Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
  • C07C381/12—Sulfonium compounds
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G41/00—Compounds of tungsten
  • C01G41/006—Compounds containing tungsten, with or without oxygen or hydrogen, and containing two or more other elements
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G41/00—Compounds of tungsten
  • C01G41/02—Oxides; Hydroxides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
  • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
  • C07D327/06—Six-membered rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
  • C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
  • C07D333/76—Dibenzothiophenes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
  • C07D335/02—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings

Definitions

• the present invention relates to a heteropolyoxotungstate compound or a solvate thereof or a mixture thereof, and a method for producing the same.
• Polyoxometalates are anionic metal oxide clusters that have a structure in which early transition metals having d0 or d1 electron configurations (e.g., Mo (hexavalent or pentavalent), W (hexavalent or pentavalent), V (pentavalent), Nb (pentavalent), Ta (pentavalent), etc.) are oxygen-bridged.
• early transition metals having d0 or d1 electron configurations e.g., Mo (hexavalent or pentavalent), W (hexavalent or pentavalent), V (pentavalent), Nb (pentavalent), Ta (pentavalent), etc.
• Patent Document 1 describes that a POM containing polyoxomolybdic acid and a compound having a pyridinium skeleton has a high photoluminescence quantum yield.
• Polyoxotungstic acid a type of POM, includes isopolyoxotungstic acid, which is composed of an oxygen acid containing tungsten, and heteropolyoxotungstic acid, which is composed of an oxygen acid containing tungsten and one or more other heteroatoms.
• the heteroatoms that make up heteropolyoxotungstic acid can be selected from many elements in groups I-VIII, including Si, Ge, and P, and by changing the combination and composition ratio, POMs with different physicochemical properties can be formed.
• Patent Document 2 discloses a photochromic article that contains a complex of a polyoxometalate anion, such as phosphotungstic acid, and a counter cation, such as an ammonium cation.
• the present invention aims to provide a novel heteropolyoxotungstate compound, a solvate thereof, or a mixture thereof, and a method for producing the same.
• Each A m+ independently represents H + , a metal ion, or an ammonium ion;
• Each B n+ independently represents a sulfonium cation;
• C- (x+y) represents heteropolyoxotungstic acid;
• m is an integer from 1 to 5
• n is an integer of 1 or 2
• x and x/m are integers, and y and y/n are natural numbers.
• heteropolyoxotungstate compound or a solvate thereof according to ⁇ 1>, wherein the heteropolyoxotungstic acid is a heteropolyoxotungstic acid represented by general formula (II-1) or (II-2), or a heteropolyoxotungstic acid represented by a defective species thereof.
• XW 12 O 40 -z1 (II-1) [X 2 W 18 O 62 ] -z2 (II-2) [Wherein, X's each independently represent B, Al, SiIV , GeIV , PV , AsV , VV , CrIII , FeIII , CoIII , CoII , CuII , CuI , Zn, SeVI , or SVI ; z1 and z2 are natural numbers.
• heteropolyoxotungstate compound or a solvate thereof according to ⁇ 2> , wherein the heteropolyoxotungstic acid represented by (II-1) is [PW 12 O 40 ] 3 ⁇ , [SiW 12 O 40 ] 4 ⁇ , [BW 12 O 40 ] 5 ⁇ or [SW 12 O 40 ] 2 ⁇ .
• heteropolyoxotungstate compound or a solvate thereof according to ⁇ 2>, wherein the heteropolyoxotungstic acid represented by (II-2) is [P 2 W 18 O 62 ] 6 ⁇ , [Si 2 W 18 O 62 ] 8 ⁇ or [S 2 W 18 O 62 ] 4 ⁇ .
• the heteropolyoxotungstic acid is a Keggin type or Dawson type, or a silicotungstic acid that is a defective species thereof, and the heteropolyoxotungstic acid comprises two or more different heteropolyoxotungstate compounds or solvates thereof according to ⁇ 1>,
• the heteropolyoxotungstic acid is a Keggin type or a Dawson type, or a phosphotungstic acid which is a defective species thereof, and the heteropolyoxotungstic acid comprises two or more different heteropolyoxotungstate compounds or solvates thereof according to ⁇ 1>,
• the sulfonium cation is a sulfonium cation represented by general formula (III-1) or a sulfonium dication represented by general formula (III-2).
• R 3A , R 3B and R 3C each independently represent a C 1-18 hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group which may have a substituent;
• Any two of R 3A , R 3B and R 3C may be linked to each other directly via a single bond or via a divalent linking group, -O-, -S-, -C( ⁇ O)-, -S( ⁇ O)-, -S( ⁇ O) 2
• the sulfonium cation is a sulfonium cation represented by general formula (IV-1), (IV-2), (IV-3), (IV-4) or (IV-5).
• Ar 4A , Ar 4B , Ar 4C , Ar 4D , Ar 4E , Ar 4F and Ar 4G each independently represent a C 6-18 aryl group or a 5- to 18-membered heterocyclic group which may have a substituent;
• the C 6-18 aryl group or 5-18 membered heterocyclic group which may have a substituent is preferably a C 1-18 hydrocarbyl group, a C 1-18 hydrocarbyloxy group, a C 1-18 hydrocarbylcarbonyl group, a C 1-18 hydrocarbylcarbonyloxy group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbyloxycarbonyl group , a C 1-18 hydrocarbylamino group, a di-C 1-18 hydrocarbylamino group , C and which may be substituted by a 1-18 hydrocarbyl
• the sulfonium cation is a sulfonium cation represented by general formula (V): The heteropolyoxotungstate compound or a solvate thereof according to ⁇ 1>.
• R 5A to R 5C are each independently a halogen atom, a hydroxy group, a thiol group, a nitro group, a carboxy group, an amino group, a sulfo group, a group in which the hydrogen atom of a carboxy group or a hydroxy group is substituted with an acid dissociable group, or a C 1-18 hydrocarbyl group in which some of the hydrogen atoms may be substituted with a halogen atom, a hydroxy group, a thiol group, a nitro group, a cyano group, a carboxy group, an amino group, a sulfo group, a carboxy group or a hydroxy group in which the hydrogen atom of a hydroxy group is substitute
• R 5A to R 5C is a halogen atom, a C 1-4 haloalkyl group, a C 1-4 haloalkyloxy group, a C 1-18 hydrocarbyloxy group in which at least a portion of the hydrogen atoms are substituted with halogen atoms, or a C 1-18 hydrocarbylcarbonyloxy group in which at least a portion of the hydrogen atoms are substituted with halogen atoms;
• At least one of R 5A to R 5C is a C 4-18 hydrocarbyl group, a C 4-18 hydrocarbyloxy group, a C 4-18 hydrocarbylcarbonyl group, a C 4-18 hydrocarbylcarbonyloxy group, a C 4-18 hydrocarbyloxycarbonyl group, a C 4-18 hydrocarbyloxycarbonyl group, a C 4-18 hydrocarbylamino group, a di-C 4-18 hydrocarbylamino group, a C 4-18 hydrocarbylaminocarbonyl group, a di-C 4-18 hydrocarbylaminocarbonyl group, a C 44-18 hydrocarbylcarbonylamino group, a C 4-18 hydrocarbylaminocarbonyloxy group, a di-C 4-18 hydrocarbylaminocarbonyloxy group, a C 4-18 hydrocarbylaminocarbonyloxy group, a C 4-18 hydrocarbylaminocarbonyloxy group, a C 4-18 hydrocarbylaminocarbon
• R 5A to R 5C is a C 1-18 hydrocarbyl group, a C 1-18 hydrocarbyloxy group, a C 1-18 hydrocarbylcarbonyl group, a C 1-18 hydrocarbylcarbonyloxy group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbylamino group, a di-C 1-18 hydrocarbylamino group, a C 1-18 hydrocarbylaminocarbonyl group, a C 1-18 hydrocarbylaminocarbonyl group, a C 1-18 hydrocarbylaminocarbonyl group, a C 1-18 hydrocarbylaminocarbonyloxy group , a di-C 1-18 hydrocarbylaminocarbonyloxy group, a C 1-18 hydrocarbylaminocarbonyloxy group, a C 1-18 hydrocarbylaminocarbonyloxy group , a di-C 1-18 hydrocarbylaminocarbonyl
• the acid dissociable group, wherein the carbon bonded to the carboxy group or the hydroxy group is a tertiary carbon.
• a method for producing a heteropolyoxotungstate compound represented by general formula (I) or a solvate thereof comprising the steps of: A production method comprising a step of reacting a compound represented by general formula (VI-1) with a compound represented by general formula (VI-2) to carry out salt exchange.
• a method for producing a heteropolyoxotungstate compound represented by general formula (I) or a solvate thereof comprising the steps of: A step of reacting a compound represented by general formula (VI-1) with a compound represented by general formula (VI-2) to carry out salt exchange; removing the compound represented by general formula (VI-3) from the produced compounds represented by general formulas (I) and (VI-3);
• the manufacturing method according to claim 1, (A m+ ) x/m (B n+ ) y/n (C- (x+y) ) (I) (A m+ ) x/m (A' m'+ ) y/m' (C - (x+y) ) (VI-1) (B n+ ) y/n (Y ⁇ ) y (VI-2) (A' m'+ ) y/m' (Y - ) y (VI-3) [Wherein, Each A m+ independently represents H + , a metal ion
• a method for producing a heteropolyoxotungstate compound represented by general formula (I) or a solvate thereof comprising: A step of ion-exchanging A'm'+ of the compound represented by general formula (VI-1) with H + using an ion exchange resin; A step of reacting the compound represented by general formula (VI-4) produced by the above step with a compound represented by general formula (VI-2);
• the manufacturing method according to claim 1, (A m+ ) x/m (B n+ ) y/n (C- (x+y) ) (I) (A m+ ) x/m (A' m'+ ) y/m' (C - (x+y) ) (VI-1) (A m+ ) x/m (H + ) y (C - (x+y) ) (VI-4) (B n+ ) y/n (Y - ) y (VI-2) [Wherein, Each A m+ independently represents H
• the present invention provides a novel heteropolyoxotungstate compound, a solvate thereof, or a mixture thereof, and a method for producing the same.
• the heteropolyoxotungstate compound according to one embodiment of the present invention is represented by the following general formula (I).
• Each A m+ independently represents H + , a metal ion, or an ammonium ion;
• Each B n+ independently represents a sulfonium cation;
• C- (x+y) represents heteropolyoxotungstic acid;
• m is an integer from 1 to 5
• n is an integer of 1 or 2
• x and x/m are integers, and y and y/n are natural numbers.
• a m+ is also referred to as "another counter cation”.
• the heteropolyoxotungstate compound according to this embodiment is represented by the following general formula (I). (A m+ ) x/m (B n+ ) y/n (C- (x+y) ) (I) C- (x+y) represents heteropolyoxotungstic acid; x is an integer and y is a natural number.
• the heteropolyoxotungstic acid according to the present embodiment is not particularly limited, and may be any known or commonly used one.
• the heteropolyoxotungstic acid may be a Keggin type or a Dawson type or a defective type thereof, as well as an Anderson type, a Lacuna-Kegin type, a substituted Keggin type, or a Strandberg type, and any of these may be used.
• the heteropolyoxotungstic acid may include all isomers and mixtures of isomers, such as geometric isomers, optical isomers, rotational isomers, stereoisomers, and tautomers, that exist structurally, and is not limited to the description of the chemical formula for convenience.
• Keggin type heteropolyoxotungstic acid ([ XW12O40 ] -z1 : X each independently represents B, Al, SiIV , GeIV , PV , AsV, VV , CrIII , FeIII , CoIII, CoII , CuII , CuI , Zn , SeVI , or SVI ; z1 is a natural number) is known to exist in ⁇ -Keggin type, ⁇ - Keggin type, ⁇ - Keggin type, etc.
• the chemical formula [ XW12O40 ] -z1 includes the above isomers or a mixture of these isomers.
• Dawson-type heteropolyoxotungstic acids ([X 2 W 18 O 62 ] -z2 : X each independently represents B, Al, Si IV , Ge IV , P V , As V , V V , Cr III , Fe III , Co III , Co II , Cu II , Cu I , Zn, Se VI or S VI ; z2 is a natural number) are known to include ⁇ -Dawson type, ⁇ -Dawson type, ⁇ -Dawson type and the like.
• the chemical formula [X 2 W 18 O 62 ] -z2 includes the above isomers or a mixture of these isomers.
• heteropolyoxotungstic acid it is preferable to use a Keggin type or a Dawson type, or a defective type thereof, from the viewpoint of excellent thermal stability and stability under an oxidizing atmosphere.
• Keggin type heteropolyoxotungstic acids include [PW 12 O 40 ] 3 ⁇ , [SiW 12 O 40 ] 4 ⁇ , [BW 12 O 40 ] 5 ⁇ , [SW 12 O 40 ] 2 ⁇ , etc.
• Examples of Dawson type heteropolyoxotungstic acids include [P 2 W 18 O 62 ] 6 ⁇ , [Si 2 W 18 O 62 ] 8 ⁇ , [S 2 W 18 O 62 ] 4 ⁇ , etc.
• Keggin type or Dawson type defect type heteropolyoxotungstic acids include, for example, [PW 9 O 34 ] 9 ⁇ , [PW 10 O 36 ] 7 ⁇ , [PW 11 O 39 ] 7 ⁇ , [SiW 9 O 34 ] 10 ⁇ , [SiW 10 O 36 ] 8 ⁇ , [SiW 11 O 39 ] 8 ⁇ , [P 2 W 17 O 61 ] 10 ⁇ , and the like.
• the heteropolyoxotungstic acid according to this embodiment is preferably [ PW12O40 ] 3- , [ SiW12O40 ] 4- , [BW12O40] 5- , [ SW12O40 ] 2- , [ P2W18O62 ]6-, [Si2W18O62]8-, or [S2W18O62 ] 4- , and more preferably [ PW12O40 ] 3- , [ SiW12O40 ] 4- , [BW12O40 ] 5- , or [ SW12O40 ] 2- .
• the heteropolyoxotungstate compound according to this embodiment is represented by the following general formula (I). (A m+ ) x/m (B n+ ) y/n (C- (x+y) ) (I) Each B n+ independently represents a sulfonium cation; n is an integer of 1 or 2, and y and y/n are natural numbers.
• halogen atom means a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
• C 1-6 refers to the number of carbon atoms in the core group.
• C 1-18 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.
• Hydrocarbylene groups include alkylene groups and arylene groups.
• the "C 1-18 hydrocarbylene group” is not particularly limited, and examples thereof include “C 1-18 hydrocarbylene groups” 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.
• C 1-18 hydrocarbylene groups such as methylene group, ethylene group, n-propylene group, i-propylene group, cyclopentadiyl group, cyclohexanediyl group, oxyethane-1,1-diyl group, oxyethane-1
• C 6-18 arylene groups such as a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a 1,4-naphthylene group, a 1,5 - naphthylene group, a 1,8-naphthylene group, a 4,4'-biphenylene group, an anthracenediyl group, a phenanthrenediyl group, a naphthacenediyl group, a pyrenediyl group, a perylenediyl group, and a chrysenediyl group.
• a 1,4-phenylene group such as a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a 1,4-naphthylene group, a 1,5 - naphthylene group, a 1,8-naphthylene group, a 4,4'-biphenylene group
• C 1-18 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, and a 3-methylpentyl group.
• a "C 1-18 haloalkyl group” refers to a “C 1-18 alkyl group” in which one or more hydrogen atoms have been substituted with halogen atoms.
• the "C 1-18 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.
• C2-18 alkenyl group refers to an alkenyl group having one or more double bonds in a " C1-18 alkyl group” having 2 or more carbon atoms, and is intended to include alkadienyl groups, alkatrienyl groups, and the like.
• the " C2-18 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.
• a "C 2-18 alkynyl group” refers to an alkynyl group having one or more triple bonds in a "C 1-18 alkyl group” having 2 or more carbon atoms.
• the "C 2-18 alkynyl group” is not particularly limited, and examples thereof include ethynyl, 1-propynyl, 2-propynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, and dodecynyl groups.
• C 3-18 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, and the like.
• the "C 3-18 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
• 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 condensed 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
• C 6-18 aryl group refers to an aromatic hydrocarbon cyclic group having 6 to 18 carbon atoms, which may be a monocyclic ring, a polycyclic ring, or a condensed ring.
• the "C 6-18 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, and an anthracenyl group.
• C 7-18 aralkyl group refers to a "C 1-12 alkyl group” in which a substitutable moiety is substituted with the above-mentioned "C 6-12 aryl group”.
• the "C 7-18 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.
• 5- to 18-membered aromatic heterocyclic group refers to a monocyclic, polycyclic or fused 5- to 18-membered aromatic heterocyclic group containing one or more heteroatoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms.
• the "5- to 18-membered aromatic heterocyclic group” is not particularly limited, and examples thereof include a pyrrolyl group, a furyl group, a thienyl group, an imidazolyl group, a triazolyl group, a tetrazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a furazanyl group, a thiadiazolyl group, an oxadiazolyl group, a pyridyl group, a pyrazinyl group, a pyridazinyl group, a pyrimidinyl group, a triazinyl group, a purinyl group, a pteridinyl group, a quinolyl group, an isoquinolyl group, a naphthyridinyl group, and the like.
• Examples of such groups include an isyl group, a quinoxalinyl group, a cinnolinyl group, a quinazolinyl group, a phthalazinyl group, an imidazopyridyl group, an imidazothiazolyl group, an imidazooxazolyl group, a benzothiazolyl group, a benzoxazolyl group, a benzimidazolyl group, an indolyl group, an isoindolyl group, an indazolyl group, a pyrrolopyridyl group, a thienopyridyl group, a furopyridyl group, a benzothiadiazolyl group, a benzoxadiazolyl group, a pyridopyrimidinyl group, a benzofuryl group, and a benzothienyl group.
• C1-18 hydrocarbyl group refers to a monovalent group generated 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.
• the “ C1-18 hydrocarbyl group” is not particularly limited, and examples thereof include a “ C1-18 alkyl group”, a “ C2-18 alkenyl group”, a “ C2-18 alkynyl group”, a “ C3-18 alicyclic group”, a “ C6-18 aryl group”, a “ C7-18 aralkyl group” and the like.
• a "C 1-18 hydrocarbyloxy group” refers to a "C 1-18 hydrocarbyl group” to which an oxygen atom (-O-) is bonded.
• the "C 1-18 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-methylpropyloxy group, a 2,3-dimethylpropyloxy group, a 2,4-dimethylpropyloxy group,
• C such as 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.
• Specific examples of the hydrocarbyloxy include optionally substituted ethylcyclopentyloxy, methyladamantyloxy, ethyladamantyloxy, t-butyloxy, and the like.
• the "C 1-18 hydrocarbyl carbonyl group” is not particularly limited, and examples thereof include “C 1-18 alkyl carbonyl groups” such as acetyl group, propionyl group, isopropionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pentanoyl group, 3-methylbutanoyl group, pivaloyl group, hexanoyl group, and heptanoyl group; "C 3-18 alicyclic carbonyl groups” such as cyclopropyl carbonyl group, cyclobutyl carbonyl group, cyclopentyl carbonyl group, 2-methylcyclopentyl carbonyl group, 3-methylcyclopentyl carbonyl group, cyclo
• a "C 1-18 hydrocarbylcarbonyloxy group” refers to a group in which an oxygen atom (-O-) is bonded to a "C 1-18 hydrocarbylcarbonyl group.”
• the "C 1-18 hydrocarbylcarbonyloxy group” is not particularly limited, and examples include "C 1-18 alkylcarbonyloxy groups” such as methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group, isobutylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, isopentylcarbonyloxy group, and hexylcarbonyloxy group; "C 3-18 alicyclic carbonyloxy groups” such as cyclopropylcarbonyloxy group, cyclobutylcarbonyloxy group, cyclopentylcarbon
• the "C 1-18 hydrocarbyloxycarbonyl group” is not particularly limited, and examples thereof include “C 1-18 alkoxycarbonyl groups” 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, or a neopentyloxycarbonyl group; "C 1-18 alkoxycarbonyl groups” such as a cyclopropyloxycarbonyl group, a cyclobutyloxycarbonyl group, a
• a "C 1-18 hydrocarbyloxycarbonyloxy group” refers to a "C 1-18 hydrocarbyloxycarbonyl group” to which an oxygen atom (-O-) is bonded.
• the "C 1-18 hydrocarbyloxycarbonyloxy group” is not particularly limited, and examples thereof include “C 1-18 alkoxycarbonyloxy groups” 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, or an n-hexyloxycarbonyloxy group; "C 1-18 alkoxycarbonyloxy groups” such
• C 1-18 hydrocarbylamino group refers to a group in which one "C 1-18 hydrocarbyl group” is bonded to an amino group.
• the “C 1-18 hydrocarbylamino group” is not particularly limited, and examples include “C 1-18 alkylamino groups” such as methylamino group, ethylamino group, n-propylamino group, i-propylamino group, n-butylamino group, i-butylamino group, sec-butylamino group, t-butylamino group, n-pentylamino group, i-pentylamino group, neopentylamino group, and n-hexylamino group; "C 3-18 alicyclic amino groups” such as cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, 2-methylcyclopentylamino group, 3-
• a "di-C 1-18 hydrocarbylamino group” refers to a group in which two identical or different "C 1-18 hydrocarbyl groups” are bonded to an amino group.
• the "di-C 1-18 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, and an N-n-butyl-N-methylamino group.
• Di-C alicyclic amino groups such as dicyclopropylamino group, dicyclobutylamino group, dicyclopentylamino group, and dicyclohexylamino group
• di-C arylamino groups such as diphenylamino group and phenylnaphthylamino group
• N-C 1-18 alkyl-N-C 3-18 cycloalkylamino groups such as N-methylcyclopentanamino group and N-methylcyclohexylamino group
• N-C 1-18 alkyl-N-C 6-18 arylamino groups such as N-methyl- 2- phenylethylamino group and N - ethyl-N-(4-methylphenyl)amino group.
• the "C 1-18 hydrocarbylaminocarbonyl group” is not particularly limited, and examples thereof include “C 1-18 hydrocarbylaminocarbonyl group", 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-pentylamino
• C 1-18 alkylaminocarbonyl group ;
• C 3-18 alicyclic aminocarbonyl groups such as a cyclopropylaminocarbonyl group, a cyclobutylaminocarbonyl group, a cyclopentylaminocarbonyl group, a cyclohexylaminocarbonyl group, a 2-methylcyclopentylaminocarbonyl group, a 3-methylcyclopentylaminocarbonyl group, a 2-methylcyclohexylaminocarbonyl group, a 3-methylcyclohexylaminocarbonyl group, or a 4-methylcyclohexylaminocarbonyl group; and "C 6-18 arylaminocarbonyl groups” such as a phenylaminocarbonyl group, a 1-naphthylaminocarbonyl group, or a 2-naphthylaminocarbonyl group.
• the "di-C 1-18 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-
• C 1-18 hydrocarbylcarbonylamino group refers to a group in which an amino group is bonded to a "C 1-18 hydrocarbylcarbonyl group”.
• the "C 1-18 hydrocarbylcarbonylamino group” is not particularly limited, and examples thereof include “C 1-18 alkylcarbonylamino groups” 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; "C 3-18 alicyclic carbonylamino groups” such as cycloprop
• a "C 1-18 hydrocarbylaminocarbonyloxy group” refers to a group in which an oxygen atom (-O-) is bonded to a "C 1-18 hydrocarbylaminocarbonyl group.”
• the "C 1-18 hydrocarbylaminocarbonyloxy group” is not particularly limited, and examples include "C 1-18 alkylaminocarbonyloxy groups” such as a methylaminocarbonyloxy group, an ethylaminocarbonyloxy group, an n-propylaminocarbonyloxy group, etc.; "C 3-18 alicyclic aminocarbonyloxy groups” such as a cyclopropylaminocarbonyloxy group , an cyclohexylaminocarbonyloxy group, etc.; and “C 6-18 arylaminocarbonyloxy groups” such as a phenylaminocarbonyloxy group, an 1-naphthylaminocarbonyloxy group, etc.
• a "di-C 1-18 hydrocarbylaminocarbonyloxy group” refers to a group in which an oxygen atom (-O-) is bonded to a "di-C 1-18 hydrocarbylaminocarbonyl group.”
• the "di-C 1-18 hydrocarbylaminocarbonyloxy group” is not particularly limited, and examples thereof include “di-C 1-18 alkylaminocarbonyloxy groups” such as a dimethylaminocarbonyloxy group, a diethylaminocarbonyloxy group, and a di-n-propylaminocarbonyloxy group.
• C 1-18 hydrocarbylaminocarbonylamino group refers to a group in which a “C 1-18 hydrocarbylaminocarbonyl group” is bonded to an amino group.
• the "C 1-18 hydrocarbylaminocarbonylamino group” is not particularly limited, and examples include “C 1-18 alkylaminocarbonylamino groups” such as a methylaminocarbonylamino group, an ethylaminocarbonyloxy group, an n-propylaminocarbonylamino group, etc.; "C 3-18 alicyclic aminocarbonylamino groups” such as a cyclopropylaminocarbonylamino group , an cyclohexylaminocarbonylamino group, etc.; and “C 6-18 arylaminocarbonylamino groups” such as a phenylaminocarbonylamino group, an 1-naphthylaminocarbonylamino group
• a "di-C 1-18 hydrocarbylaminocarbonylamino group” refers to a group in which a “di-C 1-18 hydrocarbylaminocarbonyl group” is bonded to an amino group.
• the "di-C 1-18 hydrocarbylaminocarbonylamino group” is not particularly limited, and examples thereof include “di-C 1-18 alkylaminocarbonylamino groups” such as a dimethylaminocarbonylamino group, a diethylaminocarbonylamino group, and a di-n-propylaminocarbonylamino group.
• a "C 1-18 hydrocarbyloxycarbonylamino group” refers to a group in which a “C 1-18 hydrocarbyloxycarbonyl group” is bonded to an amino group.
• the "C 1-18 hydrocarbyloxycarbonylamino group” is not particularly limited, and examples include “C 1-18 alkoxycarbonylamino groups” 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; "C 3-18 alicyclic oxycarbonylamino groups” such as a cyclopropyloxycarbonylamino group and a cyclohexyloxycarbonylamino group; and "C 6-18 aryloxycarbonylamino groups” such as a phenyloxycarbonylamin
• a "C 1-18 hydrocarbylthio group” refers to a group in which a sulfur atom (-S-) is bonded to a "C 1-18 hydrocarbyl group".
• the "C 1-18 hydrocarbylthio group” is not particularly limited, and examples thereof include “C 1-18 alkylthio groups” such as a 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, or an n-hexylthio group; "C 3-18 alicyclic thio groups” such as a cyclopropylthio group, a cyclobutylthio group, a cyclopentylthio group, a cyclohexylthio group, a 2-methyl
• C 1-18 hydrocarbylsulfinyl group is not particularly limited, and examples thereof include "C 1-18 alkylsulfinyl groups” such as methylsulfinyl group, ethylsulfinyl group, n-propylsulfinyl group, i-propylsulfinyl group, n-butylsulfinyl group, t-butylsulfinyl group, pentylsulfinyl group, and hexylsulfinyl group; "C 3-18 alicyclic sulfinyl groups” such as cyclopropylsulfinyl group, cyclobutylsulfinyl group, cyclopentylsulfinyl group, cyclohexylsulfinyl group, 2-methylcyclopentylsulfinyl group, 3-methylcyclopentylsulfinyl group, 2-
• C 1-18 hydrocarbylsulfonyl group refers to a “C 1-18 hydrocarbyl group” having a sulfonyl group (-SO 2 -) bonded to it.
• the "C 1-18 hydrocarbylsulfonyl group” is not particularly limited, and examples thereof include “C 1-18 alkylsulfonyl groups” such as methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, i-propylsulfonyl group, n-butylsulfonyl group, t-butylsulfonyl group, and pentylsulfonyl group; "C 3-18 alicyclic sulfonyl groups” such as cyclopropylsulfonyl group, cyclobutylsulfonyl group, cyclopentylsulfonyl
• the term "acid dissociable group” refers to a group that substitutes a hydrogen atom of a carboxy group or a hydroxy group (including a phenolic hydroxyl group), and that dissociates due to the action of an acid.
• the “acid dissociable group” is not particularly limited, and examples thereof 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, and a 2-ethyl-2-adamantyl group.
• 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.
• the "substituent” include (1) a halogen atom, (2) a hydroxy group, (3) a thiol group, (4) a nitro group, (5) a cyano group, (6) a carboxy group, (7) an amino group, (8) a sulfo group, (9) a group in which a hydrogen atom of a carboxy group or a hydroxy group is substituted with an acid dissociable group, or (10) a C 1-18 hydrocarbyl group in which at least a portion of the hydrogen atoms may be substituted with the above (1) to (9), a C 1-18 hydrocarbyloxy group, a C 1-18 hydrocarbylcarbonyl group, a C 1-18 hydrocarbylcarbonyloxy group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbyloxycarbonyl group
• R 3A , R 3B and R 3C each independently represent a C 1-18 hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, which may have a substituent;
• any one or more of R 3A to R 3C may be a C 1-18 hydrocarbyl group which may have a substituent.
• any of R 3A to R 3C is an optionally substituted C 1-18 alkyl group, C 2-18 alkenyl group, C 2-18 alkynyl group, C 3-18 cycloalkyl group, C 3-18 cycloalkenyl group, C 3-18 cycloalkenyl group, or C 7-18 aralkyl group
• examples of such a group include the following sulfonium cations.
• any one or more of R 3A to R 3C are A C 4-18 hydrocarbyl group which contains a linear alkyl group having from 4 to 18 carbon atoms and which may have a substituent, a C 4-18 hydrocarbyloxy group, a C 4-18 hydrocarbylcarbonyl group, a C 4-18 hydrocarbylcarbonyloxy group, a C 4-18 hydrocarbyloxycarbonyl group, a C 4-18 hydrocarbyloxycarbonyl group, a C 4-18 hydrocarbylamino group, a di-C 4-18 hydrocarbylamino group, a C 4-18 hydrocarbylaminocarbonyl group, a C 4-18 hydrocarbylaminocarbonyl group , a C 4-18 hydrocarbylaminocarbonyl group , a C 4-18 hydrocarbylaminocarbonyl group , a C 4-18 hydrocarbylaminocarbonyl group, a C 4-18 hydrocarbylaminocarbonyl group, a C 4-18 hydrocar
• R 3A , R 3B and R 3C is A C 1-18 hydrocarbyl group, a C 1-18 hydrocarbyloxy group, a C 1-18 hydrocarbylcarbonyl group, a C 1-18 hydrocarbylcarbonyloxy group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbylamino group, a di-C 1-18 hydrocarbylamino group, a C 1-18 hydrocarbylaminocarbonyl group, a di -C 1-18 hydrocarbylaminocarbonyl group, a C 1-18 hydrocarbylaminocarbonyl group, a di -C 1-18 hydrocarbylaminocarbonyl group, a C 1-18 hydrocarbylaminocarbonyl group, a C 1-18 hydrocarbylaminocarbonyloxy group , a di-C 1-18 hydrocarbylamino
• the acid dissociable group D 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.
• the acid dissociable group D in this embodiment can be an acid dissociable group represented by the following formula (iii) in which the carbon bonded to the carboxyl group or hydroxyl group is a tertiary carbon.
• Examples of the acid-dissociable group in which the carbon bonded to the carboxy group or hydroxy group is a tertiary carbon 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, and a 2-ethyl-2-adamantyl group.
• R 31 may be a C 1-12 hydrocarbyl group which may have a substituent.
• R 32 and R 33 may each independently be a C 1-12 hydrocarbyl group which may have a substituent, or R 32 and R 33 may together constitute a C 3-18 alicyclic group which may have a substituent.
• R 31 is preferably a C 1-6 alkyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group.
• R 32 and R 33 are preferably a C 3-18 cycloalkyl group, a C 3-18 cycloalkenyl group or a C 3-18 polycycloalkyl group, more preferably a cyclopropane skeleton, cyclobutane skeleton, cyclopentane skeleton, cyclohexane skeleton, cycloheptane skeleton, cyclooctane skeleton, norbornane skeleton or adamantane skeleton which may have a substituent, and further preferably a cyclopentyl group, 1-i-propylcyclopentan-1-yl group, cyclohexyl group, t-butylcyclohexyl group, 2-methyladamantan-2-yl group, 2-i-propyladamantan-2-yl group, cyclopropyl group, cyclooctyl group,
• R 3A to R 3C are an optionally substituted C 6-18 aryl group
• examples include the following sulfonium cations.
• an electron donating group or an electron withdrawing group as a substituent on the C 6-18 aryl group, the stability, reactivity, etc. of the heteropolyoxotungstate can be adjusted.
• the substituent on the C 6-18 aryl group is preferably a halogen atom, a hydroxy group, a nitro group, a cyano group, a C 1-18 haloalkyl group which may have a substituent, a C 1-18 hydrocarbyloxy group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbylcarbonyloxy group, or a C 1-18 hydrocarbylthio group, more preferably a halogen atom, a nitro group, a cyano group, a C 1-4 haloalkyl group which may have a substituent, a C 1-12 hydrocarbyloxy group, a C 1-12 hydrocarbyloxycarbonyl group, a C 1-12 hydrocarbylcarbonyloxy group, or a C 1-12 hydrocarbylthio group, and even more preferably a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an
• any one or more of R 3A to R 3C may be a 5- to 18-membered aromatic heterocyclic group which may have a substituent.
• R 3D , R 3E , R 3F and R 3G each independently represent a C 1-18 hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group or a 5- to 18-membered aromatic heterocyclic group, which may have a substituent;
• K 3A , K 3B and L each independently represent a C 1-18 hydrocarbylene group which may have
• any one or more of K 3A , K 3B and L may be a C 1-18 alkylene group which may have a substituent, or a C 6-18 arylene group, among C 1-18 hydrocarbylene groups which may have a substituent.
• K 2A , K 2B and L is a C 1-18 alkylene group or a C 6-18 arylene group which may have a substituent, for example, the following sulfonium dication can be exemplified.
• Ar 4A to Ar 4C each independently represent a C 6-18 aryl group or a 5- to 18-membered heterocyclic group which may have a substituent;
• the C 6-18 aryl group or 5-18 membered heterocyclic group which may have a substituent is preferably a C 1-18 hydrocarbyl group, a C 1-18 hydrocarbyloxy group, a C 1-18 hydrocarbylcarbonyl group, a C 1-18 hydrocarbylcarbonyloxy group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbyloxycarbonyl group , a C 1-18 hydrocarbylamino group, a di-C 1-18 hydrocarbylamino group , C and which may be substituted by a 1-18 hydrocarbyl aminocarbonyl group
• any one or more of Ar 4A to Ar 4C may be a C 6-18 aryl group or a 5- to 18-membered heterocyclic group which may have a substituent.
• sulfonium cation represented by general formula (IV-1) when, for example, all of Ar 4A to Ar 4C are C 6-18 aryl groups which may have a substituent, examples include the following sulfonium cations.
• an electron donating group or an electron withdrawing group as a substituent on the C 6-18 aryl group, the stability, reactivity, etc. of the heteropolyoxotungstate can be adjusted.
• the substituent of the C6-18 aryl group is preferably a halogen atom, a hydroxy group, a nitro group, a cyano group, a C1-18 haloalkyl group which may have a substituent, a C1-18 hydrocarbyloxy group, a C1-18 hydrocarbyloxycarbonyl group, a C1-18 hydrocarbylcarbonyloxy group, or a C1-18 hydrocarbylthio group, more preferably a halogen atom, a nitro group, a cyano group, a C1-4 haloalkyl group which may have a substituent, a C1-12 hydrocarbyloxy group, a C1-12 hydrocarbyloxycarbonyl group, a C1-12 hydrocarbylcarbonyloxy group, or a C1-12 hydrocarbylthio group, and more preferably a C1-12 hydrocarbyloxy group in which at least a part of the hydrogen atoms is a halogen atom,
• any one or more of Ar 4A to Ar 4C may be a 5- to 18-membered heterocyclic group which may have a substituent.
• Ar 4A to Ar 4C are an optionally substituted 5- to 18-membered heterocyclic group, the following sulfonium cations can be exemplified.
• Ar 4D represents a C 6-18 aryl group or a 5- to 18-membered heterocyclic group which may have a substituent;
• the C 6-18 aryl group or 5-18 membered heterocyclic group which may have a substituent is preferably a C 1-18 hydrocarbyl group, a C 1-18 hydrocarbyloxy group, a C 1-18 hydrocarbylcarbonyl group, a C 1-18 hydrocarbylcarbonyloxy group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbyloxycarbonyl group , a C 1-18 hydrocarbylamino group, a di-C 1-18 hydrocarbylamino group , C and which may be substituted by a 1-18 hydrocarbyl aminocarbonyl group, a di-C
• Ar 4D is preferably a C 6-18 aryl group which may have a substituent, and more preferably a C 6-18 aryl group which may be substituted with a halogen atom, a hydroxy group, a carboxy group, a nitro group, a group in which the hydrogen atoms of a carboxy group or a hydroxy group are substituted with an acid dissociable group, or a C 1-18 haloalkyl group in which at least a part of the hydrogen atoms of a halogen atom, a hydroxy group, a carboxy group, a nitro group, a carboxy group or a hydroxy group may be substituted with an acid dissociable group, a C 1-18 hydrocarbyloxy group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbylcarbonyloxy group, or a C 1-18 hydrocarbylthio group.
• R 4A and R 4B are preferably a halogen atom, a hydroxy group, a nitro group, a cyano group, or a C 1-4 haloalkyl group, a C 1-18 hydrocarbyloxy group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbylcarbonyloxy group, or a C 1-18 hydrocarbylthio group as an electron donating group, an electron withdrawing group, or the like, which may have a substituent, and more preferably a halogen atom, a nitro group, a cyano group, or a C 1-4 haloalkyl group, a C 1-12 hydrocarbyloxy group, a C 1-12 hydrocarbyloxycarbonyl group, a C 1-12 hydrocarbylcarbonyloxy group, or a C 1-12 hydrocarbylthio group.
• the sulfonium cation include the following sulfonium cations.
• Ar 4E represents a C 6-18 aryl group or a 5- to 18-membered heterocyclic group which may have a substituent;
• the C 6-18 aryl group or 5-18 membered heterocyclic group which may have a substituent is preferably a C 1-18 hydrocarbyl group, a C 1-18 hydrocarbyloxy group, a C 1-18 hydrocarbylcarbonyl group, a C 1-18 hydrocarbylcarbonyloxy group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbyloxycarbonyl group , a C 1-18 hydrocarbylamino group, a di-C 1-18 hydrocarbylamino group , C and which may be substituted by a 1-18 hydrocarbyl aminocarbonyl group, a di-C
• Ar 4E may be a C 6-18 aryl group which may have a substituent
• R 4C and R 4D may be, as an electron-donating group or electron-withdrawing group, a halogen atom, a hydroxy group, a nitro group, a cyano group, a C 1-4 haloalkyl group which may have a substituent, a C 1-18 hydrocarbyloxy group which may have a substituent, a C 1-18 hydrocarbyloxycarbonyl group which may have a substituent, a C 1-18 hydrocarbylcarbonyloxy group which may have a substituent, a C 1-18 hydrocarbylthio group which may have a substituent, or the like.
• the sulfonium cation include the following sulfonium cations.
• Ar 4F represents a C 6-18 aryl group or a 5- to 18-membered heterocyclic group which may have a substituent;
• the C 6-18 aryl group or 5-18 membered heterocyclic group which may have a substituent is preferably a C 1-18 hydrocarbyl group, a C 1-18 hydrocarbyloxy group, a C 1-18 hydrocarbylcarbonyl group, a C 1-18 hydrocarbylcarbonyloxy group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbyloxycarbonyl group , a C 1-18 hydrocarbylamino group, a di-C 1-18 hydrocarbylamino group , C and which may be substituted by a 1-18 hydrocarbyl aminocarbonyl group, a di-C
• Ar 4F may be a C 6-18 aryl group which may have a substituent
• R 4E may be, as an electron-donating group or an electron-withdrawing group, a halogen atom, a hydroxy group, a nitro group, a cyano group, a C 1-4 haloalkyl group which may have a substituent, a C 1-18 hydrocarbyloxy group which may have a substituent, a C 1-18 hydrocarbyloxycarbonyl group which may have a substituent, a C 1-18 hydrocarbylcarbonyloxy group which may have a substituent, a C 1-18 hydrocarbylthio group which may have a substituent, or the like.
• Ar 4G each independently represents a C 6-18 aryl group or a 5- to 18-membered heterocyclic group which may have a substituent;
• the C 6-18 aryl group or 5-18 membered heterocyclic group which may have a substituent is preferably a C 1-18 hydrocarbyl group, a C 1-18 hydrocarbyloxy group, a C 1-18 hydrocarbylcarbonyl group, a C 1-18 hydrocarbylcarbonyloxy group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbyloxycarbonyl group , a C 1-18 hydrocarbylamino group, a di-C 1-18 hydrocarbylamino group , C and which may be substituted by a 1-18 hydrocarbyl aminocarbonyl group, a di
• Ar 4G may be a C 6-18 aryl group which may have a substituent
• R 4F and R 4G may be, as an electron-donating group or electron-withdrawing group, a halogen atom, a hydroxy group, a nitro group, a cyano group, a C 1-4 haloalkyl group which may have a substituent, a C 1-18 hydrocarbyloxy group which may have a substituent, a C 1-18 hydrocarbyloxycarbonyl group which may have a substituent, a C 1-18 hydrocarbylcarbonyloxy group which may have a substituent, a C 1-18 hydrocarbylthio group which may have a substituent, or the like.
• the sulfonium cation include the following sulfonium cations.
• R 5A to R 5C are each independently a halogen atom, a hydroxy group, a thiol group, a nitro group, a carboxy group, an amino group, a sulfo group, a group in which the hydrogen atom of a carboxy group or a hydroxy group is substituted with an acid dissociable group, or a C 1-18 hydrocarbyl group in which some of the hydrogen atoms may be substituted with a halogen atom, a hydroxy group, a thiol group, a nitro group, a cyano group, a carboxy group, an amino group, a sulfo group, a carboxy group or a hydroxy group in which the hydrogen atom of a hydroxy group is substituted with an acid dissociable group, a C 1-18 hydrocarbyloxy group, a C 1-18 hydrocarbylcarbonyl group, a C 1-18 hydrocarby
• R 5A , R 5B and R 5C is is preferably a halogen atom, a C 1-4 haloalkyl group (for example, a trifluoromethyl group, a tetrafluoroethyl group, etc.), a C 1-4 haloalkyloxy group, a C 1-18 hydrocarbyloxy group in which at least a portion of the hydrogen atoms are substituted with halogen atoms, or a C 1-18 hydrocarbylcarbonyloxy group in which at least a portion of the hydrogen atoms are substituted with halogen atoms, More preferred is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethyl group, a tetrafluoroethyl group, a trifluoromethyloxy group
• R 5A , R 5B , and R 5C is A C 4-18 hydrocarbyl group which contains a linear alkyl group having from 4 to 18 carbon atoms and which may have a substituent, a C 4-18 hydrocarbyloxy group, a C 4-18 hydrocarbylcarbonyl group, a C 4-18 hydrocarbylcarbonyloxy group, a C 4-18 hydrocarbyloxycarbonyl group, a C 4-18 hydrocarbyloxycarbonyl group, a C 4-18 hydrocarbylamino group, a di-C 4-18 hydrocarbylamino group, a C 4-18 hydrocarbylaminocarbonyl group, a C 4-18 hydrocarbylaminocarbonyl group , a C 4-18 hydrocarbylaminocarbonyl group , a C 4-18 hydrocarbylamino group, a C 4-18 hydrocarbylamino group, a C 4-18 hydrocarbylamino group, a C 4-18 hydrocarbylamino group, a
• R 5A , R 5B and R 5C is A C 1-18 hydrocarbyl group, a C 1-18 hydrocarbyloxy group, a C 1-18 hydrocarbylcarbonyl group, a C 1-18 hydrocarbylcarbonyloxy group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbylamino group, a di-C 1-18 hydrocarbylamino group, a C 1-18 hydrocarbylaminocarbonyl group, a di -C 1-18 hydrocarbylaminocarbonyl group, a C 1-18 hydrocarbylaminocarbonyl group, a di -C 1-18 hydrocarbylaminocarbonyl group, a C 1-18 hydrocarbylaminocarbonyl group, a C 1-18 hydrocarbylaminocarbonyloxy group , a di-C 1-18 hydrocarbylamino
• the acid dissociable group D 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.
• the acid dissociable group D in this embodiment can be an acid dissociable group represented by the following formula (iii) in which the carbon bonded to the carboxyl group or hydroxyl group is a tertiary carbon.
• Examples of the acid-dissociable group in which the carbon bonded to the carboxy group or hydroxy group is a tertiary carbon 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, and a 2-ethyl-2-adamantyl group.
• R 51 may be a C 1-12 hydrocarbyl group which may have a substituent.
• R 52 and R 53 may each independently be a C 1-12 hydrocarbyl group which may have a substituent, or R 52 and R 53 may together constitute a C 3-18 alicyclic group which may have a substituent.
• R 51 is preferably a C 1-6 alkyl group, and more preferably a methyl group, an ethyl group, a propyl group or a butyl group.
• R 52 and R 53 are preferably a C 3-18 cycloalkyl group, a C 3-18 cycloalkenyl group or a C 3-18 polycycloalkyl group, more preferably a cyclopropane skeleton, cyclobutane skeleton, cyclopentane skeleton, cyclohexane skeleton, cycloheptane skeleton, cyclooctane skeleton, norbornane skeleton or adamantane skeleton which may have a substituent, and further preferably a cyclopentyl group, 1-i-propylcyclopentan-1-yl group, cyclohexyl group, t-butylcyclohexyl group, 2-methyladamantan-2-yl group, 2-i-propyladamantan-2-yl group, cyclopropyl group, cyclooctyl group,
• Specific examples of sulfonium cations include dibutyl(pentyl)sulfonium cation, 1-phenylhexahydrothiopyrylium cation, (ethane-1,2-diylbisoxy)bis(4,1-phenylene)bis(diphenylsulfonium) dication, (thiodi-4,1-phenylene)bis(diphenylsulfonium) dication, diphenyl(thiophen-2-yl)sulfonium cation, diphenyl(thiophen-3-yl)sulfonium cation, di(naphthalene-1-yl)(phenyl)sulfonium cation, phenylbis(2-(trifluoromethyl) phenyl)sulfonium
• the heteropolyoxotungstate compound according to this embodiment is represented by the following general formula (I). (A m+ ) x/m (B n+ ) y/n (C- (x+y) ) (I) Each A m+ independently represents H + , a metal ion, or an ammonium ion; m is an integer from 1 to 5, and x and x/m are integers.
• the metal ions usable as A m+ are not particularly limited, and examples thereof include Li + , Na + , K + , Rb + , Cs + , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Co 3+ , Bi 3+ , Zr 4+ , Hf 4+ , Bi 5+ , etc. These metal ions may be used alone or in combination of two or more.
• the ammonium cation that can be used as A m+ is not particularly limited, and examples thereof include NH 4+ and quaternary ammonium cations.
• the quaternary ammonium cation can be represented by (R) 4 N + .
• Each R is independent and may be the same or different.
• R is not particularly limited, and examples thereof include a C 1-18 hydrocarbyl group which may have a substituent.
• R is preferably a C 1-12 hydrocarbyl group which may have a substituent, and more preferably a C 1-8 hydrocarbyl group which may have a substituent.
• a m+ is preferably Li + , Na + , K + , Rb + , Cs + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Co 3+ , NH 4+ , or a quaternary ammonium cation, more preferably Na + , K + , Rb + , Cs + , Co 3+ , NH 4+ , or a quaternary ammonium cation, and even more preferably NH 4+ or a quaternary ammonium cation.
• x:y 0-3:1-4, more preferably 0-2:1-4, and even more preferably 0-2:2-4.
• x is an integer of 0-3 and y is an integer of 1-4, more preferably that x is an integer of 0-2 and y is an integer of 1-4, and even more preferably that x is an integer of 0-2 and y is an integer of 2-4.
• the heteropolyoxotungstic acid represented by C- (x+y) is not particularly limited, and examples thereof include, for example, [ PW12O40 ] 3- , [ SiW12O40 ] 4- , [ BW12O40 ]5-, [SW12O40]2-, [P2W18O62]6-, [Si2W18O62]8- , [ S2W18O62 ] 4- , [ PW9O34 ] 9- , [ PW10O36 ] 7- , [ PW11O39 ] 7- , [ SiW9O34 ] 10- , [ SiW10O36 ] 8 ⁇ , [SiW 11 O 39 ] 8 ⁇ , [P 2 W 17 O 61 ] 10 ⁇ , etc. can be used.
• the number of B n+ (sulfonium cations) bonded to one heteropolyoxotungstic acid is not particularly limited, and may contain, for example, two or more different heteropolyoxotungstate compounds in which two or more B n+ are bonded to one heteropolyoxotungstic acid selected from integers of 1 to 10. Specific examples include those in which one B n+ is bonded to one heteropolyoxotungstic acid, those in which two or three B n+ are bonded to one heteropolyoxotungstic acid.
• Each A m+ independently represents H + , a metal ion, or an ammonium ion;
• Each B n+ independently represents a sulfonium cation;
• C- (x'+y') represents a heteropolyoxotungstic acid;
• m is an integer from 1 to 5
• n is an integer of 1 or 2
• x' and x'/m are real numbers equal to or greater than
• y' and y'/n are real numbers greater than 0, and
• x'+y' is a natural number.
• the elemental composition of S and W contained in the heteropolyoxotungstate compound or mixture can be determined by XRF or XPS analysis.
• XRF analysis a known and commonly used method can be used.
• the molar ratio of S and W in the heteropolyoxotungstate compound or mixture can be determined by SQX analysis using a calibration curve method or a fundamental parameter (FP) method.
• FP fundamental parameter
• a known, commonly used method can be used.
• the molar ratio of S and W in the heteropolyoxotungstate compound or mixture can be determined by determining the atomic % of each element based on the peak areas of S2p and W4f.
• solvate of the heteropolyoxotungstate compound or mixture according to this embodiment is not particularly limited, and examples thereof include alcohol solvates such as methanol solvates, ethanol solvates, and isopropanol solvates; and hydrates such as monohydrates, dihydrates, trihydrates, and tetrahydrates.
• the method for producing the heteropolyoxotungstate compound or a solvate thereof according to another embodiment of the present invention is not particularly limited, and for example, a salt exchange method, an ion exchange method, or the like can be used.
• the method for producing a heteropolyoxotungstate compound represented by general formula (I) or a solvate thereof is characterized by having a step of reacting a compound represented by general formula (VI-1) with a compound represented by general formula (VI-2) to carry out salt exchange.
• a method for producing a heteropolyoxotungstate compound represented by general formula (I) or a solvate thereof includes the following steps: A step of reacting a compound represented by general formula (VI-1) with a compound represented by general formula (VI-2) to carry out salt exchange; removing the compound represented by general formula (VI-3) from the produced compounds represented by general formulas (I) and (VI-3); [0043] (A m+ ) x/m (B n+ ) y/n (C- (x+y) ) (I) (A m+ ) x/m (A' m'+ ) y/m' (C - (x+y) ) (VI-1) (B n+ ) y/n (Y - ) y (VI-2) (A' m'+ ) y/m' (Y - ) y (VI-3) [Wherein, Each A m+ independently represents H + , a metal ion, or an
• A'm '+ is preferably H + , Li + , Na + , K + , Rb + , Cs + , Be2+ , Mg2 + , Ca2 + , Sr2 + , Ba2 + , Co3 + , Bi3 + , Zr4 + , Hf4 + , Bi5 + , NH4 + , a quaternary ammonium cation, or a combination thereof, more preferably H + , Na + , K + , Mg2+ , Ca2 + , NH4 + , a quaternary ammonium cation, or a combination thereof, and even more preferably H + , Na + , K + , NH4 + , a quaternary ammonium cation, or a combination thereof.
• the compound represented by the general formula (VI-1) can be synthesized by a known synthesis method.
• Commercially available products of the compound represented by the general formula (VI-1) include, for example, phosphotungstic acid (H 3 [PW 12 O 40 ] ⁇ nH 2 O) manufactured by Nippon Inorganic Chemical Industry Co., Ltd. and Fujifilm Wako Pure Chemical Industries Co., Ltd., and silicotungstic acid (H 4 [SiW 12 O 40 ] ⁇ 26H 2 O) manufactured by Nippon Inorganic Chemical Industry Co., Ltd.
• Y- is preferably Br- , Cl- , I- , OH- , CF3SO3- , C2F5SO3- , C3F7SO3- , C4F9SO3- , p- CH3 ( C6H4 ) SO3- , ClSO3- , ClO4- , ( C6F5 ) 4B- , BF4- , PF6- , SbF6- , AlCl4- , BiF6- , or AsF6- , and more preferably Br- , Cl- , I- , OH- , CF3SO3- , or C4F9SO3- .
• BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ are more preferred, and Br ⁇ , Cl ⁇ , CF 3 SO 3 ⁇ , BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ are even more preferred.
• WPAG-336 diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate
• WPAG-367 diphenyl-2,4,6-trimethylphenylsulfonium p-toluenesulfonate
• WPAG-370 diphenyl(4-methoxyphenyl)sulfonium trifluoromethanesulfonate
• WPAG-469 (4-methylphenyldiphenylsulfonium nonafluorobutanesulfonate
• WPAG-638 tris(4-methylphenyl)sulfonium nonafluorobutanesulfonate) manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
• benzyl(4-hydroxyphenyl)methylsulfonium hexafluoroantimonate diphenyl(methyl)sulfonium
• trimethylsulfonium hydroxide triphenylsulfonium nonafluoro-1-butanesulfonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, diphenyl(4-(phenylthio)phenyl)sulfonium hexafluoroantimonate, diphenyl(4-(phenylthio)phenyl)sulfonium hexafluorophosphate, (3-chloropropyl)diphenylsulfonium tetrafluoroborate, (2-carboxyethyl)dimethylsulfonium chloride, (2-carboxyethyl)dimethylsulfonium bromide, tri-p-tolylsulfonium trifluoromethanesulfonate, (difluoromethyl)bis(2,5-dimethylpheny
• the blending molar ratio of the compound represented by general formula (VI-1) to the compound represented by general formula (VI-2) is not particularly limited, and can be appropriately set according to the molar ratio of A m+ and B n+ contained in the target heteropolyoxotungstate or solvate thereof.
• the blending molar ratio of the compound represented by general formula (VI-1) to the compound represented by general formula (VI-2) is preferably 1-3:1-20, more preferably 1-3:1-18, and even more preferably 2:1-15.
• reaction conditions for the compound represented by general formula (VI-1) and the compound represented by general formula (VI-2) are not particularly limited, and the reaction can be carried out under known and commonly used reaction conditions.
• the type of solvent, reaction temperature, reaction time, pressure, and the like can be appropriately set.
• the type of solvent is not particularly limited, and examples thereof include water, methanol, ethanol, 1,4-dioxane, acetonitrile, 1-propanol, 2-propanol, ethyl acetate, acetonitrile, acetone, dichloromethane, chloroform, dimethylformamide, diethyl ether, etc.
• the reaction temperature is not particularly limited, and may be, for example, room temperature or heated.
• the reaction time is not particularly limited, but is preferably from 1 minute to 24 hours, and more preferably from 1 minute to 5 hours.
• the pressure is not particularly limited, and may be normal pressure or increased pressure.
• the method for removing the compound represented by general formula (VI-3) is not particularly limited, and examples thereof include a method of extracting the by-produced compound represented by general formula (VI-3) into an aqueous layer and removing it, a method of precipitating it as an inorganic salt and filtering it off, and a method of crystallizing the target compound represented by general formula (I) or a solvate thereof and filtering it off.
• A' m'+ ) y/m' (Y - ) y (VI-3) (A m+ ) x/m (B n+ ) y/n (C- (x+y) ) (I)
• the method for crystallizing the target compound represented by general formula (I) or a solvate thereof and filtering it is not particularly limited, and examples thereof include a method in which the target compound is heated to dissolve it in a solvent and then slowly cooled to precipitate crystals, and a method in which a poor solvent and a good solvent are combined to cause crystallization.
• the poor solvent can be appropriately selected depending on the target product. For example, diethyl ether, dipropyl ether, ethyl acetate, butyl acetate, hexane, toluene, 2-propanol, ethanol, methanol, etc. may be used.
• the good solvent can be appropriately selected depending on the intended product. For example, water, methanol, ethanol, 1,4-dioxane, dimethylformamide, chloroform, dichloromethane, etc. may be used.
• a method for producing a heteropolyoxotungstate compound represented by general formula (I) or a solvate thereof includes the following steps: A step of ion-exchanging A'm'+ of the compound represented by general formula (VI-1) with H + using an ion exchange resin; A step of reacting the compound represented by general formula (VI-4) produced by the above step with a compound represented by general formula (VI-2);
• the present invention is characterized by having the following.
• the ion exchange resin is not particularly limited as long as it can ion-exchange A'm '+ of the compound represented by the general formula (VI-1) with H + , and any known and commonly used ion exchange resin can be used.
• the ion exchange resin is not particularly limited, and for example, a strong acid cation exchange resin, a weak acid cation exchange resin, or the like can be used.
• ion exchange resins include Amberlite(TM) IR-200CT, HPR1200 H, HPR1024 H, HPR1006NNC H, and Dowex(TM) 50W manufactured by Dow Chemical; and ORLITE(TM) DS-1 and DS-4 manufactured by Organo Corporation.
• a known and commonly used method can be used as a method for ion-exchanging A'm'+ of the compound represented by the general formula (VI-1) with H + using an ion-exchange resin.
• the above method is not particularly limited, and examples thereof include a method in which an ion exchange resin is packed in a column, and then a solution of water, an organic solvent or the like containing the compound represented by general formula (VI-1) is passed through the column to bring the compound represented by general formula (VI-1) into contact with the ion exchange resin, and then the compound is eluted with an elution solvent; a method in which an ion exchange resin and the compound represented by general formula (VI-1) are mixed in a beaker, and then the ion exchange resin is removed by filtration; and the like.
• the elution solvent that can be used when passing a solution containing a compound represented by general formula (VI-1) through a column packed with an ion exchange resin is not particularly limited, and examples that can be used include Milli-Q water, pure water (ion-exchanged water, demineralized water), methanol, ethanol, etc.
• the SV space velocity, h -1
• the SV space velocity, h -1
• the compound represented by general formula (VI-1) is contacted using a column packed with an ion exchange resin is not particularly limited as long as it is capable of ion-exchanging A' m'+ of the compound represented by general formula (VI-1) with H + .
• the SV is preferably 0.1 to 100, more preferably 0.5 to 50, and even more preferably 1 to 30.
• the SV is a unit indicating how many times the resin capacity the amount of liquid is passed through per hour.
• ⁇ Ion exchange method 60.41 g of sodium silicate was dissolved in 240 g of ion-exchanged water to prepare an aqueous solution of sodium silicate.
• a column with an inner diameter of 30 mm was packed with 60 cm3 of strongly acidic cation exchange resin ORLITETM DS-1 (manufactured by Organo Corporation).
• ORLITETM DS-1 strongly acidic cation exchange resin
• the aqueous solution of sodium silicate was passed through the column at a rate of about 1 to 15 cm3 /min, and then ion-exchanged water was passed through at the same rate.
• the eluate with an acidic pH was collected.
• the target compound was obtained in the same manner as in the salt exchange method of Synthesis Example 1, except that the raw material compound was changed from 37.27 g of phenylbis(2-(trifluoromethyl)phenyl)sulfonium chloride to 27.95 g, and 41.97 g of phosphotungstic acid (H 3 [PW 12 O 40 ] ⁇ 30H 2 O) was used instead of silicotungstic acid.
• 183 W-NMR (20.84 MHz, DMSO-D6): ⁇ (ppm) -86.7 (s, 12 W).
• ESI-MS NEGATIVE m/z 959 (median) ([PW 12 O 40 ] 3- )
• S:W (molar ratio of S and W) 3:12
• the target compound was obtained in the same manner as in the salt exchange method of Synthesis Example 1, except that 32.60 g of 5-(3-(trifluoromethyl)phenyl)-5H-dibenzo[b,d]thiophen-5-ium chloride was used instead of 37.27 g of phenylbis(2-(trifluoromethyl)phenyl)sulfonium chloride as the raw material compound.
• 1 H-NMR (400MHz, DMSO-D6): ⁇ (ppm) 7.35 (d, 4H), 7.65-7.83 (m, 12H), 7.95 (t, 8H), 8.05 (d, 4H), 8.40 (d, 8H), 8.55 (d, 8H), 8.63 (s, 4H).
• the target compound was obtained in the same manner as in the salt exchange method of Synthesis Example 1, except that 34.87 g of tris(3,5-difluorophenyl)sulfonium chloride was used instead of 37.27 g of phenylbis(2-(trifluoromethyl)phenyl)sulfonium chloride as the raw material compound.
• 183 W-NMR (20.84 MHz, DMSO-D6): ⁇ (ppm) -92.7 (s, 12 W).
• ESI-MS NEGATIVE m/z 718.5 (median) ([SiW 12 O 40 ] 4- )
• S:W (molar ratio of S and W) 4:12
• the target compound was obtained in the same manner as in the salt exchange method of Synthesis Example 1, except that 36.40 g of (4-iodophenyl)diphenylsulfonium chloride was used instead of 37.27 g of phenylbis(2-(trifluoromethyl)phenyl)sulfonium chloride as the raw material compound.
• 183 W-NMR (20.84 MHz, DMSO-D6): ⁇ (ppm) -92.7 (s, 12 W).
• ESI-MS NEGATIVE m/z 718.5 (median) ([SiW 12 O 40 ] 4- )
• S:W (molar ratio of S and W) 4:12
• the target compound was obtained in the same manner as in the salt exchange method of Synthesis Example 1, except that 20.47 g of tri-n-butylsulfonium chloride was used instead of 37.27 g of phenylbis(2-(trifluoromethyl)phenyl)sulfonium chloride as the raw material compound.
• 1 H-NMR (400MHz, DMSO-D6): ⁇ (ppm) 0.81-0.93 (m, 36H), 1.35-1.44 (m, 24H), 1.68 (quint, 24H), 3.36 (t, 24H).
• 183 W-NMR (20.84 MHz, DMSO-D6): ⁇ (ppm) -92.7 (s, 12 W).
• ESI-MS NEGATIVE m/z 718.5 (median) ([SiW 12 O 40 ] 4- )
• S:W (molar ratio of S and W) 4:12
• the target compound was obtained in the same manner as in the salt exchange method of Synthesis Example 1, except that 43.81 g of (3,5-dimethyl-4-(undecanoyloxy)phenyl)diphenylsulfonium chloride was used instead of 37.27 g of phenylbis(2-(trifluoromethyl)phenyl)sulfonium chloride as the raw material compound.
• 1 H-NMR (400MHz, DMSO-D6): ⁇ (ppm) 7.79-7.93 (m, 48H), 2.73 (t, 8H), 2.19 (s, 24H), 1.65-1.72 (m, 8H), 1.25-1.38 (m, 56H), 0.85 (t, 12H).
• the target compound was obtained in the same manner as in the salt exchange method of Synthesis Example 1, except that, as the raw material compound, 32.86 g of tris((3,5-dimethyl-4-(undecanoyloxy)phenyl)diphenylsulfonium chloride was used instead of 37.27 g of phenylbis(2-(trifluoromethyl)phenyl)sulfonium chloride, and 41.97 g of phosphotungstic acid (H 3 [PW 12 O 40 ] ⁇ 30H 2 O) was used instead of silicotungstic acid.
• the target compound was obtained in the same manner as in the salt exchange method of Synthesis Example 1, except that 27.68 g of (1-(4-butoxynaphthalen-1-yl)tetrahydro-1H-thiophen-1-ium) chloride was used instead of 37.27 g of phenylbis(2-(trifluoromethyl)phenyl)sulfonium chloride as the raw material compound.
• the target compound was obtained in the same manner as in the salt exchange method of Synthesis Example 1, except that 29.56 g of (1-(2-(((1r,3r,5r,7r)-2-methyladamantan-2-yl)oxy)-2-oxoethyl)hexahydrothiopyrylium) chloride was used instead of 37.27 g of phenylbis(2-(trifluoromethyl)phenyl)sulfonium chloride as the starting compound.
• the target compound was obtained in the same manner as in the salt exchange method of Synthesis Example 1, except that 42.60 g of ((4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium chloride was used instead of 37.27 g of phenylbis(2-(trifluoromethyl)phenyl)sulfonium chloride as the raw material compound.
• the target compound was obtained in the same manner as in the salt exchange method of Synthesis Example 1, except that 42.60 g of (4-(2-((ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium chloride was used instead of 37.27 g of phenylbis(2-(trifluoromethyl)phenyl)sulfonium chloride as the raw material compound, and 41.97 g of phosphotungstic acid was used instead of tungstic silicate.
• the target compound was obtained in the same manner as in the salt exchange method of Synthesis Example 1, except that 46.89 g of (5-(3,5-dimethyl-4-(2-(((1R,3S,5r,7r)-2-methyladamantan-2-yl)oxy)-2-oxoethoxy)phenyl)-5H-dibenzo[b,d]thiophen-5-ium) chloride was used instead of 37.27 g of phenylbis(2-(trifluoromethyl)phenyl)sulfonium chloride as the starting compound.
• the target compound was obtained in the same manner as in the salt exchange method of Synthesis Example 1, except that 23.39 g of (4-(4-(t-butyl)phenyl)-1,4-oxathiane-4-ium) chloride was used instead of 37.27 g of phenylbis(2-(trifluoromethyl)phenyl)sulfonium chloride as the raw material compound.
• 1 H-NMR (400MHz, DMSO-D6): ⁇ (ppm) 1.32 (s, 36H), 2.49-2.79 (m, 16H), 3.80-3.95 (m, 16H), 7.75 (dd, 8H), 7.98 (d, 8H).
• the target compound was obtained in the same manner as in the salt exchange method of Synthesis Example 1, except that 25.61 g of triphenylsulfonium chloride was used instead of 37.27 g of phenylbis(2-(trifluoromethyl)phenyl)sulfonium chloride as the raw material compound.
• 183 W-NMR (20.84 MHz, DMSO-D6): ⁇ (ppm) -92.7 (s, 12 W).
• ESI-MS NEGATIVE m/z 718.5 (median) ([SiW 12 O 40 ] 4- )
• S:W (molar ratio of S and W) 4:12
• the target compound was obtained in the same manner as in the salt exchange method of Synthesis Example 1, except that, as the raw material compound, 19.21 g of triphenylsulfonium chloride was used instead of 37.27 g of phenylbis(2-(trifluoromethyl)phenyl)sulfonium chloride, and 41.97 g of phosphotungstic acid (H 3 [PW 12 O 40 ] ⁇ 30H 2 O) was used instead of silicotungstic acid.
• ESI-MS NEGATIVE m/z 959 (median) ([PW 12 O 40 ] 3- )
• S:W (molar ratio of S and W) 3:12
• M-8, M-9, M-13 and M-14, like M-7 and M-12, have bulky substituents concentrated on one benzene ring as sulfonium cations, which shows a tendency for crystallinity to be suppressed and for solvent solubility to be improved.
• the heteropolyoxotungstate compound which has good solvent solubility, can be dissolved in a solvent to form a uniform film, etc., and can be suitably used as a catalyst with oxidation-reduction ability, a magnetic material, or an actinic ray- or radiation-sensitive compound.

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