoms, making them highly reactive and nucleophilic. Therefore, by reacting the terminal oxygen atoms with electrophilic atoms or molecules, various functional polyacid complexes and organic / inorganic hybrid structures can be formed.

[0004] Patent Document 1 discloses a method for producing a metal-substituted polyoxometalate, which comprises a step of reacting a polyoxometalate having one or more defect sites with a metal complex having a central metal and an organic ligand in a reaction solution containing the polyoxometalate and the metal complex to produce the metal-substituted polyoxometalate.

[0005] U.S. Pat. No. 1,142,0871

[0006] An object of the present invention is to provide a novel method for producing a heteropolyacid salt or a mixture thereof in which defect sites have been modified.

[0007] As a result of intensive research into solving the above-mentioned problems, the present inventors have found that a novel method for producing a heteropolyacid salt having modified defect sites or a mixture thereof can be provided by using a production method comprising the steps of: converting a Keggin or Dawson type heteropolyacid salt into a single-defect Keggin or Dawson type heteropolyacid salt; and reacting the single-defect Keggin or Dawson type heteropolyacid salt with a P, Si, Ge, or Sn compound having one or more hydro groups or organic groups and two or more leaving groups to obtain a heteropolyacid salt having modified defect sites, thereby completing the present invention.

[0008] That is, the present invention relates to the following inventions: <1> A method for producing a heteropolyacid salt having modified defect sites, or a mixture thereof, comprising: (1) a step of converting a Keggin or Dawson type heteropolyacid salt into a one-deficient Keggin or Dawson type heteropolyacid salt; and (2) a step of reacting the one-deficient Keggin or Dawson type heteropolyacid salt with a P, Si, Ge, or Sn compound having one or more hydro groups or organic groups and two or more leaving groups to obtain a heteropolyacid salt having modified defect sites represented by general formula (I) or a mixture thereof. (A ｐ＋ ) ｑ [C （ｐ×ｑ）－ ] (I) [In formula (I), A ｐ＋ are each independently H ＋ , a metal ion, or an ammonium ion; （ｐ×ｑ）－represents a heteropolyacid anion in which the defect site is modified in a one-defect Keggin or Dawson type heteropolyacid anion; p is an integer from 1 to 5, and q is a real number.] <2> A method for producing a heteropolyacid salt or a mixture thereof in which the defect site is modified according to <1>, wherein the step (1) comprises: (1a) adjusting the pH of a solution containing the Keggin or Dawson type heteropolyacid salt to 5.0 or less. <3> A method for producing a heteropolyacid salt or a mixture thereof in which the defect site is modified according to <1>, wherein the step (1) comprises: (1a) adjusting the pH of a solution containing the Keggin or Dawson type heteropolyacid salt to 5.0 or less; and (1b) adjusting the pH of the solution to 4 to 8 using a weak base or a base. <4> A method for producing a heteropolyacid salt or a mixture thereof having modified defect sites according to <1>, wherein the step (2) comprises: (2a) reacting the singly defective Keggin or Dawson type heteropolyacid salt with a P, Si, Ge, or Sn compound having one or more hydro groups or organic groups and two or more leaving groups in a solution of pH 5.0 or less. <5> A method for producing a heteropolyacid salt or a mixture thereof having modified defect sites according to <1>, wherein the polyatom of the Keggin or Dawson type heteropolyacid salt is Mo, W, V, Nb, or Ta, and the heteroatom is P, Si, B, S, or Ge. <6> A method for producing a heteropolyacid salt or a mixture thereof having modified defect sites according to <1>, wherein the singly defective Keggin or Dawson type heteropolyacid salt is represented by general formula (III-1) or (III-2): [XM １１ O ３９ ] ｃ２１－ (III-1) [X ２ M １７ O ６１ ] ｃ２２－(III-2) [wherein X represents a heteroatom of P, Si, B, S, or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; and c21 and c22 are natural numbers.] <7> A method for producing a heteropolyacid salt or a mixture thereof having modified defect sites according to <1>, wherein the organic group has one or more halogen atoms, haloalkyl groups, hydroxy groups, thiol groups, nitro groups, cyano groups, carboxy groups, amino groups, sulfo groups, epoxy groups, glycidyl groups, or amide groups. <8> A method for producing a heteropolyacid salt or a mixture thereof having modified defect sites according to <1>, wherein the organic group has one or more ethylenically unsaturated double bonds. <9> A method for producing a heteropolyacid salt or a mixture thereof having modified defect sites according to <1>, wherein the organic group has one or more hydroxy groups or carboxy groups having a protecting group.

[0009] <10> The above C （ｐ×ｑ）－ is represented by any one of general formulas (VI-1) to (VI-8), or a heteropolyacid salt or a mixture thereof, according to <1>. １１ O ３９ (R １Ａ X') ２ O] ｃ３１－ (VI-1) [XM １１ O ３９ (R １Ｂ１ R １Ｂ２ Si) ２ ] ｃ３１－ (VI-2) [XM １１ O ３９ (R １Ｃ P=O) ２ ] ｃ３１－ (VI-3) [XM １１ O ３９ (R １Ｄ X'') ｃ３１－ (VI-4) [X ２ M １７ O ６１ (R １Ａ X') ２ O] ｃ３２－ (VI-5) [X ２ M １７ O ６１ (R １Ｂ１ R １Ｂ２Si) ２ ] ｃ３２－ (VI-6) [X ２ M １７ O ６１ (R １Ｃ P=O) ２ ] ｃ３２－ (VI-7) [X ２ M １７ O ６１ (R １Ｄ X'') ｃ３２－ (VI-8) [Wherein, X represents a heteroatom of P, Si, B, S, or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; X' represents a heteroatom of Si or Ge; X'' represents a heteroatom of Si, Ge, or Sn; R １Ａ ~R １Ｄ are each independently a hydro group or an optionally substituted C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, １Ａ ~R １Ｄ The divalent carbon atom at any position excluding the terminal may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), １Ａ ~R １Ｄ a hydrogen atom contained in may be substituted with, for example, (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, or (s) a hydroxy group or carboxy group having a protecting group; and c31 and c32 are natural numbers.]

[0010] <11> A method for producing a heteropolyacid salt or a mixture thereof having modified defect sites according to <1>, further comprising (3) a step of salt-exchanging the heteropolyacid salt or mixture thereof having modified defect sites represented by the general formula (I). <12> A method for producing a heteropolyacid salt or a mixture thereof having modified defect sites according to <11>, wherein the step (3) comprises: (3a) a step of salt-exchanging the heteropolyacid salt or mixture thereof having modified defect sites represented by the general formula (I) with an alkali metal salt, an alkaline earth metal salt, an aluminum salt, or an onium salt. <13> A method for producing a heteropolyacid salt or a mixture thereof having modified defect sites according to <12>, wherein the onium salt is an organic sulfonium salt, an organic iodonium salt, an organic ammonium salt, or an organic phosphonium salt. <14> A method for producing a heteropolyacid salt or a mixture thereof having modified defect sites according to <11>, wherein the step (3) comprises: (3b) a step of obtaining a heteropolyacid salt or a mixture thereof having modified defect sites represented by general formula (VII). (A ｍ＋ ) ａ (B ｎ＋ ) ｂ (C （ａｍ＋ｂｎ）－ ) (VII) [Wherein, when b is 0, A ｍ＋ are each independently H ＋ , a metal ion, or an ammonium ion, and at least one of them is ｐ＋ Alkali metal ions, alkaline earth metal ions, or Al ３＋ and if b is a real number greater than 0, then A ｍ＋ are each independently H ＋ , a metal ion, or an ammonium ion; B ｎ＋ each independently represents an organic sulfonium cation, an organic sulfonium dication, an organic iodonium cation, an organic ammonium cation, an organic ammonium dication, an organic phosphonium cation, or an organic phosphonium dication; （ａｍ＋ｂｎ）－represents a heteropolyanion in which the defective site of a Keggin or Dawson heteropolyanion has been modified; m is an integer of 1 to 5, n is an integer of 1 or 2, and a is a real number.

[0011] <15> A method for producing a heteropolyacid salt or a mixture thereof in which defect sites have been modified and which is represented by general formula (VII), the method comprising: a step of substituting a cation moiety of a heteropolyacid salt or a mixture thereof in which defect sites have been modified and which is represented by general formula (I) with a metal ion, an ammonium ion, or an organic ammonium cation by a salt exchange reaction; and a step of further performing salt exchange with an onium salt. (A ｍ＋ ) ａ (B ｎ＋ ) ｂ (C （ａｍ＋ｂｎ）－ ) (VII) [wherein, A ｍ＋ are each independently H ＋ , a metal ion, or an ammonium ion; B ｎ＋ each independently represents an organic sulfonium cation, an organic sulfonium dication, an organic iodonium cation, an organic ammonium cation, an organic ammonium dication, an organic phosphonium cation, or an organic phosphonium dication; （ａｍ＋ｂｎ）－ represents a heteropolyanion in which the defective site of a Keggin or Dawson heteropolyanion has been modified; m is an integer of 1 to 5, n is an integer of 1 or 2, a is a real number, and b is a real number greater than 0.

[0012] <16> A method for producing a heteropolyacid salt or a mixture thereof having modified defect sites, the method comprising the step of washing a heteropolyacid salt or a mixture thereof having modified defect sites represented by general formula (VII) with an acidic aqueous solution having a pH of 6 or less. (A ｍ＋ ) ａ (B ｎ＋ ) ｂ (C （ａｍ＋ｂｎ）－ ) (VII) [wherein, A ｍ＋ are each independently H ＋ , a metal ion, or an ammonium ion; B ｎ＋each independently represents an organic sulfonium cation, an organic sulfonium dication, an organic iodonium cation, an organic ammonium cation, an organic ammonium dication, an organic phosphonium cation, or an organic phosphonium dication; （ａｍ＋ｂｎ）－ represents a heteropolyacid anion in which the defect site is modified in a heteropolyacid anion of one defect Keggin type or Dawson type; m is an integer of 1 to 5, n is an integer of 1 or 2, a is a real number, and b is a real number greater than 0.] <17> The step of washing with an acidic aqueous solution of pH 6 or less is carried out by removing metals or metal ions selected from Li, Na, Mg, Al, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Sr, Zr, Mo, Ag, Cd, Sn, Sb, Ba, W, Pb, and Au from the heteropolyacid salt of general formula (VII) in which the defect site is modified or the mixture thereof, and removing the polyatoms, heteroatoms, and A of the heteropolyacid salt of general formula (VII) in which the defect site is modified or the mixture thereof. ｍ＋ <16>. The method for producing a heteropolyacid salt or a mixture thereof having modified defect sites according to <16>, wherein the content of each of the metals or metal ions excluding the metals or metal ions contained in <16> is less than 100 ppb.

[0013] According to the present invention, a novel method for producing a heteropolyacid salt or a mixture thereof having modified defect sites can be provided. The production method according to the present invention makes it possible to obtain a heteropolyacid salt or a mixture thereof having modified defect sites with few impurities.

[0014] Preferred embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments.

[0015] In this specification, the term "(meth)acryloyl group" is used to mean both an acryloyl group and a methacryloyl group.

[0016] As used herein, the term "halogen atom" refers to a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0017] In this specification, for example, "C １－６" and other terms refer to the number of carbon atoms in the core group.

[0018] 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-, -NH(C=O)O-, -S-, -SO-, or -SO ２ - may be substituted (however, adjacent divalent carbon atoms may not be substituted at the same time). １－１８ The "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.

[0019] 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)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２However, adjacent divalent carbon atoms may not be replaced at the same time. １－１８ The "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)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -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.

[0020] 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.

[0021] As used herein, "C ２－１８The 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.

[0022] 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.

[0023] 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 A divalent carbon atom at any position excluding the terminals contained in the "alicyclic group" may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -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.

[0024] 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.

[0025] As used herein, "C ２－１８The term "aryl group" means an aromatic hydrocarbon cyclic group having 6 to 18 carbon atoms or an aromatic heterocyclic group having 2 to 10 carbon atoms. In the case of an aromatic heterocyclic group, a ring is formed by a carbon atom having 2 to 10 carbon atoms and one or more heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and each may be a monocyclic ring, a polycyclic ring, or a fused ring. ２－１８ The "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.

[0026] As used herein, "C ７－１８ The term "aralkyl group" refers to "C １－１２ The substitutable portion of the "C alkyl group" is ２－１２ "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.

[0027] As used herein, "C １－１８ The 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 terminal contained in the "hydrocarbyl group" may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - (however, adjacent divalent carbon atoms cannot be replaced at the same time). １－１８ The term "C" used in the definition of "hydrocarbyloxy group" and the like is used in the definition of "C" １－１８ The same applies to "hydrocarbyl group" and the like. １－１８ The "hydrocarbyl group" is not particularly limited, and examples thereof include "C １－１８alkyl group," "C ２－１８ alkenyl group," "C ２－１８ alkynyl group," "C ３－１８ “Alicyclic group”, “C ２－１８ aryl group," "C ７－１８ aralkyl groups, etc.

[0028] 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 １－１８ alkoxy 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."１－１８ The "hydrocarbyloxy group" includes "C １－１８ It is preferred that a divalent carbon atom at any position except the terminal contained in the "hydrocarbyl group" is replaced with -O-, -C(=O)-, and / or -C(=O)O-. １－１８ A "hydrocarbyloxycarbonylalkyloxy group" is more preferred, and from the viewpoint of solubility, it is even more preferred that the carbon bonded to the oxygen atom of the hydrocarbyloxy is a tertiary carbon. Specific examples of the hydrocarbyloxy include optionally substituted ethylcyclopentyloxy, methyladamantyloxy, ethyladamantyloxy, t-butyloxy, etc.

[0029] 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.

[0030] 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." １－１８The "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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] As used herein, the term "acid-dissociable group" refers to a group that substitutes a hydrogen atom of a hydroxy group (including a phenolic hydroxy group) or a carboxy group, and that dissociates under the action of an acid. Examples of the acid-dissociable group include acid-dissociable groups G for hydroxy groups or carboxy groups, which are represented by the following general formula (G-1) or (G-2):

[0047] The acid-dissociable group G is not particularly limited as long as it dissociates under the action of an acid, and any known and commonly used group can be used. Examples of the acid-dissociable group G include "tertiary carbon-type acid-dissociable groups G" represented by the following general formula (g-1): Ａ " etc.

[0048] <Tertiary carbon type acid dissociable group G Ａ The acid-dissociable group G is a "tertiary carbon-type acid-dissociable group G" represented by the following general formula (g-1): Ａ ", a carbon atom directly bonded to a polar group, and R Ａ ｇ１ ~R Ａ ｇ３ An acid-labile group in which the carbon atom to which the group is bonded is a tertiary carbon atom can be used.

[0049] "R Ａ ｇ１ " is an optionally substituted C １－１２ In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0050] R Ａ ｇ１ As the C １－１２ Alkyl group, C ３－１２ Alicyclic group, C ６－１２ an aryl group, or C７－１２ An aralkyl group in which any divalent carbon atom excluding the terminal carbon atom is —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－１２ an alkyl group or C ３－１２ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0051] Also, "R Ａ ｇ２ " and "R Ａ ｇ３ " are each independently a C １－１２ A hydrocarbyl group in which a divalent carbon atom at any position except the terminal is —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), or R Ａ ｇ２ and R Ａ ｇ３ are combined to form C which may have a substituent. ３－１８ An alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group is formed, and a divalent carbon atom at any position except the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0052] R Ａ ｇ２ and R Ａ ｇ３ As for R Ａｇ２ and R Ａ ｇ３ are combined to form C which may have a substituent. ３－１８ An alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group is formed, and a divalent carbon atom at any position except the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and ３－１８ The alicyclic group or the 3- to 18-membered non-aromatic heterocyclic group contains a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a cyclooctane skeleton, a cyclononane skeleton, a cyclodecane skeleton, a cyclododecane skeleton, a cyclopentene skeleton, a cyclohexene skeleton, a cycloheptene skeleton, a cyclooctene skeleton, a cyclodecene skeleton, a norbornane skeleton, an adamantane skeleton, a tricyclodecane skeleton, a tetracyclododecane skeleton, a norbornene skeleton, or a tricyclodecene skeleton, and a divalent carbon atom at any position excluding the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is more preferable that the divalent carbon atoms may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0053] A tertiary carbon-type acid-dissociable group G represented by general formula (g-1): Ａ Examples of the aryl group include a t-butyl group, a t-amyl group, a 1,1-dimethylpropyl group, a 1-methyl-1-cyclopentyl group, a 1-ethyl-1-cyclopentyl group, a 1-methyl-1-cyclohexyl group, a 1-ethyl-1-cyclohexyl group, a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group, a 1-(1-methoxy-2-methylpropan-2-yl)cyclopentyl group, and a 1-(1-ethoxy-2-methylpropan-2-yl)cyclopentyl group.

[0054] <<Tertiary carbon type acid dissociable group G Ａ１ and G Ａ２>> Also, the "tertiary carbon-type acid-dissociable group G" represented by general formula (g-1) Ａ " In R Ａ ｇ２ and R Ａ ｇ３ are combined to form C which may have a substituent. ３－１８ In the case where an alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group is formed, for example, a tertiary carbon-type acid-dissociable group G represented by the following general formula (g-1-1) is included: Ａ１ and a tertiary carbon-type oxygen-dissociating group G represented by (g-1-2): Ａ２ etc.

[0055] <<Tertiary carbon-type acid-dissociable group G represented by general formula (g-1-1) Ａ１ >> A tertiary carbon-type acid-dissociable group G represented by the above general formula (g-1-1): Ａ１ In this case, R Ａ ｇ１１ is a C which may have a substituent １－１２ Alkyl group, C ３－１２ Alicyclic group, C ６－１２ an aryl group, or C ７－１２ An aralkyl group in which any divalent carbon atom excluding the terminal carbon atom is —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0056] Also Cy Ａ ｇ１ represents a C which may have a substituent together with the tertiary carbon atom. ３－１８ An alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group is formed, and any divalent carbon atom is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0057] Cy Ａ ｇ１The tertiary carbon atom may be, together with the tertiary carbon atom, a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a cyclooctane skeleton, a cyclononane skeleton, a cyclodecane skeleton, a cyclododecane skeleton, a cyclopentene skeleton, a cyclohexene skeleton, a cycloheptene skeleton, a cyclooctene skeleton, a cyclodecene skeleton, a norbornane skeleton, an adamantane skeleton, a tricyclodecane skeleton, a tetracyclododecane skeleton, a norbornene skeleton, or a tricyclodecene skeleton, and the divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferably one which may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0058] A tertiary carbon-type acid-dissociable group G represented by general formula (g-1-1): Ａ１ Examples of the tertiary carbon-type acid-dissociable group include the following:

[0059]

[0060]

[0061]

[0062] <<Tertiary carbon-type acid-dissociable group G represented by general formula (g-1-2) Ａ２ >> In the above general formula (g-1-2), R Ａ ｇ２１ ~R Ａ ｇ２３ are each independently a hydro group or an optionally substituted C １－１２ In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), R Ａ ｇ２１ and R Ａ ｇ２２ , and / or R Ａｇ２２ and R Ａ ｇ２３ are directly connected to each other by a single bond or are divalently connected to each other by -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.

[0063] R Ａ ｇ２１ and R Ａ ｇ２２ , and / or R Ａ ｇ２２ and R Ａ ｇ２３ Examples of the case where R 1 forms a ring together with the carbon atom contained in the ethylenically unsaturated double bond include the case where R 1 forms a cyclopentenyl group, a cyclohexenyl group, a cyclopentylideneethenyl group, a cyclohexylideneethenyl group, or the like, which may have a substituent.

[0064] Also Cy Ａ ｇ２ represents a C which may have a substituent together with the tertiary carbon atom. ３－１８ An alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group is formed, and any divalent carbon atom is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0065] Cy Ａ ｇ２The tertiary carbon atom may be, together with the tertiary carbon atom, a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a cyclooctane skeleton, a cyclononane skeleton, a cyclodecane skeleton, a cyclododecane skeleton, a cyclopentene skeleton, a cyclohexene skeleton, a cycloheptene skeleton, a cyclooctene skeleton, a cyclodecene skeleton, a norbornane skeleton, an adamantane skeleton, a tricyclodecane skeleton, a tetracyclododecane skeleton, a norbornene skeleton, or a tricyclodecene skeleton, and the divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferably one which may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0066] A tertiary carbon-type acid-dissociable group G represented by general formula (g-1-2): Ａ２ Examples of the tertiary carbon-type acid-dissociable group include the following:

[0067]

[0068] As used herein, the term "hydroxy group or carboxy group having a protecting group" refers to a hydroxy group (including a phenolic hydroxy group) or a carboxy group protected with an ether-based protecting group, a silyl ether-based protecting group, an acetal-based protecting group, an acyl-based protecting group, an oxycarbonyl (alkyl)-based protecting group, a dihydrocarbylaminocarbonyl-based protecting group, or the like, or a hydroxy group (including a phenolic hydroxy group) or a carboxy group having an acid-dissociable group.

[0069] The ether-based protecting group is not particularly limited, and examples thereof include a methyl group, a benzyl group, a p-methoxybenzyl group, a t-butyl group, a triphenylmethyl group, a p-methoxyphenyldiphenylmethyl group, and a di(p-methoxyphenyl)phenylmethyl group. The silyl ether-based protecting group is not particularly limited, and examples thereof include a t-butyldimethylsilyl group (TBS), a triisopropylsilyl group (TIPS), a trimethylsilyl group (TMS), a triethylsilyl group (TES), and a t-butyldiphenylsilyl group (TBDPS). The acetal-based protecting group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxyethyl group, a 2-tetrahydropyranyl group (THP), and a methoxyethoxymethyl group. The acyl-based protecting group is not particularly limited, and examples thereof include an acetyl group, a pivaloyl group, and a benzoyl group. The oxycarbonyl (alkyl)-based protecting group is not particularly limited, and examples thereof include a t-butoxycarbonyl group. The dihydrocarbylaminocarbonyl protecting group is not particularly limited, and examples thereof include a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a diisopropylaminocarbonyl group, and an N-phenyl-N-methyl-aminocarbonyl group.

[0070] Examples of the protecting group include protecting groups P for hydroxy or carboxy groups represented by the following general formulae (P-1) and (P-2).

[0071] The protecting group P is not particularly limited, and known and commonly used protecting groups can be used. Examples of the protecting group P include, other than the above-mentioned "acid-dissociable group", "acetal-based protecting groups P" represented by the following general formula (p-1): Ａ ", "silyl ether-based protecting group P Ｂ ", "aminocarbonyl-based protecting group P Ｃ Each of these will be explained in turn below.

[0072] <Acetal-based protecting group PＡ The protecting group P is an acetal protecting group P represented by the following general formula (p-1): Ａ A protecting group having an oxygen atom bonded to the carbon atom directly bonded to the oxygen atom of a hydroxy group, a phenolic hydroxy group, or a carboxy group, such as:

[0073] "R Ａ ｐ１ " and "R Ａ ｐ３ " are each independently a hydro group or an optionally substituted C １－１２ In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (however, adjacent divalent carbon atoms are not replaced at the same time). Ａ ｐ２ " is an optionally substituted C １－１２ In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0074] R Ａ ｐ１ and R Ａ ｐ３ is a hydro group or a C １－１２ Alkyl group or C ３－１２ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－６ Alkyl group or C ３－８In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0075] R Ａ ｐ２ As the C １－１２ Alkyl group or C ３－１２ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－６ Alkyl group or C ３－８ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0076] An acetal-based protecting group P represented by general formula (p-1) Ａ Examples of the alkoxy group include a methoxymethoxy group, an ethoxymethoxy group, an n-propoxymethoxy group, an n-butoxymethoxy group, a 2,2-dimethylpropoxymethoxy group, a 2,2-dimethylbutoxymethoxy group, a cyclohexyloxymethoxy group, a 1-ethoxyethoxy group, a 1-n-butoxyethoxy group, and a 1-cyclohexyloxyethoxy group.

[0077] <Silyl ether protecting group P Ｂ The protecting group P is a silyl ether protecting group P represented by the following general formula (p-2): Ｂ A protecting group in which a silicon atom is directly bonded to the oxygen atom of a hydroxy group, a phenolic hydroxy group, or a carboxy group, such as:

[0078] "R Ｂ ｐ１ " ~ "R Ｂ ｐ３ " each independently represents a C １－１２ In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0079] R Ｂ ｐ１ ~R Ｂ ｐ３ As the C １－１２ Alkyl group or C ３－１２ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－６ Alkyl group or C ３－８ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0080] A silyl ether protecting group P represented by general formula (p-2) Ｂ Examples of the silyl group include a t-butyldimethylsilyl group (TBS), a triisopropylsilyl group (TIPS), a trimethylsilyl group (TMS), a triethylsilyl group (TES), and a t-butyldiphenylsilyl group (TBDPS).

[0081]

[0082] <Aminocarbonyl protecting group P Ｃ The protecting group P is an aminocarbonyl protecting group P represented by the following general formula (p-3): Ｃ A protecting group in which an aminocarbonyl group is bonded to the oxygen atom of a hydroxy group, a phenolic hydroxy group, or a carboxy group, such as

[0083] "R Ｃ ｐ１ " and "R Ｃ ｐ２ " are each independently a hydro group or an optionally substituted C １－１２ In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0084] R Ｃ ｐ１ and R Ｃ ｐ２ is a hydro group or a C １－１２ Alkyl group or C ３－１２ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－６ Alkyl group or C ３－８ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0085] An aminocarbonyl-based protecting group P represented by general formula (p-3)Ｃ Examples of the aminocarbonyl group include a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a diisopropylaminocarbonyl group, and an N-phenyl-N-methyl-aminocarbonyl group.

[0086]

[0087] 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 haloalkyl group, (3) a hydroxy group, (4) a thiol group, (5) a nitro group, (6) a cyano group, (7) a carboxy group, (8) an amino group, (9) a sulfo group, (10) a vinyl group, (11) an allyl group, (12) a (meth)acryloyl group, (13) a (meth)acryloyloxy group, (14) a (meth)acrylamide group, (15) a styryl group, (16) an epoxy group, (17) a glycidyl group, (18) an amide group, (19) a hydroxy group or a carboxy group having a protecting group, or (20) a C group in which at least a part of the hydrogen atoms may be substituted with the above (1) to (19). 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, C１－１８ Hydrocarbylthio group, C １－１８ Hydrocarbylsulfinyl group, C １－１８ A hydrocarbylsulfonyl group, in which a divalent carbon atom at any position except the terminal of the substituent is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time), etc.

[0088] [1. Step (1)] The method for producing a heteropolyacid salt having modified defect sites or a mixture thereof according to this embodiment includes, as step (1), a step of converting a Keggin-type or Dawson-type heteropolyacid salt into a one-defective Keggin-type or Dawson-type heteropolyacid salt or a mixture thereof.

[0089] The step (1) may include, as step (1a), a step of adjusting the pH value of the solution containing the Keggin type or Dawson type heteropolyacid salt to not more than 5. The step (1) may also include, after the step (1a), a step (1b) of adjusting the pH value of the solution to 4 to 8 using a weak base or a base.

[0090] <Keggin-type or Dawson-type Heteropolyacid Salt> As the heteropolyacid anion which is the anion moiety of the Keggin-type or Dawson-type heteropolyacid salt, there can be used a heteropolyacid anion in which the polyatom is Mo, W, V, Nb, or Ta and the heteroatom is P, Si, B, S, or Ge.

[0091] The Keggin or Dawson type heteropolyacid anion may be a Keggin or Dawson type heteropolyacid anion represented by general formula (II-1) or (II-2): [XM １２ O ４０ ] ｃ１１－ (II-1) [X ２ M １８ O ６２ ] ｃ１２－(II-2) [In formulas (II-1) and (II-2), X represents a heteroatom of P, Si, B, S, or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; c11- and c12- represent the number of negative charges, and c11 and c12 are natural numbers.]

[0092] Examples of Keggin-type heteropolyacid anions include [PW １２ O ４０ ] ３－ , [SiW １２ O ４０ ] ４－ , [B.W. １２ O ４０ ] ５－ , [SW １２ O ４０ ] ２－ , [GeW １２ O ４０ ] ４－ Examples of the Dawson-type heteropolyacid anion include [P ２ W １８ O ６２ ] ６－ , [Si ２ W １８ O ６２ ] ８－ , [S ２ W １８ O ６２ ] ４－ The above-mentioned Keggin type or Dawson type heteropoly acid anions may include all isomers and isomer mixtures, such as geometric isomers, optical isomers, rotational isomers, stereoisomers, and tautomers, that exist structurally, and are not limited to the descriptions of the chemical formulas for convenience.

[0093] The counter cation, which is the cation moiety of the Keggin or Dawson heteropolyacid salt, is not particularly limited, and examples thereof include H ＋ , Li ＋ , Na ＋ , K. ＋ , Rb ＋ , Cs ＋ , Be ２＋ , Mg ２＋ , Ca ２＋ , Sr ２＋ , Ba ２＋ , Al ３＋, Co ３＋ , Bi ３＋ , Zr ４＋ , Hf ４＋ , Bi ５＋ , N.H. ４＋ , quaternary ammonium cations, or combinations thereof.

[0094] <Single-Defect Keggin or Dawson Type Heteropolyacid Salt> Examples of the heteropolyacid anion that is the anion moiety of the single-defect Keggin or Dawson type heteropolyacid salt include heteropolyacid anions in which the polyatom is Mo, W, V, Nb, or Ta and the heteroatom is P, Si, B, S, or Ge.

[0095] The one-defect Keggin or Dawson heteropolyanion may be a one-defect Keggin or Dawson heteropolyanion represented by the general formula (III-1) or (III-2): [XM １１ O ３９ ] ｃ２１－ (III-1) [X ２ M １７ O ６１ ] ｃ２２－ (III-2) [In formulas (III-1) and (III-2), X represents a heteroatom of P, Si, B, S, or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; c21- and c22- represent the number of negative charges, and c21 and c22 are natural numbers.]

[0096] As the one-deficient Keggin type heteropolyanion, for example, [PMo １１ O ３９ ] ７－ , [P.W. １１ O ３９ ] ７－ , [SiMo １１ O ３９ ] ８－ , [SiW １１ O ３９ ] ８－ , [BMo １１ O ３９ ] ９－ , [B.W. １１ O ３９ ] ９－ , [SMo １１ O３９ ] ６－ , [SW １１ O ３９ ] ６－ , [BMo １１ O ３９ ] ９－ , [B.W. １１ O ３９ ] ９－ , [GeMo １１ O ３９ ] ８－ , [GeW １１ O ３９ ] ８－ Examples of the one-deficient Dawson heteropolyanion include [P ２ W １７ O ６１ ] １０－ , [S ２ W １７ O ６１ ] ８－ The one-deficient Keggin type or Dawson type heteropolyacid salt may include all structurally existing isomers such as geometric isomers, optical isomers, rotational isomers, stereoisomers, tautomers, and isomer mixtures, and is not limited to the description of the chemical formula for convenience.

[0097] The counter cation, which is the cation moiety of the one-deficient Keggin or Dawson heteropolyacid salt, is not particularly limited, and examples thereof include H ＋ , Li ＋ , Na ＋ , K. ＋ , Rb ＋ , Cs ＋ , Be ２＋ , Mg ２＋ , Ca ２＋ , Sr ２＋ , Ba ２＋ , Al ３＋ , Co ３＋ , Bi ３＋ , Zr ４＋ , Hf ４＋ , Bi ５＋ , N.H. ４＋ , quaternary ammonium cations, or combinations thereof.

[0098] [1-1. Step (1a)] The step (1) may include, as step (1a), a step of adjusting the pH value of a solution containing the Keggin type or Dawson type heteropolyacid salt to 5 or less.

[0099] By including the step (1a) in the step (1), the heteropolyacid salt or mixture thereof finally obtained, in which the defect sites have been modified, contains fewer impurities than when the publicly known and commonly used method described below is used. For this reason, it is preferable that the step (1) includes the step (1a).

[0100] The solution used in step (1a) is not particularly limited, and may contain, for example, water and / or one or more organic solvents, such as methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, glycerin, acetone, ethyl acetate, dichloroethane, chloroform, acetone, tetrahydrofuran, acetonitrile, dimethyl sulfoxide, and dimethylformamide.

[0101] The pH of the solution in step (1a) is preferably 5.0 or less, more preferably 4.8 or less, more preferably -1 to 4.5, and even more preferably -0.5 to 4.0.

[0102] In the step (1a), the method for adjusting the pH value of the solution to 5.0 or less is not particularly limited, and examples thereof include a method of adding an acidic solution. Examples of the acid contained in the acidic solution include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, sulfamic acid, and phosphoric acid; organic acids having a carboxy group such as tartaric acid, oxalic acid, formic acid, acetic acid, propionic acid, malic acid, lactic acid, citric acid, succinic acid, maleic acid, fumaric acid, glycolic acid, trifluoroacetic acid, and trichloroacetic acid; and organic acids having a sulfo group such as methanesulfonic acid, ethanesulfonic acid, sulfosuccinic acid, m-toluenesulfonic acid, and paratoluenesulfonic acid. The above acids may be used alone or in combination of two or more. Although the acid varies depending on the type of solution, hydrochloric acid, phosphoric acid, lactic acid, and acetic acid are preferred, and hydrochloric acid and acetic acid are more preferred.

[0103] In the step (1a), after adjusting the pH of the solution to 5.0 or less, the solution may be heated to raise the temperature for reaction, preferably 15° C. or more, 25° C. or more, or 35° C. or more, and preferably 80° C. or less, 70° C. or less, or 60° C. or less.

[0104] On the other hand, a known and commonly used method for producing a one-defect Keggin type or Dawson type heteropolyacid salt is to react a solution containing a salt of an oxide containing a polyatom of a heteropolyacid with a salt of an oxide containing a heteroatom of a heteropolyacid by adjusting the pH of the solution to about 5 to 7 using a 4 M aqueous hydrochloric acid solution or the like, and then adjusting the pH to 6 to 7 to obtain a one-defect Keggin type or Dawson type heteropolyacid salt. Note that, because the salt of an oxide containing a polyatom of a heteropolyacid is usually basic, the pH is adjusted to about 5 to 7 using a 4 M aqueous hydrochloric acid solution or the like.

[0105] Examples of the salts of oxides containing polyatoms of heteropolyacids include Na ２ MoO ４ , K. ２ MoO ４ , Rb ２ MoO ４ , Cs ２ MoO ４ , CaMoO４ , MgMoO ４ , SrMoO ４ , BaMoO ４ Molybdates such as Na ２ WO ４ , K. ２ WO ４ , Rb ２ Wo ４ , Cs ２ WO ４ , CaWO ４ , MgWO ４ , SrWO ４ ,BaWO ４ Tungstates such as NH ４ VO ３ , Na ３ VO ４ , NaVO ３ Vanadates such as NaNbO ３ , BaNb ２ O ６ , SrNb ２ O ６ Niobates such as KTaO ３ , NaTaO ３ , SrTa ２ O ６ and the like tantalates.

[0106] Examples of the heteroatom-containing oxide salts of the heteropolyacid salts include Li ３ P.O. ４ , Na ３ P.O. ４ , K. ３ P.O. ４ , Rb ３ P.O. ４ phosphates such as Li ２ SiO ３ , Na ２ SiO ３ , MgSiO ３ , CaSiO ３ , FeSiO ３ , MnSiO ３ , K. ２ SiO ３ Silicates such as Na ２ GeO ３ , BaGeO ３ , Ca ２ GeO ４ , Sr２ GeO ４ Germanates such as LiBO ２ , NaBO ２ , KBO ２ , RbBO ２ , MgB ２ O ４ , SrB ２ O ４ , BaB ２ O ４ , CoB ２ O ４ , MnB ２ O ４ Borates such as those mentioned above can be mentioned.

[0107] However, when the above-mentioned known and commonly used methods were used to prepare heteropolyacid salts or mixtures thereof with modified defect sites, the obtained heteropolyacid salts or mixtures thereof contained a large amount of impurities. Therefore, it is necessary to adopt a method other than the above-mentioned known and commonly used methods to prepare heteropolyacid salts or mixtures thereof with modified defect sites.

[0108] [1-2. Step (1b)] The step (1) may further include, after the step (1a), step (1b) of adjusting the pH of the solution to 4 to 8 using a weak base or a base.

[0109] As the solution, water and / or one or more organic solvents can be used, similar to the solutions exemplified in step (1a).

[0110] The weak base or base is not particularly limited, and examples thereof include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, lithium carbonate, lithium bicarbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, trisodium phosphate, disodium hydrogen phosphate, tripotassium hydrogen phosphate, dipotassium hydrogen phosphate, triethylamine, diethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,4-diazabicyclo[2.2.2]octane, pyridine, and 2-amino-2-methyl-1-propanol. The weak base or base may be used alone or in combination of two or more. Although the weak base or base varies depending on the type of solution, it is preferably sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, disodium hydrogen phosphate, or dipotassium hydrogen phosphate, which are weak bases, and more preferably sodium bicarbonate, potassium carbonate, or potassium bicarbonate.

[0111] [2. Step (2)] The method for producing a heteropolyacid salt having modified defect sites or a mixture thereof according to this embodiment includes, as step (2), a step of reacting a mono-defective Keggin or Dawson type heteropolyacid salt with a P, Si, Ge, or Sn compound having one or more hydro groups or organic groups and two or more leaving groups to obtain a heteropolyacid salt having modified defect sites represented by the following general formula (I) or a mixture thereof: (A ｐ＋ ) ｑ [C （ｐ×ｑ）－ ] (I) [wherein, A ｐ＋ are each independently H ＋ , a metal ion, or an ammonium ion; （ｐ×ｑ）－ represents a heteropolyanion in which the defective site of a Keggin or Dawson heteropolyanion is modified; p is an integer of 1 to 5, and q is a real number.

[0112] The step (2) may include, as step (2a), a step of reacting the singly defective Keggin or Dawson heteropolyacid salt with a P, Si, Ge, or Sn compound having one or more hydro groups or organic groups and two or more leaving groups in a solution having a pH of 5 or less.

[0113] <P, Si, Ge, or Sn Compound Having One or More Hydro Groups or Organic Groups and Two or More Leaving Groups> The P, Si, Ge, or Sn compound having one or more hydro groups or organic groups and two or more leaving groups is not particularly limited, and known and commonly used compounds can be used. The P, Si, Ge, or Sn compound having one or more hydro groups or organic groups and two or more leaving groups is not particularly limited, and for example, P, Si, Ge, or Sn compounds having hydro groups or organic groups and two or more leaving groups represented by general formulas (IV-1) to (IV-4) can be used. (R １Ａ ) X'Y ３ (IV-1) (R １Ｂ１ ) (R １Ｂ２ ) X'Y ２ (IV-2) (R １Ｃ ) P(=O)Y ２ (IV-3) (R １Ｄ ) X''Y ３ (IV-4) [In formulas (IV-1) to (IV-4), X′ represents a heteroatom of Si or Ge; X″ represents a heteroatom of Si, Ge, or Sn; R １Ａ ~R １Ｄ are each independently a hydro group or an optionally substituted C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, １Ａ ~R １Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); １Ａ ~R １Ｄa hydrogen atom contained in the formula (I) may be replaced by, for example, (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, or (s) a hydroxy group or carboxy group having a protecting group; and Y represents a leaving group.]

[0114] As the leaving group, known and commonly used ones can be used. The leaving group is not particularly limited, and examples thereof include a halogen atom, a hydroxy group, an alkoxy group (C １－４ An alkoxy group is preferred, and C １－２ An alkoxy group is more preferred.), an alkylcarbonyloxy group (C １－４ alkylcarbonyloxy group), hydrocarbylsulfonyloxy group (C １－６ Alkyl or C ７－１０ An aralkylsulfonyloxy group is preferred. Examples include a methanesulfonyloxy group and a p-toluenesulfonyloxy group.

[0115] (an organic group having one or more substituents such as a hydroxy group, a halogen atom, an epoxy group, etc.) Here, R in the general formulas (IV-1) to (IV-4) １Ａ ~R １Ｄ From the viewpoint of producing functional building blocks, １Ａ ~R １Ｄ C which may have a substituent １－１８ is a hydrocarbyl group; １Ａ ~R １Ｄ Any divalent carbon atom excluding the terminal may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); １Ａ~R １Ｄ and one or more hydrogen atoms contained in the group represented by the formula (I) are replaced by (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (o) an epoxy group, (p) a glycidyl group, or (r) an amide group. １－１８ Alkyl group, C ３－１８ Alicyclic group, C ７－１８ an aralkyl group; １Ａ ~R １Ｄ Any divalent carbon atom excluding the terminal may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); １Ａ ~R １Ｄ More preferably, one or more of the hydrogen atoms contained in the above formula (I) are substituted with (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (o) an epoxy group, (p) a glycidyl group, or (r) an amide group.

[0116] The above R １Ａ ~R １Ｄ Specific examples of the group include, but are not limited to, a 1-glycidyloxypropan-3-yl group, a 1-glycidyloxy-n-octan-8-yl group, a 1-aminopropan-3-yl group, a 1-(2-aminoethylamino)-propan-3-yl group, a 3,3,3-trifluoropropan-1-yl group, a chloromethyl group, a 1-chloropropan-3-yl group, a 1-bromopropan-3-yl group, and a 1-iodopropan-3-yl group.

[0117] (Organic Group Having One or More Ethylenically Unsaturated Double Bonds) From the viewpoint of producing a building block reactive to actinic rays, it is preferable that the organic group contains at least one ethylenically unsaturated double bond. That is, R１Ａ ~R １Ｄ The C １－１８ is a hydrocarbyl group; １Ａ ~R １Ｄ Any divalent carbon atom excluding the terminal may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); １Ａ ~R １Ｄ and one or more hydrogen atoms contained in the group represented by the formula (I) are substituted with (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (o) a (meth)acrylamide group, or (p) a styryl group. １－１８ Alkyl group, C ３－１８ Alicyclic group, C ７－１８ an aralkyl group; １Ａ ~R １Ｄ Any divalent carbon atom excluding the terminal may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); １Ａ ~R １Ｄ More preferred are those in which one or more hydrogen atoms contained in the above are substituted with (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (o) a (meth)acrylamide group, or (p) a styryl group.

[0118] The organic group R having an ethylenically unsaturated double bond １Ａ ~R １Ｄ Specific examples of the alkyl group include, but are not limited to, a vinyl group, an allyl group, a 5-hexen-1-yl group, a 6-hepten-1-yl group, a 7-octen-1-yl group, a 1-acryloyloxypropan-3-yl group, a 1-methacryloyloxypropan-3-yl group, and a 1-vinylbenzene-4-yl group.

[0119] (Organic group having one or more hydroxy or carboxy groups having a protecting group) Furthermore, from the viewpoint of providing a building block whose functionality such as solubility can be changed by deprotection by the action of an acid or the like, it is preferable that the organic group contains one or more hydroxy or carboxy groups having a protecting group. That is, １Ａ ~R １Ｄ The C １－１８ is a hydrocarbyl group; １Ａ ~R １Ｄ Any divalent carbon atom excluding the terminal may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); １Ａ ~R １Ｄ In the formula (I), one or more hydrogen atoms are replaced by a hydroxy group or a carboxy group having a protecting group (s), and optionally substituted C １－１８ Alkyl group, C ３－１８ Alicyclic group, C ７－１８ an aralkyl group; １Ａ ~R １Ｄ Any divalent carbon atom excluding the terminal may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); １Ａ ~R １Ｄ More preferably, one or more hydrogen atoms contained in (a) are replaced by a hydroxy group or a carboxy group having a protecting group (s).

[0120] The protecting group for the hydroxy group or carboxy group is not particularly limited, and may be an ether-based protecting group, a silyl ether-based protecting group, an acetal-based protecting group, an acyl-based protecting group, an oxycarbonyl (alkyl)-based protecting group, a dihydrocarbylaminocarbonyl-based protecting group, or the like. The protecting group for a hydroxy group or a carboxy group is preferably an ether-based protecting group such as a t-butyl group or a benzyl group; a silyl ether-based protecting group such as a t-butyldimethylsilyl group, a triisopropylsilyl group, a trimethylsilyl group, a triethylsilyl group or a t-butyldiphenylsilyl group; an acetal-based protecting group such as a methoxymethyl group, an ethoxyethyl group, a 2-tetrahydropyranyl group or a methoxyethoxymethyl group; an acyl-based protecting group such as an acetyl group, a pivaloyl group or a benzoyl group; an oxycarbonyl (alkyl)-based protecting group such as a t-butoxycarbonyl group; a dihydrocarbylaminocarbonyl-based protecting group such as a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a diisopropylaminocarbonyl group or an N-phenyl-N-methyl-aminocarbonyl group; or an acid-dissociable group in which the carbon bonded to the hydroxy group or the carboxy group is a tertiary carbon. More preferred are acetal-based protecting groups such as a methoxymethyl group, an ethoxyethyl group, a 2-tetrahydropyranyl group, or a methoxyethoxymethyl group; oxycarbonyl (alkyl)-based protecting groups such as a t-butoxycarbonyl group; dihydrocarbylaminocarbonyl-based protecting groups such as a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a diisopropylaminocarbonyl group, or an N-phenyl-N-methyl-aminocarbonyl group; and acid-dissociable groups in which the carbon bonded to the hydroxy group or the carboxy group is a tertiary carbon and which have a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a norbornane skeleton, or an adamantane skeleton.

[0121] The protecting group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxyethyl group, a methoxyethoxymethyl group, a t-butoxycarbonyl group, a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a diisopropylaminocarbonyl group, an N-phenyl-N-methyl-aminocarbonyl group, a 1-methylcyclopentyl group, a 1-ethylcyclopentyl group, a 1-phenylcyclopentyl group, a 1-tolylcyclopentyl group, a 1-methylcyclohex ... Examples thereof include a silyl group, a 1-ethylcyclohexyl group, a 1-phenylcyclohexyl group, a 1-tolylcyclohexyl group, a 1-(naphthalen-2-yl)cyclohexyl group, a 1-(1-methoxy-2-methylpropan-2-yl)cyclopentyl group, a 1-(1-ethoxy-2-methylpropan-2-yl)cyclopentyl group, a 2-methyladamantan-2-yl group, a 2-ethyladamantan-2-yl group, and a 2-phenyladamantan-2-yl group.

[0122] <Heteropolyacid salt having modified defect sites or a mixture thereof (I)> A mono-defective Keggin type or Dawson type heteropolyacid salt reacts with the P, Si, Ge, or Sn compound having one or more hydro groups or organic groups and two or more leaving groups to give a heteropolyacid salt having modified defect sites or a mixture thereof.

[0123] The state in which the defect site is modified with a P, Si, Ge, or Sn compound having one or more hydro groups or organic groups and two or more leaving groups represented by the above general formulas (IV-1) to (IV-4) can be represented by the following general formulas (V-1) to (V-4). [In formulas (V-1) to (V-4), X′ represents Si or Ge; X″ represents a heteroatom of Si, Ge, or Sn; R １Ａ ~R １Ｄ are each independently a hydro group or an optionally substituted C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, １Ａ ~R １ＤThe divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); １Ａ ~R １Ｄ The hydrogen atoms contained in may be replaced by (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, or (s) hydroxy groups or carboxy groups having a protecting group; * represents the bond with the terminal oxygen atom of the missing site.]

[0124] In this specification, heteropoly acid anions whose deficiency sites are modified with a P, Si, Ge, or Sn compound having one or more hydro groups or organic groups and two or more leaving groups, as represented by general formulas (V-1) to (V-4), may be represented for convenience as shown in the following general formulas (VI-1) to (VI-8): [XM １１ O ３９ (R １Ａ X') ２ O] ｃ３１－ (VI-1) [XM １１ O ３９ (R １Ｂ１ R １Ｂ２ X') ２ ] ｃ３１－ (VI-2) [XM １１ O ３９ (R １Ｃ P=O) ２ ] ｃ３１－ (VI-3) [XM １１ O ３９ (R １Ｄ X'') ｃ３１－ (VI-4) [X ２ M １７ O ６１ (R １Ａ X')２ O] ｃ３２－ (VI-5) [X ２ M １７ O ６１ (R １Ｂ１ R １Ｂ２ X') ２ ] ｃ３２－ (VI-5) [X ２ M １７ O ６１ (R １Ｃ P=O) ２ ] ｃ３２－ (VI-7) [X ２ M １７ O ６１ (R １Ｄ X'') ｃ３２－ (VI-8) [Wherein, X represents a heteroatom of P, Si, B, S, or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; X' represents a heteroatom of Si or Ge; X'' represents a heteroatom of Si, Ge, or Sn; R １Ａ ~R １Ｄ are each independently a hydro group or an optionally substituted C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, １Ａ ~R １Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced). １Ａ ~R １Ｄa hydrogen atom contained in may be replaced by (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, or (s) a hydroxy group or carboxy group having a protecting group; and c31 and c32 are natural numbers.]

[0125] In a heteropolyacid anion in which the vacant site is modified, four terminal oxygen atoms of the vacant site are modified, and therefore the value of c31 above is usually c21 - 4, and the value of c32 above is c22 - 4. On the other hand, for example, when the organic group contains an amino group which is protonated to form an ammonium cation, or when the organic group contains a carboxy group which is formed into a carboxy anion, the values ​​of c31 and c32 will differ from the above values.

[0126] [2-1. Step (2a)] Step (2) may include, as step (2a), a step of reacting the singly defective Keggin or Dawson type heteropolyacid salt with a P, Si, Ge, or Sn compound having one or more hydro groups or organic groups and two or more leaving groups in a solution having a pH of 5 or less. When step (2) includes step (2a), the reaction rate and efficiency of modifying the defective sites of the singly defective Keggin or Dawson type heteropolyacid salt with the P, Si, Ge, or Sn compound having one or more hydro groups or organic groups and two or more leaving groups can be further increased.

[0127] The solution used in the step (2a) is not particularly limited, and may be, for example, water and / or one or more organic solvents similar to those exemplified in the step (1a).

[0128] The pH value of the solution in step (2a) is preferably 5 or less, more preferably 4.8 or less, even more preferably -1 to 4.5, even more preferably -1 to 4, and even more preferably 0 to 4.

[0129] In the step (2a), the method for adjusting the pH value of the solution to 5 or less is not particularly limited, and examples thereof include a method of adding an acidic solution. Examples of the acid contained in the acidic solution include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, sulfamic acid, and phosphoric acid; organic acids having a carboxy group such as tartaric acid, oxalic acid, formic acid, acetic acid, propionic acid, malic acid, lactic acid, citric acid, succinic acid, maleic acid, fumaric acid, glycolic acid, trifluoroacetic acid, and trichloroacetic acid; and organic acids having a sulfo group such as methanesulfonic acid, ethanesulfonic acid, sulfosuccinic acid, meta-toluenesulfonic acid, and para-toluenesulfonic acid. The above acids may be used alone or in combination of two or more. Although the acid varies depending on the type of solution, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and acetic acid are preferred, and hydrochloric acid, sulfuric acid, and acetic acid are more preferred.

[0130] [3. Step (3)] The method for producing a heteropolyacid salt having modified defect sites or a mixture thereof according to this embodiment includes, as step (3), a step of salt-exchanging a heteropolyacid salt having modified defect sites represented by the general formula (I) above or a mixture thereof.

[0131] The step (3) may include, as step (3a), a step of salt-exchanging the heteropolyacid salt represented by the general formula (I) or a mixture thereof in which the defective site has been modified with an alkali metal salt, an alkaline earth metal salt, an aluminum salt, or an onium salt.

[0132] Furthermore, the step (3) may include, after the step (3a), a step (3b) of obtaining a heteropolyacid salt having modified defect sites represented by the following general formula (VII) or a mixture thereof: ｍ＋ ) ａ (B ｎ＋ ) ｂ (C （ａｍ＋ｂｎ）－) (VII) [Wherein, when b is 0, A ｍ＋ are each independently H ＋ , a metal ion, or an ammonium ion, at least one of which is ｐ＋ Alkali metal ions, alkaline earth metal ions, or Al ３＋ and if b is a real number greater than 0, then A ｍ＋ are each independently H ＋ , a metal ion, or an ammonium ion; B ｎ＋ each independently represents an organic sulfonium cation, an organic sulfonium dication, an organic iodonium cation, an organic ammonium cation, an organic ammonium dication, an organic phosphonium cation, or an organic phosphonium dication; （ａｍ＋ｂｎ）－ represents a heteropolyanion in which the defective site of a Keggin or Dawson heteropolyanion has been modified; m is an integer of 1 to 5, n is an integer of 1 or 2, and a is a real number.

[0133] [3-1. Step (3a)] The step (3) may include, as step (3a), a step of salt-exchanging the heteropolyacid salt represented by general formula (I) above, in which the defective sites have been modified, or a mixture thereof, with an alkali metal salt, an alkaline earth metal salt, an aluminum salt, or an onium salt.

[0134] <Alkali Metal Salt, Alkaline Earth Metal Salt, or Aluminum Salt> The metal cation of the alkali metal salt, alkaline earth metal salt, or aluminum salt is not particularly limited, and examples thereof include Li ＋ , Na ＋ , K. ＋ , Rb ＋ , Cs ＋ alkali metal ions such as Be ２＋ , Mg ２＋ , Ca ２＋ , Sr ２＋ , Ba ２＋ alkaline earth metal ions such as Al; ３＋The counter anion of the alkali metal salt, alkaline earth metal salt or aluminum salt is not particularly limited, and examples thereof include Cl － ,Br － , 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 － , B.F. ４ － , P.F. ６ － , SbF ６ － , AlCl ４ － , BiF ６ － , AsF ６ － etc. can be used.

[0135] Specific examples of the alkali metal salts, alkaline earth metal salts, or aluminum salts include sodium chloride, potassium chloride, rubidium chloride, cesium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, aluminum chloride, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, magnesium bromide, calcium bromide, strontium bromide, barium bromide, aluminum bromide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, magnesium iodide, calcium iodide, strontium iodide, barium iodide, and aluminum iodide.

[0136] <Onium Salt> The onium salt is not particularly limited, and for example, an organic sulfonium salt, an organic iodonium salt, an organic ammonium salt, an organic phosphonium salt, etc. Below, the cation moiety and the anion moiety of the onium salt are separately described.

[0137] <<Cation Moiety of Onium Salt>> (Cation Moiety of Organic Sulfonium Salt) As the cation moiety of the organic sulfonium salt, an organic sulfonium cation or an organic sulfonium dication can be used.

[0138] As the organic sulfonium cation, an organic sulfonium cation represented by the following general formula (VIII) can be used.

[0139] In formula (VIII), R ２Ａ , R ２Ｂ and R ２Ｃ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ２Ａ , R ２Ｂ and R ２Ｃ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２- (provided that adjacent divalent carbon atoms are not simultaneously replaced); ２Ａ , R ２Ｂ and R ２Ｃ The hydrogen atoms contained in the formula (I) are (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, or (t) C groups in which at least a part of the hydrogen atoms may be substituted with the above (a) to (s). 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 a hydrocarbyloxycarbonylamino group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２- (provided that adjacent divalent carbon atoms are not simultaneously replaced); ２Ａ , R ２Ｂ and R ２Ｃ Any two of these are directly connected to each other by a single bond, or are divalent linking groups -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 sulfur atom in formula (VIII).

[0140] From the viewpoint of providing a functional building block, the organic sulfonium cation represented by the general formula (VIII) is preferably R ２Ａ , R ２Ｂ and R ２Ｃ each independently represents an optionally substituted C １－１８ is a hydrocarbyl group; ２Ａ , R ２Ｂ and R ２Ｃ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ２Ａ , R ２Ｂ and R ２Ｃ at least one hydrogen atom of the optionally substituted C is preferably replaced by (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, or (s) a hydroxy group or carboxy group having a protecting group; １－１８ Alkyl group, C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C７－１８ an aralkyl group; ２Ａ , R ２Ｂ and R ２Ｃ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ２Ａ , R ２Ｂ and R ２Ｃ It is more preferable that at least one hydrogen atom of the above is replaced with (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, or (s) a hydroxy group or carboxy group having a protecting group.

[0141] As the organic sulfonium dication, an organic sulfonium dication represented by the following general formula (IX) can be used.

[0142] In formula (IX), R ３Ａ ~R ３Ｄ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ３Ａ ~R ３Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); ３Ａ is an optionally substituted C １－１８ represents a hydrocarbylene group,３Ａ The divalent carbon atom at any position in ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ３Ａ ~R ３Ｄ and L ３Ａ The hydrogen atoms contained in the formula (I) are (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, or (t) C groups in which at least a part of the hydrogen atoms may be substituted with the above (a) to (s). 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 a hydrocarbyloxycarbonylamino group, or C １－１８A divalent carbon atom at any position excluding the terminal of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); R ３Ａ ~R ３Ｄ and L ３Ａ Any two of these 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 sulfur atom in formula (IX).

[0143] (Cation Moiety of Organic Iodonium Salt) As the cation moiety of the organic iodonium salt, an organic iodonium cation represented by the following general formula (X) can be used.

[0144] In general formula (X), R ４Ａ and R ４Ｂ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ４Ａ and R ４Ｂ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ４Ａ and R ４ＢThe hydrogen atoms contained in the formula (I) are (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, or (t) C groups in which at least a part of the hydrogen atoms may be substituted with the above (a) to (s). 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 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 a hydrocarbyloxycarbonylamino group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be substituted with a hydrocarbyloxycarbonyloxy group, and may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ４Ａ and R 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 (X).

[0145] From the viewpoint of providing a functional building block, the organic iodonium cation represented by the general formula (X) is preferably R ４Ａ and R ４Ｂ each independently represents an optionally substituted C １－１８ is a hydrocarbyl group; ４Ａ and R ４Ｂ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ４Ａ and R ４Ｂ at least one hydrogen atom of the optionally substituted C is preferably replaced by (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, or (s) a hydroxy group or carboxy group having a protecting group; １－１８ Alkyl group, C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８ an aralkyl group; ４Ａ and R ４Ｂ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２- (provided that adjacent divalent carbon atoms are not simultaneously replaced); ４Ａ and R ４Ｂ It is more preferable that at least one hydrogen atom of the above is replaced with (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, or (s) a hydroxy group or carboxy group having a protecting group.

[0146] (Cation Moiety of Organic Ammonium Salt) As the cation moiety of the organic ammonium salt, an organic ammonium cation or an organic ammonium dication can be used. The organic ammonium cation is not particularly limited, and examples thereof include organic primary ammonium cations (NH ３ (R ５Ａ ) ＋ )), organic secondary ammonium cations (NH ２ (R ５Ａ ) (R ５Ｂ )) ＋ ), organic tertiary ammonium cation (NH(R ５Ａ ) (R ５Ｂ ) (R ５Ｃ ) ＋ ), organic quaternary ammonium cation (N(R ５Ａ ) (R ５Ｂ ) (R ５Ｃ ) (R ５Ｄ ) ＋ ) can be mentioned. ５Ａ ~R ５Ｄ represents the same as defined below. The organic ammonium cation is preferably an organic tertiary ammonium cation or an organic quaternary ammonium cation, and more preferably an organic quaternary ammonium cation.

[0147] As the organic quaternary ammonium cation, an organic quaternary ammonium cation represented by the following general formula (XI) can be used.

[0148] In general formula (XI), R ５Ａ ~R ５Ｄ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ５Ａ ~R ５Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), ５Ａ ~R ５Ｄ The hydrogen atoms contained in the formula (I) are (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, or (t) C groups in which at least a part of the hydrogen atoms may be substituted with the above (a) to (s). 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 Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ a hydrocarbyloxycarbonylamino group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be substituted with a hydrocarbyloxycarbonyloxy group, and may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ５Ａ ~R ５Ｄ Any two of these 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 nitrogen atom in formula (XI).

[0149] From the viewpoint of providing a functional building block, the organic quaternary ammonium cation represented by the general formula (XI) is preferably R ５Ａ ~R ５Ｄ each independently represents an optionally substituted C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ５Ａ ~R ５Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), ５Ａ ~R ５ＤIt is more preferable that at least one hydrogen atom contained in the formula (I) is replaced by (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, or (s) a hydroxy group or carboxy group having a protecting group; １－１８ Alkyl group, C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８ is an aralkyl group, and the R ５Ａ ~R ５Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), ５Ａ ~R ５Ｄ It is more preferable that at least one hydrogen atom of the above is replaced with (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, or (s) a hydroxy group or carboxy group having a protecting group.

[0150] The organic ammonium dication is not particularly limited, and known and commonly used organic ammonium dications can be used. Examples of the organic ammonium dication include organic ammonium dications containing two organic primary to quaternary ammonium cations. Examples of organic quaternary ammonium dications containing two organic quaternary ammonium cations include organic quaternary ammonium dications represented by the following general formula (XII):

[0151] In general formula (XII), R ６Ａ ~R ６Ｆ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ６Ａ ~R ６Ｆ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); ６Ａ is an optionally substituted C １－１８ represents a hydrocarbylene group, ６Ａ The divalent carbon atom at any position in ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ６Ａ ~R ６Ｆ and L ６ＡThe hydrogen atoms contained in the formula (I) are (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, or (t) C groups in which at least a part of the hydrogen atoms may be substituted with the above (a) to (s). 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 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 a hydrocarbyloxycarbonylamino group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be substituted with a hydrocarbyloxycarbonyloxy group, and may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); R ６Ａ ~R ６Ｆ and L ６ＡAny two of these 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 nitrogen atom in formula (XII).

[0152] (Cation Moiety of Organic Phosphonium Salt) As the cation moiety of the organic phosphonium salt, an organic phosphonium cation or an organic phosphonium dication can be used.

[0153] As the organic phosphonium cation, an organic phosphonium cation represented by the following general formula (XIII) can be used.

[0154] In general formula (XIII), R ７Ａ ~R ７Ｄ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ７Ａ ~R ７Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), ７Ａ ~R ７Ｄ The hydrogen atoms contained in the formula (I) are (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, or (t) C groups in which at least a part of the hydrogen atoms may be substituted with the above (a) to (s). １－１８ Hydrocarbyl group, C１－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl 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 a hydrocarbyloxycarbonylamino group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be substituted with a hydrocarbyloxycarbonyloxy group, and may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ７Ａ ~R ７Ｄ Any two of these 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 phosphorus atom in formula (XIII).

[0155] From the viewpoint of providing a functional building block, the organic quaternary phosphonium cation represented by the general formula (XIII) is preferably R ７Ａ ~R ７Ｄ each independently represents an optionally substituted C １－１８represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group; ７Ａ ~R ７Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ７Ａ ~R ７Ｄ at least one hydrogen atom of the optionally substituted C is preferably replaced by (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, or (s) a hydroxy group or carboxy group having a protecting group; １－１８ Alkyl group, C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８ an aralkyl group; ４Ａ ~R ４Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ４Ａ ~R ４ＤIt is more preferable that at least one hydrogen atom of the above is replaced with (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, or (s) a hydroxy group or carboxy group having a protecting group.

[0156] As the organic phosphonium dication, an organic phosphonium dication represented by the following general formula (XIV) can be used.

[0157] In general formula (XI), R ８Ａ ~R ８Ｆ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ８Ａ ~R ８Ｆ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), L ８Ａ is an optionally substituted C １－１８ represents a hydrocarbylene group, ８Ａ The divalent carbon atom at any position in ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ８Ａ ~R ８Ｆ and L ８ＡThe hydrogen atoms contained in the formula (I) are (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, or (t) C groups in which at least a part of the hydrogen atoms may be substituted with the above (a) to (s). 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 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 a hydrocarbyloxycarbonylamino group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be substituted with a hydrocarbyloxycarbonyloxy group, and may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); R ８Ａ ~R ８Ｆ and L ８ＡAny two of these 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 phosphorus atom in formula (XIV).

[0158] <<Anion Moiety of Onium Salt>> The anion moiety of the onium salt is not particularly limited, and examples thereof include Cl － ,Br － , 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 － , B.F. ４ － , P.F. ６ － , SbF ６ － , AlCl ４ － , BiF ６ － , AsF ６ － The anion moiety of the onium salt may be Cl, from the viewpoint of promoting the salt exchange reaction. － ,Br － , I － , O.H. － , C.F. ３ SO３ － , C ４ F ９ SO ３ － , B.F. ４ － , P.F. ６ － , SbF ６ － More preferably, Cl － ,Br － , C.F. ３ SO ３ － , B.F. ４ － , P.F. ６ － , SbF ６ － It is more preferable that:

[0159] <<Examples of Onium Salts>> Specific examples of the onium salts include organic sulfonium salts such as methionine methylsulfonium chloride, (2-bromoethyl)diphenylsulfonium trifluoromethanesulfonate, benzyl(4-hydroxyphenyl)methylsulfonium hexafluoroantimonate, (2-carboxyethyl)dimethylsulfonium bromide, dimesityl(trifluoromethyl)sulfonium trifluoromethanesulfonate, diphenyl(4-(phenylthio)phenyl)sulfonium hexafluoroantimonate, 5-vinyl-5H-thianthren-5-ium tetrafluoroborate, triphenylsulfonium tetrafluoroborate, tri-p-tolylsulfonium trifluoromethanesulfonate, and (thiodi-4,1-phenylene)bis(diphenylsulfonium)bis(hexafluorophosphate);Bis(4-t-butylphenyl)iodonium hexafluorophosphate, bis(4-bromophenyl)iodonium trifluoromethanesulfonate, bis(2,4,6-trimethylphenyl)iodonium trifluoromethanesulfonate, (3-bromophenyl)(mesityl)iodonium trifluoromethanesulfonate, diphenyliodonium chloride, (2-methylphenyl)(2,4,6-trimethylphenyl)iodonium trifluoromethanesulfonate, (4-nitrophenyl)(phenyl)iodonium trifluoromethanesulfonate, phenyl(3-(trifluoromethyl)phenyl)iodonium trifluoromethanesulfonate, (3-(trifluoromethyl)phenyl)iodonium trifluoromethanesulfonate), organic iodonium salts such as (4-(trifluoromethyl)phenyl)(2,4,6-trimethylphenyl)iodonium trifluoromethanesulfonate, (4-(trifluoromethyl)phenyl)(2,4,6-trimethylphenyl)iodonium trifluoromethanesulfonate, bis(4-fluorophenyl)iodonium trifluoromethanesulfonate, ((4-trifluoromethyl)phenyl)(2,4,6-trimethoxyphenyl)iodonium p-toluenesulfonate, 4-biphenylyl(2,4,6-trimethoxyphenyl)iodonium trifluoromethanesulfonate, and (3,5-dichlorophenyl)(2,4,6-trimethoxyphenyl)iodonium p-toluenesulfonate;Organic quaternary ammonium salts such as benzyltrimethylammonium chloride, tetrabutylammonium chloride, dodecyltrimethylammonium chloride, acetylcholine chloride, benzoylcholine chloride, benzyldimethylphenylammonium chloride, bis(2-hydroxyethyl)dimethylammonium chloride, bethanechol chloride, (3-acrylamidopropyl)trimethylammonium chloride, N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride, diallyldimethylammonium chloride, glycidyltrimethylammonium chloride, methacryloylcholine chloride, hexyltrimethylammonium bromide, 1-methyl-1-propylpiperidinium bromide, 3-(trifluoromethyl)phenyltrimethylammonium bromide, trimethylvinylammonium bromide, acetylthiocholine iodide, (3-bromopropyl)trimethylammonium bromide, (2-hydroxyethyl)triethylammonium iodide, hexamethonium chloride, and decamethonium bromide;(Methoxymethyl)triphenylphosphonium chloride, tetrabutylphosphonium bromide, amyltriphenylphosphonium bromide, allyltriphenylphosphonium bromide, acetonyltriphenylphosphonium chloride, benzyltriphenylphosphonium chloride, butyltriphenylphosphonium bromide, (bromomethyl)triphenylphosphonium bromide, 3-bromopropyltriphenylphosphonium bromide, (4-bromobenzyl)triphenylphosphonium bromide, (chloromethyl)triphenylphosphonium chloride, 4-(carboxybutyl)triphenylphosphonium Examples of organic phosphonium salts include iodide, triphenylphosphonium bromide, (cyanomethyl)triphenylphosphonium chloride, (2-chlorobenzyl)triphenylphosphonium chloride, 2-(1,3-dioxan-2-yl)ethyltriphenylphosphonium bromide, (2,4-dichlorobenzyl)triphenylphosphonium chloride, ethyltriphenylphosphonium iodide, triphenylpropargylphosphonium bromide, tetraphenylphosphonium bromide, cyclopropyltriphenylphosphonium bromide, and trans-2-butene-1,4-bis(triphenylphosphonium chloride);

[0160] <Salt Exchange Reaction> The reaction conditions for the salt exchange between the heteropolyacid salt represented by general formula (I) in which the defective portions have been modified or a mixture thereof and an alkali metal salt, an alkaline earth metal salt, an aluminum salt, or an onium salt are not particularly limited, and the reaction 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 set as appropriate.

[0161] 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.

[0162] [3-2. Step (3b)] The step (3) may include, after the step (3a), a step (3b) of obtaining a heteropolyacid salt having modified defect sites represented by general formula (VII) or a mixture thereof. ｍ＋ ) ａ (B ｎ＋ ) ｂ (C （ａｍ＋ｂｎ）－ ) (VII) [Wherein, when b is 0, A ｍ＋ are each independently H ＋ , a metal ion, or an ammonium ion, at least one of which is ｐ＋ Alkali metal ions, alkaline earth metal ions, or Al ３＋ and if b is a real number greater than 0, then A ｍ＋ are each independently H ＋ , a metal ion, or an ammonium ion; B ｎ＋ each independently represents an organic sulfonium cation, an organic sulfonium dication, an organic iodonium cation, an organic ammonium cation, an organic ammonium dication, an organic phosphonium cation, or an organic phosphonium dication; （ａｍ＋ｂｎ）－ represents a heteropolyanion in which the defective site of a Keggin or Dawson heteropolyanion has been modified; m is an integer of 1 to 5, n is an integer of 1 or 2, and a is a real number.

[0163] The alkali metal ions, alkaline earth metal ions, organic sulfonium cations, organic sulfonium dications, organic iodonium cations, organic ammonium cations, organic ammonium dications, organic phosphonium cations, and organic phosphonium dications can be the same as those described above.

[0164] Also C （ａｍ＋ｂｎ）－ is a heteropoly acid anion in which the defect site in a one-defect Keggin type or Dawson type heteropoly acid anion is modified, and may be a heteropoly acid anion in which the defect site is modified, represented by any of the general formulae (VI-1) to (VI-8).

[0165] In the general formula (VII), m is an integer of 1 to 5, n is an integer of 1 or 2, and a and b are real numbers. ｍ＋ and B ｎ＋ In this case, the values ​​of a and b can be determined by, for example, NMR analysis, XRF analysis, XPS analysis, or the like.

[0166] The ratio of a to b is as follows: ｍ＋ , B ｎ＋ Although it depends on the type of compound, a:b is preferably 0-3:0-12, more preferably 0-2:0-8, and even more preferably 0-1:1-4. In particular, when the value of a+b is a real number of 3-7 and m is 1, it is preferable that a is a real number of 0-3 and b is a real number of 0-7, and it is more preferable that a is a real number of 0-2 and b is a real number of 2-7.

[0167] After the salt exchange reaction, the method for obtaining the heteropolyacid salt having modified defect sites represented by general formula (VII) or a mixture thereof is not particularly limited, and for example, a method may be used in which the by-product is extracted into a water tank and removed, or an inorganic salt is precipitated and separated by filtration, or the heteropolyacid salt having modified defect sites represented by general formula (VII) or a mixture thereof is crystallized and separated by filtration.

[0168] [3-3. Step (3a')] In another method for producing a heteropolyacid salt or a mixture thereof having modified defect sites according to this embodiment, the above step (3) may include the following step (3a') instead of step (3a). Step (3a') comprises a step of substituting a cation moiety of a heteropolyacid salt or a mixture thereof having modified defect sites represented by the above general formula (I) with a metal ion, ammonium ion, or organic ammonium cation by a salt exchange reaction, and a further step of salt-exchanging the resulting cation with an onium salt. By including the above two-stage salt exchange reaction step, it is possible to produce a heteropolyacid salt or a mixture thereof having modified defect sites with few impurities. The metal ion may be, for example, Li ＋ , Na ＋ , K. ＋ , Rb ＋ , Cs ＋ alkali metal ions such as Be ２＋ , Mg ２＋ , Ca ２＋ , Sr ２＋ , Ba ２＋ alkaline earth metal ions such as Al; ３＋ Alkali metal ions or alkaline earth metal ions are preferred, alkali metal ions are more preferred, and Na ＋ , K. ＋ , Rb ＋ , Cs ＋ Further, as the organic ammonium cation, the above-mentioned organic primary ammonium cation (NH ３ (R ５Ａ ) ＋ )), organic secondary ammonium cations (NH ２ (R ５Ａ ) (R ５Ｂ )) ＋ ), organic tertiary ammonium cation (NH(R ５Ａ ) (R ５Ｂ ) (R ５Ｃ ) ＋ ), organic quaternary ammonium cation (N(R ５Ａ ) (R ５Ｂ ) (R ５Ｃ ) (R ５Ｄ )＋ ) can be used.

[0169] More specifically, a preferred method for producing a heteropolyacid salt having defect sites represented by general formula (VII) or a mixture thereof includes the steps of reacting a heteropolyacid salt having defect sites represented by general formula (I) modified or a mixture thereof with a compound having a metal ion, an ammonium ion, or an organic ammonium cation represented by general formula (XV-1) to perform salt exchange, and further salt-exchanging the compound represented by general formula (XV-2) thus produced with an onium salt. (A ｐ＋ ) ｑ [C （ｐ×ｑ）－ ] (I) (A ’＋ ) (Y － ) ｎ (XV-1) (A ’＋ ) ｐ×ｑ [C （ｐ×ｑ）－ ] (XV-2) [wherein, A ｐ＋ are each independently H ＋ , a metal ion, or an ammonium ion; ’＋ each independently represents a metal ion, an ammonium ion, or an organic ammonium cation; （ｐ×ｑ）－ represents a heteropolyanion of one defective Keggin type or Dawson type in which the defective site is modified; Y － represents a monovalent counter anion; p is an integer of 1 to 5, and q is a real number. ｍ＋ ) ａ (B ｎ＋ ) ｂ (C （ａｍ＋ｂｎ）－ ) (VII) [wherein, A ｍ＋ are each independently H ＋ , a metal ion, or an ammonium ion; B ｎ＋ each independently represents an organic sulfonium cation, an organic sulfonium dication, an organic iodonium cation, an organic ammonium cation, an organic ammonium dication, an organic phosphonium cation, or an organic phosphonium dication; （ａｍ＋ｂｎ）－represents a heteropolyanion in which the defective site of a Keggin or Dawson heteropolyanion has been modified; m is an integer of 1 to 5, n is an integer of 1 or 2, a is a real number, and b is a real number greater than 0.

[0170] Examples of the compound represented by general formula (XV-1) include sodium chloride, potassium chloride, rubidium chloride, cesium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, aluminum chloride, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, magnesium bromide, calcium bromide, strontium bromide, barium bromide, aluminum bromide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, magnesium iodide, calcium iodide, strontium iodide, barium iodide, aluminum iodide, ammonium chloride, ammonium bromide, salts of any of the above-mentioned organic quaternary ammonium cations with halide ions, and the like.

[0171] When reacting the compound represented by general formula (XV-1) with an onium salt, a salt exchange reaction can be carried out using a two-phase system of an organic solvent and water. By using a two-phase system of an organic solvent and water, the heteropolyacid salt having modified vacancies represented by general formula (VII) or a mixture thereof is contained in the organic solvent layer, while by-product compounds such as metal salts and ammonium salts are mainly contained in the aqueous layer. Examples of the organic solvent that can be used include methanol, ethanol, 1,4-dioxane, acetonitrile, 1-propanol, 2-propanol, ethyl acetate, acetonitrile, acetone, dichloromethane, chloroform, dimethylformamide, and diethyl ether. Ethyl acetate, dichloromethane, chloroform, and diethyl ether are preferred.

[0172] [3-4. Step (3b')] In another embodiment of the method for producing a heteropolyacid salt or a mixture thereof having modified defect sites, step (3) may include the following step (3b') subsequent to step (3a) or step (3a'). In the salt exchange reaction of step (3a) or step (3a'), the generated by-products are extracted into the aqueous layer and removed, while the heteropolyacid salt or mixture thereof having modified defect sites represented by general formula (VII) is contained in the organic solvent layer. Alternatively, after the salt exchange reaction of step (3a) or step (3a'), the heteropolyacid salt or mixture thereof having modified defect sites represented by general formula (VII) can be precipitated by a recrystallization method or the like to obtain the heteropolyacid salt or mixture thereof having modified defect sites. Step (3b') is a step of washing the heteropolyacid salt or mixture thereof having modified defect sites represented by general formula (VII) contained in the organic solvent layer or the precipitate with an acidic aqueous solution having a pH of 6 or less. By including step (3b'), it is possible to obtain a heteropolyacid salt or mixture thereof having modified defect sites with fewer impurities.

[0173] The pH of the acidic aqueous solution is preferably 6 or less, more preferably 5.8 or less, more preferably -1 to 4.5, even more preferably -0.5 to 3.5, and even more preferably 0 to 2.0.

[0174] Examples of the acid contained in the acidic aqueous solution include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, sulfamic acid, and phosphoric acid; organic acids having a carboxy group such as tartaric acid, oxalic acid, formic acid, malic acid, citric acid, succinic acid, maleic acid, fumaric acid, glycolic acid, trifluoroacetic acid, and trichloroacetic acid; and organic acids having a sulfo group such as methanesulfonic acid, ethanesulfonic acid, sulfosuccinic acid, metatoluenesulfonic acid, and paratoluenesulfonic acid. These acids may be used alone or in combination of two or more. The acid is preferably hydrochloric acid, sulfuric acid, tartaric acid, formic acid, citric acid, succinic acid, or malic acid.

[0175] After the step of washing the heteropolyacid salt having modified defect sites represented by general formula (VII) or a mixture thereof with an acidic aqueous solution having a pH of 6 or less, a step of washing the organic solvent layer or precipitate containing the heteropolyacid salt having modified defect sites or the mixture thereof multiple times with pure water or the like may be included.

[0176] By carrying out the step (3b'), metals or metal ions contained as impurities in the heteropolyacid salt or mixture thereof in which the defect sites represented by general formula (VII) have been modified, such as Li, Na, Mg, Al, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Sr, Zr, Mo, Ag, Cd, Sn, Sb, Ba, W, Pb, and Au (provided that the polyatoms, heteroatoms, and Au in the heteropolyacid salt or mixture thereof are not included). ｍ＋ (excluding the metals or metal ions contained in the above) can be removed, and the content of each can be reduced to a value of less than 100 ppb.

[0177] The content of metals or metal ions contained as impurities in the heteropolyacid or mixture thereof whose defect sites have been modified can be measured by inductively coupled plasma mass spectrometry (ICP-MS).

[0178] The mechanism by which the content of metal or metal ion impurities can be effectively reduced by the step of washing a heteropolyacid salt or mixture thereof in which the defect sites represented by general formula (VII) have been modified with an acidic aqueous solution having a pH of 6 or less is unclear. Heteropolyacid anions are generally susceptible to various chemical changes, such as pH, ionic strength, and redox potential, and these chemical changes are known to affect the cluster structure / frame, formation mechanism, interaction network, etc., of the heteropolyacid anion. Therefore, the mechanism behind this is thought to be that by exposing the heteropolyacid salt or mixture thereof in which the defect sites have been modified with an acidic aqueous solution having a pH of 6 or less, the structure / frame, formation mechanism, interaction network, etc. of the heteropolyacid anion are loosened, making it possible to effectively wash out and remove the metal or metal ion impurities that had been clinging to the structure / frame or interaction network of the heteropolyacid anion.

[0179] EXAMPLES The present invention will be specifically explained below by showing examples, but the present invention is not limited to these examples.

[0180] [1. Production of Heteropolyacid Salts Having Modified Defect Sites] Heteropolyacid salts M-1-1, M-1-2, M-2, and M-3 having modified defect sites were each produced by the production method described below.

[0181] [Production Example 1 (Example of Step (1)): Potassium silicotungstate (K ８ [SiW １１ O ３９ Synthesis of tungstosilicic acid hydrate (H ４ [SiW １２ O ４０ ]・xH ２To 63 g of 1M acetic acid (C10), 380 g was added, and the reaction solution was heated to 45 ° C. Potassium bicarbonate (52 g) was added so that the pH was 6.0. The reaction solution was then cooled to room temperature and filtered off by suction, yielding 56 g of a crude product. 216 g of pure water was added to the obtained crude product, and the mixture was redissolved by heating to a water temperature of 73 ° C. The solution was cooled at 4 ° C. for 16 hours to recrystallize, filtered off by suction, and vacuum dried to obtain 34 g of the target compound. ２９ Si-NMR (119.22MHz, D ２ O): δ (ppm) = -84.6 (s, 1Si). １８３ W-NMR (20.84MHz, D ２ O): δ (ppm) = -101.85 (s, 2W), -116.26 (s, 2W), -119.29 (s, 1W), -125.62 (s, 2W), -140.85 (s, 2W), -174.53 (s, 2W).

[0182] [Production Example 2-1 (Example of Steps (2) and (3)): Synthesis of Heteropolyacid Salt (Tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-divinyldisiloxane-1,1,3,3-tetrayl)undecatungstosilicate) (M-1-1) Having Modified Defect Sites] Vinyltrimethoxysilane (CH ２ =CH-Si(OCH ３ ) ３ ) was added to the solution, and the mono-deficient potassium silicotungstate (K ８ [SiW １１ O ３９]) was added. The pH was adjusted to 1.8 using 1 M hydrochloric acid. After stirring for 2 hours, the unreacted powder was filtered off by suction, and the filtrate was concentrated to approximately 200 g using a rotary evaporator. 127 g (18.2 mmol) of a 6.3% aqueous solution of bis(2-trifluoromethylphenyl)phenylsulfonium chloride was added to this concentrated solution to precipitate a powder. The precipitated powder was filtered off by suction and washed three times each with 180 mL of pure water, 180 mL of methanol, and 180 mL of methyl t-butyl ether. The obtained powder was then dispersed and washed with 160 g of methanol for 3 hours, filtered off again by suction, and washed three times with 160 g of methanol. Further thorough vacuum drying afforded 12.6 g of the target compound M-1-1 as a white powder. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 5.94 (dd, 2H), 6.08 (dd, 2H), 6.13 (dd, 2H), 7.65-8.35 (m, 52H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -66.56 (s, 2Si), -85.29 (s, 1Si). １８３ W-NMR (20.84MHz, DMSO-d6): δ (ppm) = -105.52 (s, 2W), -107.54 (s, 2W), -112.04 (s, 1W), -126.08 (s, 2W), -170.95 (s, 2W), -247.66 (s, 2W). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 700.3 (median) ([C ４ H ６ O ４０ Si ３ W １１ ] ４－ )

[0183] [Production Example 2-2 (Example of Step (3b')): Synthesis of Heteropolyacid Salt (Tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-divinyldisiloxane-1,1,3,3-tetrayl)undecatungstosilicate) (M-1-2) Having Modified Defect Sites] 12.6 g of the powder M-1-1 obtained in Production Example 2-1 was dissolved in 50 mL of dichloromethane, and the solution was stirred and washed using 50 mL of 1% aqueous hydrochloric acid. The supernatant was then removed, and the solution was washed three times with 50 mL of pure water. 400 mL of methyl t-butyl ether was then added to the resulting dichloromethane solution, and the precipitated powder was filtered off by suction filtration and washed with 400 mL of methyl t-butyl ether. Further thorough vacuum drying afforded 11.3 g of the target compound M-1-2 as a white solid.

[0184] [Production Example 3 (Example of Steps (2) and (3)): Synthesis of Defect Site-Modified Heteropolyacid Salt ((tetrakis(2-trifluoromethylbenzyl)triallylammonium)(1,3-divinyldisiloxane-1,1,3,3-tetrayl)undecatungstosilicate) (M-2)] Vinyltrimethoxysilane (CH ２ =CH-Si(OCH ３ ) ３ 0.64 mL (1.4 mmol) of potassium silicotungstate (K ８ [SiW １１ O ３９]) was added to the mixture. The pH was adjusted to 1.8 using 1 M hydrochloric acid. After stirring for 2 hours, the unreacted powder was filtered off by suction, and the filtrate was concentrated to approximately 72 g using a rotary evaporator. 17 g (7.0 mmol) of a 20% aqueous solution of (2-trifluoromethylbenzyl)triallylammonium bromide was added to the concentrated solution to precipitate a powder. The precipitated powder was filtered off by suction and washed three times each with 70 mL of pure water, 70 mL of methanol, and 70 mL of methyl t-butyl ether. The obtained powder was then dispersed and washed with 60 g of methanol for 3 hours, filtered off by suction, and washed three times with 60 g of methanol. Further thorough vacuum drying afforded 4.5 g of the target compound M-2 as a white powder. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 4.04 (d, 24H), 4.73 (s, 8H), 5.65 (d, 12H), 5. 73 (d, 12H), 5.94 (d, 2H), 6.02-6.13 (m, 16H), 7.80-7.88 (m, 12H), 7.94 (d, 4H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -66.56 (s, 2Si), -85.29 (s, 1Si). １８３ W-NMR (20.84MHz, DMSO-d6): δ (ppm) = -105.52 (s, 2W), -107.54 (s, 2W), -112.04 (s, 1W), -126.08 (s, 2W), -170.95 (s, 2W), -247.66 (s, 2W). ESI-MS: POSITIVE m / z 296.2 ([C １７ H ２１ F ３ N] ＋ ) NEGATIVE m / z 700.3 (median) ([C ４ H ６ O ４０ Si ３ W １１ ] ４－ )

[0185] Comparative Production Example 1 (Example corresponding to step (1)): Potassium silicotungstate (K ８ [SiW １１ O ３９Synthesis of potassium silicotungstate (K ８ [SiW １１ O ３９ ]) was synthesized as follows according to the method described in Inorganic Syntheses, 1990, 27, 85-96. ２ WO ４ ・2H ２ 94 g of purified water was added to 57.5 g of sodium metasilicate nonahydrate (Na 0), and the mixture was stirred at 80° C. 52 g of a 4 M aqueous HCl solution was added dropwise to the reaction mixture, and sodium metasilicate nonahydrate (Na 0) dissolved in 31 g of purified water was added dropwise to the reaction mixture. ２ SiO ３ ・9H ２ An aqueous solution of 4.5 g of HCl (O) was quickly added, followed by 16 g of 4 M HCl aqueous solution. The reaction solution was stirred at 60°C for 1 hour and then cooled to room temperature. 47 g of KCl was then added, and the resulting precipitate was filtered off by suction filtration. The mixture was washed with 33 g of 1 M KCl aqueous solution and 33 g of cold water, and then dried under vacuum to obtain 26 g of the target compound. ２９ Si-NMR (119.22MHz, D ２ O): δ (ppm) = -84.6 (s, 1Si). １８３ W-NMR (20.84MHz, D ２ O): δ (ppm) = -97.43 (m, impurity), -101.85 (s, 2W), -116.26 (s, 2W), -119.29 (s, 1W), -125.62 (s, 2W), -140.85 (s, 2W), -174.53 (s, 2W).

[0186] Comparative Production Example 2 (Example corresponding to steps (2) and (3)): Synthesis of heteropolyacid salt (tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-divinyldisiloxane-1,1,3,3-tetrayl)undecatungstosilicate) (M-3) with modified defect sites. ８ [SiW １１ O ３９ After stirring, 3.8 g (1.3 mmol) of vinyltrimethoxysilane (CH ２ =CH-Si(OCH ３ )３ ) was added, followed by the addition of 10.5 g of 1 M hydrochloric acid, and the mixture was stirred for 20 hours. The unreacted powder was filtered off by suction, and 53 g (7.6 mmol) of a 6.3% aqueous solution of bis(2-trifluoromethylphenyl)phenylsulfonium chloride was added to precipitate a powder. The precipitated powder was poured into a suction funnel with a small amount of pure water, filtered off by suction, and washed with 151 g of isopropanol. Further thorough vacuum drying yielded 5.0 g of the target compound M-3 as a white powder. The silicon and tungsten NMR peaks shown below indicate the presence of impurities. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 5.94 (dd, 2H), 6.08 (dd, 2H), 6.13 (dd, 2H), 7.65-8.35 (m, 52H). ２９ Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -66.56 (s, 2Si), -69.74 (m, impurity), -85.29 (s, 1Si), -85.54 (s, impurity). １８３ W-NMR (20.84 MHz, DMSO-d6): δ (ppm) = -91.48 (s, impurity), -105.52 (s, 2W), -107. 54 (s, 2W), -112.04 (s, 1W), -126.08 (s, 2W), -170.95 (s, 2W), -247.66 (s, 2W). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 700.3 (median) ([C ４ H ６ O ４０ Si ３ W １１ ] ４－ )

[0187] <Synthesis Example 1: 3-(2-((1-methylcyclopentyl)oxycarbonyl)ethylthio)propyltrimethoxysilane> 20 mL of methyl ethyl ketone was added to 7.7 g of 1-methylcyclopentyl acrylate and 9.8 g of 3-mercaptopropyltrimethoxysilane, and 0.3 g of 1,1'-azobis(cyclohexane-1-carbonitrile) was added and stirred uniformly. Nitrogen was then blown in for 30 minutes, and nitrogen bubbling was performed. Thereafter, the reaction solution was heated from room temperature to 90°C over 30 minutes in nitrogen. The temperature was maintained at 90°C for 7 hours. The reaction solution was then distilled off using a rotary evaporator. Further thorough vacuum drying yielded 16.6 g of the target compound as a colorless liquid. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.56 (t, 2H), 1.39 (s, 3H), 1.56-1.81 (m, 10H), 2.42 (t, 2H), 2.58 (t, 2H), 2.83 (t, 2H), 3.55 (s, 9H).

[0188] [Production Example 4-1 (Example of the First Half of Steps (2) and (3a′)): Synthesis of Defect Site-Modified Heteropolyacid Salt (Tetrakis(benzyltriethylammonium)(1,3-di(3-(2-((1-methylcyclopentyl)oxycarbonyl)ethylthio)propyl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate) (M-4-1)] Target compound M-4-1 was obtained in the same manner as above, except that in Production Example 2-1, 3-(2-((1-methylcyclopentyl)oxycarbonyl)ethylthio)propyltrimethoxysilane was used instead of vinyltrimethoxysilane and an aqueous solution of benzyltriethylammonium chloride was used instead of the aqueous solution of (2-trifluoromethylbenzyl)triallylammonium bromide as raw materials. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.67 (t, 4H), 1.34 (t, 36H), 1.49 (s, 6H), 1.54-1.71 (m, 16H), 1. 99-2.08 (m, 4H), 2.49 (t, 4H), 2.58 (t, 4H), 2.67 (t, 4H), 3.20 (q, 24H), 4.49 (s, 8H), 7.52 (m, 20H). ２９Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.02 (s, 2Si), -85.04 (s, 1Si). ESI-MS: POSITIVE m / z 192.2 ([C １３ H ２２ N] ＋ ) NEGATIVE m / z 801.1 (median) ([C ２４ H ４２ O ４４ S ２ Si ３ W １１ ] ４－ )

[0189] [Production Example 4-2 (Example of the latter half of step (3a′) and (3b′)): Synthesis of heteropolyacid salt (tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-di(3-(2-((1-methylcyclopentyl)oxycarbonyl)ethylthio)propyl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate) (M-4-2) having modified defect sites] To 14.5 g of the powder M-4-1 obtained in Production Example 4-1, 230 mL of dichloromethane was added, followed by the addition of 264 g (18.2 mmol) of a 3% aqueous solution of bis(2-trifluoromethylphenyl)phenylsulfonium chloride. This was followed by stirring at room temperature for 1 hour, and the aqueous layer was removed. Furthermore, using a similar process, 264 g (2.9 mmol) of a 0.5% aqueous solution of bis(2-trifluoromethylphenyl)phenylsulfonium chloride was added, and the mixture was stirred for 10 minutes, after which the aqueous layer was removed. Using a similar process, the mixture was washed once with pure water, once with 1% hydrochloric acid, and three times with pure water. To the resulting dichloromethane solution, 400 mL of methyl t-butyl ether was added, and the precipitated powder was filtered off by suction filtration and washed with 400 mL of methyl t-butyl ether. Further thorough vacuum drying afforded 15.7 g of the target compound M-4-2 as a white solid. １H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.67 (t, 4H), 1.49 (s, 6H), 1.54-1.71 (m, 16H) , 1.99-2.08 (m, 4H), 2.49 (t, 4H), 2.58 (t, 4H), 2.67 (t, 4H), 7.65-8.35 (m, 52H). ２９ Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.02 (s, 2Si), -85.04 (s, 1Si). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 801.1 (median) ([C ２４ H ４２ O ４４ S ２ Si ３ W １１ ] ４－ )

[0190] [Production Example 4-3 (Example of the latter half of step (3a′) and (3b′)): Synthesis of heteropolyacid salt (tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-di(3-(2-((1-methylcyclopentyl)oxycarbonyl)ethylthio)propyl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate) (M-4-3) having modified defect sites] To 14.5 g of the powder of M-4-1 obtained in Production Example 4-1, 230 mL of dichloromethane was added, followed by 264 g (18.2 mmol) of a 3% aqueous solution of bis(2-trifluoromethylphenyl)phenylsulfonium chloride. This was then stirred at room temperature for 1 hour, and the aqueous layer was removed. Furthermore, using a similar process, 264 g (2.9 mmol) of a 0.5% aqueous solution of bis(2-trifluoromethylphenyl)phenylsulfonium chloride was added, and after stirring for 10 minutes, the aqueous layer was removed. Using a similar process, the mixture was washed once with pure water, once with 5% citric acid, and three times with pure water. To the resulting dichloromethane solution, 400 mL of methyl t-butyl ether was added, and the precipitated powder was filtered off by suction filtration and washed with 400 mL of methyl t-butyl ether. Further thorough vacuum drying afforded 15.4 g of the target compound M-4-3 as a white solid.

[0191] [Production Example 5-1 (Example of the First Half of Steps (2) and (3a′)): Synthesis of Defect Site-Modified Heteropolyacid Salt (Tetrapotassium (1,3-di(4-methoxymethoxyphenyl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate) (M-5-1)] The target compound M-5-1 was obtained in the same manner as above, except that in Production Example 3, 4-methoxymethoxyphenyltrimethoxysilane was used instead of methyltrimethoxysilane as the raw material compound, and a potassium chloride aqueous solution was used instead of the (2-trifluoromethylbenzyl)triallylammonium bromide aqueous solution. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 3.37 (s, 6H), 5.22 (s, 4H), 7.05 (d, 4H), 7.66 (d, 4H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -64.72 (s, 2Si), -85.02 (s, 1Si). ESI-MS: POSITIVE m / z 39.0 ([K] ＋ ) NEGATIVE m / z 755.1 (median) ([C １６ H １８ O ４４ Si ３ W １１ ]４－ )

[0192] [Production Example 5-2 (Example of the latter half of step (3a′) and (3b′)): Synthesis of heteropolyacid salt (tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-di(4-methoxymethoxyphenyl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate) (M-5-2) having modified defect sites] To 11.6 g of the powder M-5-1 obtained in Production Example 5-1, 230 mL of dichloromethane was added, followed by the addition of 264 g (18.2 mmol) of a 3% aqueous solution of bis(2-trifluoromethylphenyl)phenylsulfonium chloride. This was followed by stirring at room temperature for 1 hour, and the aqueous layer was removed. Furthermore, using a similar process, 264 g (2.9 mmol) of a 0.5% aqueous solution of bis(2-trifluoromethylphenyl)phenylsulfonium chloride was added, and the mixture was stirred for 10 minutes, after which the aqueous layer was removed. Using a similar process, the mixture was washed once with pure water, once with 1% hydrochloric acid, and three times with pure water. To the resulting dichloromethane solution, 400 mL of methyl t-butyl ether was added, and the precipitated powder was filtered off by suction filtration and washed with 400 mL of methyl t-butyl ether. Further thorough vacuum drying afforded 15.1 g of the target compound M-5-2 as a white solid. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 3.37 (s, 6H), 5.22 (s, 4H), 7.05 (d, 4H), 7.65-8.35 (m, 56H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -64.72 (s, 2Si), -85.02 (s, 1Si). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 755.1 (median) ([C １６ H １８ O ４４ Si ３ W １１ ] ４－ )

[0193] [2. Evaluation of Purity by NMR and Evaluation of Purity by Metal Content] The heteropolyacid salts M-1-1, M-1-2, M-2, M-3, M-4-2, M-4-3, and M-5-2 in which the defect sites are modified were evaluated. １８３ W-NMR, and ２９ In Si-NMR, samples in which no impurities were observed were rated A, and samples in which impurities were observed were rated B. The results are shown in Table 1.

[0194] Furthermore, the amount of metal or metal ion (Li, Na, Mg, Al, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Sr, Zr, Mo, Ag, Cd, Sn, Sb, Ba, W, Pb, and Au) contained in the heteropolyacid salts M-1-1, M-1-2, M-2, M-3, M-4-2, M-4-3, and M-5-2 in which the defect sites were modified was measured using an inductively coupled plasma mass spectrometer (ICP-MS (Inductively Coupled Plasma Mass Spectrometry), Agilent 8900: manufactured by Agilent Technologies). Among the above metals or metal ions, if the content of the metal or metal ion with the highest content, excluding tungsten, was less than 100 ppb, it was evaluated as A, and if it was 100 ppb or more, it was evaluated as B. The results are shown in Table 1.

[0195]

[0196] From the above, when comparing Production Example 1 and Comparative Production Example 1, impurities were observed in Comparative Production Example 1 from the production stage of the mono-defect potassium silicotungstate. Furthermore, when heteropolyacid salt M-3 with modified defect sites was produced in Comparative Production Example 2, it was found from the NMR peaks of silicon and tungsten that impurities different from the target compound were contained. These impurities were difficult to remove even by techniques such as recrystallization. On the other hand, in any of the mono-defect potassium silicotungstate and the heteropolyacid salts M-1-1, M-1-2, and M-2 with modified defect sites produced in Production Examples 1 to 3, no impurity peaks were detected in the NMR of silicon and tungsten.

[0197] Furthermore, when the heteropolyacid salt M-1-1 in which the defect sites were modified obtained in Production Example 2-1 and the heteropolyacid salt M-1-2 in which the defect sites were modified obtained in Production Example 2-2 were compared, the content of metal or metal ion impurities contained in the heteropolyacid salt M-1-2 in which the defect sites were modified was lower. This shows that by including step (3b'), which is a step of washing the heteropolyacid salt in which the defect sites were modified with an acidic aqueous solution, a heteropolyacid salt in which the defect sites were modified and which has a higher purity and less metal impurities can be produced.

[0198] Furthermore, when comparing the heteropolyacid salt M-2 in which the defect sites were modified obtained in Production Example 3 with the heteropolyacid salt M-1-1 in which the defect sites were modified obtained in Production Example 2-1, although the contents of the metals or metal ions other than tungsten, the highest content of which was 100 ppb or more in both cases, it was found that the heteropolyacid salt M-2 in which the defect sites were modified by salt exchange with an organic ammonium salt had fewer metal impurities than the heteropolyacid salt M-1-1 in which the defect sites were modified by salt exchange with an organic sulfonium salt, and thus gave a heteropolyacid salt in which the defect sites were modified with a higher purity. For this reason, in Production Examples 4-1 and 4-2, after steps (1) and (2), as step (3a'), salt exchange with an ammonium salt was performed, followed by salt exchange with an organic sulfonium salt, which is an onium salt. Furthermore, as step (3b'), the heteropolyacid salt in which the defect sites were modified was washed with an acidic aqueous solution using hydrochloric acid, whereby the heteropolyacid salt M-4-2 in which the metal impurities were further reduced could be produced. Similarly, in Production Example 4-3, after the above step (3a′), a step (3b′) was carried out in which the heteropolyacid salt having modified defect sites was washed with an acidic aqueous solution using citric acid, whereby a heteropolyacid salt M-4-3 having modified defect sites and reduced metal impurities could be produced.

[0199] In Production Examples 5-1 and 5-2, after steps (1) and (2), in step (3a'), salt exchange with a potassium salt was performed, followed by salt exchange with an organic sulfonium salt, which is an onium salt. Furthermore, in step (3b'), the heteropolyacid salt having modified defect sites was washed with an acidic aqueous solution using hydrochloric acid, thereby enabling the production of heteropolyacid salt M-5-2 having modified defect sites and further reduced metal impurities.

Claims

1. A method for producing a heteropolyacid salt or a mixture thereof having a modified defect site, comprising: (1) a step of converting a Keggin type or Dawson type heteropolyacid salt into a one-deficient Keggin type or Dawson type heteropolyacid salt; and (2) a step of reacting the one-deficient Keggin type or Dawson type heteropolyacid salt with a P, Si, Ge or Sn compound having one or more hydro groups or organic groups and two or more leaving groups to obtain a heteropolyacid salt or a mixture thereof having a modified defect site represented by general formula (1). (A ｐ＋ ) ｑ [C （ｐ×ｑ）－ (I) [In formula (I), A ｐ＋ are each independently H ＋ , a metal ion, or an ammonium ion; （ｐ×ｑ）－ represents a heteropolyacid anion in which the defective site in a one-defect Keggin type or Dawson type heteropolyacid anion is modified; p is an integer of 1 to 5, and q is a real number.

2. The method for producing a heteropolyacid salt or a mixture thereof having modified defect sites according to claim 1, wherein the step (1) comprises the step of: (1a) adjusting the pH of a solution containing the Keggin type or Dawson type heteropolyacid salt to 5.0 or less.

3. A method for producing a heteropolyacid salt or a mixture thereof having modified defect sites according to claim 1, wherein the step (1) comprises: (1a) adjusting the pH of a solution containing the Keggin type or Dawson type heteropolyacid salt to 5.0 or less; and (1b) adjusting the pH of the solution to 4 to 8 using a weak base or a base.

4. The method for producing a heteropolyacid salt or a mixture thereof having modified defect sites according to claim 1, wherein the step (2) comprises the step of: (2a) reacting the singly defective Keggin type or Dawson type heteropolyacid salt with a P, Si, Ge or Sn compound having one or more hydro groups or organic groups and two or more leaving groups in a solution having a pH of 5.0 or less.

5. A method for producing a heteropolyacid salt or a mixture thereof having modified defect sites according to claim 1, wherein the polyatom of the Keggin type or Dawson type heteropolyacid salt is Mo, W, V, Nb or Ta, and the heteroatom is P, Si, B, S or Ge.

6. The method for producing a heteropolyacid salt having a modified defect site or a mixture thereof according to claim 1, wherein the one-defect Keggin type or Dawson type heteropolyacid salt is represented by general formula (III-1) or (III-2). [XM １１ O ３９ ] ｃ２１－ (III-1) [X ２ M １７ O ６１ ] ｃ２２－ (III-2) [In the formula, X represents a heteroatom of P, Si, B, S, or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; and c21 and c22 are natural numbers.] 7. A method for producing a heteropolyacid salt or a mixture thereof having a modified defective site as described in claim 1, wherein the organic group has one or more of a halogen atom, a haloalkyl group, a hydroxyl group, a thiol group, a nitro group, a cyano group, a carboxyl group, an amino group, a sulfo group, an epoxy group, a glycidyl group, or an amide group.

8. The method for producing a heteropolyacid salt or a mixture thereof having modified defect sites according to claim 1, wherein the organic group has one or more ethylenically unsaturated double bonds.

9. The method for producing a heteropolyacid salt or a mixture thereof having a modified defect site according to claim 1, wherein the organic group has one or more hydroxyl groups or carboxyl groups having a protecting group.

10. Said C （ｐ×ｑ）－ The method for producing a heteropolyacid salt or a mixture thereof having a modified defect site according to claim 1, wherein [XM １１ O ３９ (R １Ａ X') ２ O] ｃ３１－ (VI-1) [XM １１ O ３９ (R １Ｂ１ R １Ｂ２ Si) ２ ] ｃ３１－ (VI-2) [XM １１ O ３９ (R １Ｃ P = O) ２ ] ｃ３１－ (VI-3) [XM １１ O ３９ (R １Ｄ X'')] ｃ３１－ (VI-4) [X ２ M １７ O ６１ (R １Ａ X') ２ O] ｃ３２－ (VI-5) [X ２ M １７ O ６１ (R １Ｂ１ R １Ｂ２ Si) ２ ] ｃ３２－ (VI-6) [X ２ M １７ O ６１ (R １Ｃ P = O) ２ ] ｃ３２－ (VI-7) [X ２ M １７ O ６１ (R １Ｄ X'')] ｃ３２－ (VI-8) [wherein, X represents a heteroatom of P, Si, B, S or Ge; M represents a polyatom of Mo, W, V, Nb or Ta; X' represents a heteroatom of Si or Ge; X'' represents a heteroatom of Si, Ge or Sn; R １Ａ ~R １Ｄ each independently represents a hydro group or a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, １Ａ ~R １Ｄ The divalent carbon atom at any position except the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), １Ａ ~R １Ｄ The hydrogen atom contained in may be replaced by (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, or (s) a hydroxy group or a carboxy group having a protecting group; c31 and c32 are natural numbers.] 11. A method for producing a heteropolyacid salt or a mixture thereof having a modified defect site according to claim 1, further comprising the step of (3) salt-exchanging the heteropolyacid salt or a mixture thereof having a modified defect site represented by the general formula (I).

12. A method for producing a heteropolyacid salt or a mixture thereof having a modified defective site according to claim 11, wherein the step (3) comprises: (3a) a step of salt-exchanging the heteropolyacid salt or a mixture thereof having a modified defective site represented by the general formula (I) with an alkali metal salt, an alkaline earth metal salt, an aluminum salt, or an onium salt.

13. The method for producing a heteropolyacid salt or a mixture thereof having modified defect sites according to claim 12, wherein the onium salt is an organic sulfonium salt, an organic iodonium salt, an organic ammonium salt, or an organic phosphonium salt.

14. The method for producing a heteropolyacid salt or a mixture thereof having a modified defect site according to claim 11, wherein the step (3) comprises the step of: (3b) obtaining a heteropolyacid salt or a mixture thereof having a modified defect site represented by general formula (VII). (A ｍ＋ ) ａ (B ｎ＋ ) ｂ (C （ａｍ＋ｂｎ）－ ) (VII) [wherein, when b is 0, A ｍ＋ are each independently H ＋ , a metal ion, or an ammonium ion, at least one of which is ｐ＋ Alkali metal ions, alkaline earth metal ions, or Al ３＋ If b is a real number greater than 0, then A ｍ＋ are each independently H ＋ , a metal ion, or an ammonium ion; B ｎ＋ each independently represents an organic sulfonium cation, an organic sulfonium dication, an organic iodonium cation, an organic ammonium cation, an organic ammonium dication, an organic phosphonium cation, or an organic phosphonium dication; （ａｍ＋ｂｎ）－ represents a heteropolyacid anion in which the defective site in a one-defect Keggin type or Dawson type heteropolyacid anion is modified; m is an integer of 1 to 5, n is an integer of 1 or 2, and a is a real number.

15. A method for producing a heteropolyacid salt or a mixture thereof having modified defect sites according to claim 11, wherein the step (3) comprises: (3a') a step of replacing the cation moiety of the heteropolyacid salt or mixture thereof having modified defect sites represented by general formula (I) with a metal ion, ammonium ion or organic ammonium cation by a salt exchange reaction, and a further step of salt exchanging the heteropolyacid salt with an onium salt.

16. The method for producing a heteropolyacid salt or a mixture thereof having a modified defect site according to claim 11, wherein the step (3) comprises the step of: (3b') washing the heteropolyacid salt or a mixture thereof having a modified defect site represented by general formula (VII) with an acidic aqueous solution having a pH of 6 or less. (A ｍ＋ ) ａ (B ｎ＋ ) ｂ (C （ａｍ＋ｂｎ）－ ) (VII) [wherein, when b is a real number greater than 0, A ｍ＋ are each independently H ＋ , a metal ion, or an ammonium ion; B ｎ＋ each independently represents an organic sulfonium cation, an organic sulfonium dication, an organic iodonium cation, an organic ammonium cation, an organic ammonium dication, an organic phosphonium cation, or an organic phosphonium dication; （ａｍ＋ｂｎ）－ represents a heteropolyacid anion in which the defective site of a one-defect Keggin type or Dawson type heteropolyacid anion has been modified; m is an integer of 1 to 5, n is an integer of 1 or 2, a is a real number, and b is a real number greater than 0.

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