WO2017188485A1

WO2017188485A1 - Compound

Info

Publication number: WO2017188485A1
Application number: PCT/KR2016/004532
Authority: WO
Inventors: 후지타타쿠마
Original assignee: 동우 화인켐 주식회사
Priority date: 2016-04-29
Filing date: 2016-04-29
Publication date: 2017-11-02
Also published as: KR20180132710A; KR102145476B1

Abstract

Provided is a compound represented by formula (A-V), wherein Y represents a p-valent anion; R^1Ato R^8A each independently represent a hydrogen atom or an alkyl group having 1-10 carbon atoms; R^9A and R^10A each independently represent a hydrogen atom, an alkyl group having 1-10 carbon atoms, an optionally substituted aromatic hydrocarbon group, or an optionally substituted aralkyl group; R^11A to R^14A each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1-10 carbon atoms; and R^15A to R^20A each independently represent a hydrogen atom or an alkyl group having 1-10 carbon atoms.

Description

compound

The present invention relates to compounds.

As a blue pigment for color filters contained in a liquid crystal display device, an image sensor, etc., patent document 1 has described the compound represented by Formula (A-III-1).

[Preceding technical literature]

[Patent Documents]

Japanese Patent Publication No. 2011-186043

The compound had a low decomposition temperature and was poor in heat resistance. Therefore, an object of this invention is to provide the compound excellent in heat resistance.

This invention provides the following [1]-[4].

[1] A compound represented by the formula (A-V).

[In formula (A-V), Y represents p-valent anion.

R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R ^9A and R ^10A each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group which may be substituted, or an aralkyl group which may be substituted.

R ^11A to R ^14A each independently represent a hydrogen atom, a halogen atom and an alkyl group having 1 to 10 carbon atoms.

R ^15A , R ^16A , R ^17A , R ^18A , R ^19A and R ^20A each independently represent a hydrogen atom and an alkyl group having 1 to 10 carbon atoms.

In the R ^1A ~ R ^20A wherein the alkyl group is an oxygen atom may be inserted between methylene groups constituting.

R ⁴⁶ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group which may be substituted, and an oxygen atom may be inserted between the methylene groups constituting the alkyl group in R ⁴⁶ .

D represents an aromatic group which may be substituted.

A represents the m-valent organic group which may be substituted.

m represents the integer of 2-6.

n represents the integer of 1-6.

p represents the integer of 1-6.

q represents an integer of 1 to 6.]

[2] A compound represented by formula (A-I).

[In formula (A-I), Y represents p-valent anion.

^{^{^{R 15A, R 16A, R 17A}}} , R 18A, R 19A and R ^20A represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms independently.

In R ^1A to R ^20A , an oxygen atom may be inserted between the methylene groups constituting the alkyl group.

R ⁴⁶ is an oxygen atom may be inserted between the methylene group to a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or represents an optionally substituted aromatic hydrocarbon good, in the configuration R ⁴⁶ is the alkyl group.

R ⁵⁵ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group which may be substituted, and an oxygen atom may be inserted between the methylene groups constituting the alkyl group in R ⁵⁵ .

X represents O, S or NH.

A represents the m-valent organic group which may be substituted.

m represents the integer of 2-6.

n represents the integer of 1-6.

p represents the integer of 1-6.

q represents an integer of 1 to 6.]

[3] The compound according to [1] or [2], wherein the counter ion is an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as an essential element.

[4] A compound represented by formula (B-1).

[In formula (B-I),

X represents O, S or NH.

A represents the m-valent organic group which may be substituted.

m represents an integer of 2 to 6.]

According to the present invention, a color filter having good heat resistance can be obtained.

The novel compound according to the present invention is characterized by the following formula (A-V).

[In formula (A-V), Y represents p-valent anion.

R ^9A and R ^10A each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, optionally substituted aromatic hydrocarbon group, or which may be substituted represents an aralkyl group.

D represents an aromatic group which may be substituted.

A represents the m-valent organic group which may be substituted.

m represents the integer of 2-6.

n represents the integer of 1-6.

p represents the integer of 1-6.

q represents an integer of 1 to 6.]

The alkyl group represented by R ^1A to R ^20A may be any of straight chain, branched chain and cyclic. Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, nonyl group and decyl group. Preferably the said alkyl group is C1-C10, More preferably, it is C1-C8, More preferably, it is C1-C6.

The cyclic alkyl group represented by R ^1A to R ^20A may be monocyclic or polycyclic. Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group etc. are mentioned as said cyclic alkyl group. The cyclic alkyl group is preferably 3 to 10 carbon atoms, more preferably 6 to 10 carbon atoms.

As a specific example of the alkyl group represented by R <^1A> -R <^20A> , group represented by a following formula is mentioned. In the following formula, * represents a bonding hand.

R ^1A As group which oxygen atom is inserted among the methylene groups which comprise the said alkyl group among groups represented by -R <^20A> , group represented by a following formula is mentioned. In the following formula, * represents a bonding hand.

The group having 1 to 10 carbon atoms is preferable, and the group having 1 to 6 carbon atoms is more preferable as the group in which an oxygen atom is inserted between the methylene groups constituting the alkyl group. The alkyl group into which the oxygen atom is inserted is preferably a straight chain alkyl group. Moreover, 1-4 pieces are preferable and, as for carbon number between oxygen atoms, 2-3 pieces are more preferable.

^Examples of the aromatic hydrocarbon group in R ^9A to R ^10A include a phenyl group and a naphthyl group.

Examples of the aromatic hydrocarbon group in the aralkyl group in R ^9A to R ^10A include a phenyl group and a naphthyl group.

R ^9A ~ R ^10A the aromatic hydrocarbon group and a halogen atom such as the aralkyl as a substituent in kilgi is fluorine, chlorine, iodine of the groups denoted by; Alkoxy groups having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; Hydroxy; C1-C6 alkyl groups, such as a methyl group and an ethyl group; Sulfamoyl group; C1-C6 alkylsulfonyl groups, such as a methylsulfonyl group; C1-C6 alkoxycarbonyl groups, such as a methoxycarbonyl group and an ethoxycarbonyl group, etc. are mentioned.

Specific examples of the aromatic hydrocarbon group which may be substituted include groups represented by the following formulas. In the following formula, * represents a bonding hand.

As a specific example of the aralkyl group which may be substituted, the group which the methylene group couple | bonded with the bond of each specific example of the following aromatic hydrocarbon group is mentioned as an example.

From the standpoint of ease of synthesis, R ^1A to R ^8A are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

R ^9A ~ R ^10A are each independently an alkyl group having 1 to 10 carbon atoms, optionally substituted aromatic hydrocarbon group or an optionally substituted aralkyl group is preferred, and each independently represents an alkyl group having 1 to 8 carbon atoms in terms of ease of synthesis, Phenyl group, naphthyl group, phenyl group having methyl group, naphthyl group having methyl group; It is more preferable that it is an aralkyl group which is unsubstituted or at least one selected from a halogen atom, a methoxy group, an ethoxy group, a sulfamoyl group, a methylsulfonyl group, a methoxycarbonyl group and an ethoxycarbonyl group, in particular one species, It is further more preferable that it is a C1-C4 linear alkyl group each independently, A methyl group or an ethyl group is more preferable, A methyl group is especially preferable.

^Examples of the halogen atom in the group represented by R ^11A to R ^14A include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and a fluorine atom is preferable. R ^11A to R ^14A are preferably hydrogen atoms in view of ease of synthesis.

R ^15A to R ^20A are each preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom or a methyl group from the viewpoint of ease of synthesis. Preferred, and hydrogen atoms are particularly preferred.

The alkyl group in R ⁴⁶ includes an alkyl group having 1 to 10 carbon atoms in R ^1A to R ^20A .

Specific examples of the alkyl group having 1 to 10 carbon atoms in R ⁴⁶ are methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-de Linear alkyl groups such as practical groups; Branched alkyl groups such as isopropyl group, sec-butyl group, tert-butyl group, isopentyl group, 1-methylpentyl group and 1-propylbutyl group; Cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group; These etc. are mentioned, The group represented by a following formula is mentioned. In the following formula, * represents a bonding hand. Especially, a C1-C8 alkyl group is preferable, a C1-C6 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.

Examples of the group in which an oxygen atom is inserted between the methylene groups constituting the alkyl group in R ⁴⁶ include a group represented by the following formula. In the following formula, * represents a bonding hand.

As a group into which the oxygen atom is inserted between the methylene groups which comprise the said alkyl group, a C1-C10 group is preferable and a C1-C6 group is more preferable. The alkyl group into which the oxygen atom is inserted is preferably a straight chain alkyl group. Moreover, 1-4 pieces are preferable and, as for carbon number between oxygen atoms, 2-3 pieces are more preferable.

Aromatic hydrocarbon group in R ⁴⁶ is a phenyl group, a naphthyl group or the like.

Examples of the substituent for the aromatic hydrocarbon group in R ⁴⁶ include halogen atoms such as fluorine atom, chlorine atom and iodine; Haloalkyl groups having 1 to 6 carbon atoms such as a chloromethyl group and a trifluoromethyl group; Alkoxy groups having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; Hydroxyl group; C1-C6 alkyl groups, such as a methyl group and an ethyl group; Sulfamoyl group; C1-C6 alkylsulfonyl groups, such as a methylsulfonyl group; C1-C6 alkoxycarbonyl groups, such as a methoxycarbonyl group, etc. are mentioned.

R ⁴⁶ is preferably an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group which may be substituted in view of ease of synthesis, and an alkyl group having 1 to 8 carbon atoms or a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, and alkoxy having 1 to 4 carbon atoms. It is more preferable that it is an aromatic hydrocarbon group which may be substituted by group, a hydroxyl group, a C1-C4 alkyl group, or a methylsulfonyl group, and it is still more preferable that it is an aromatic hydrocarbon group represented by a C1-C8 alkyl group or the following formula. In the following formula, * represents a bonding hand.

A represents the m-valent organic group which may be substituted. In m-valent organic group, the organic group in which all m bonds exist on an aliphatic compound (hereinafter also referred to as m-valent aliphatic group), and the organic group in which all m-binding hands exist on the aromatic compound (hereinafter referred to as m-valent aromatic group) And some of the m bonds are present on the aliphatic compound and the remaining groups are on the aromatic compound.

m represents the integer of 2-6, the integer of 2-4 is more preferable, 2 or 3 is further more preferable, and 2 is especially preferable from a viewpoint of the ease of synthesis.

As for carbon number of m-valent aliphatic group, 1-10 are preferable, for example, More preferably, it is 2-10, More preferably, it is 4-10. Moreover, the m-valent aliphatic group in A includes not only the substituent which removed m hydrogen atoms of an aliphatic compound, but the substituent which m aliphatic groups which have a bond are connected by cyclic structure. As said cyclic structure, Monocyclic, such as cyclohexane, benzene, a pyridine; Condensed rings such as naphthalene; Temporary exchange of adamantane and the like; Etc. can be mentioned.

In addition, as a substituent of an m-valent aliphatic group, Halogen atoms, such as a fluorine atom, a chlorine atom, and iodine; Haloalkyl groups having 1 to 6 carbon atoms such as a chloromethyl group and a trifluoromethyl group; Alkoxy groups having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; Hydroxyl group; C1-C6 alkyl groups, such as a methyl group and an ethyl group; Sulfamoyl group; C1-C6 alkylsulfonyl groups, such as a methylsulfonyl group; C1-C6 alkoxycarbonyl groups, such as a methoxycarbonyl group, etc. are mentioned. Examples of the m-valent aliphatic group include a group represented by the following formula. In the following formula, * represents a bonding hand.

As for carbon number of an m-valent aromatic group, 6-40 are preferable, for example, More preferably, it is 6-30, More preferably, it is 6-25. In addition, as the m-valent aromatic group in A, not only a substituent in which m hydrogen atoms of an aromatic compound such as an aromatic hydrocarbon or an aromatic heterocyclic compound are removed, but also m aromatic groups having a bond as long as the bond is present in the aromatic compound are aliphatic groups. Linked substituents are also included.

Moreover, as a substituent of an m-valent aromatic group, Halogen atoms, such as a fluorine atom, a chlorine atom, and iodine; Haloalkyl groups having 1 to 6 carbon atoms such as a chloromethyl group and a trifluoromethyl group; Alkoxy groups having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; Hydroxyl group; C1-C6 alkyl groups, such as a methyl group and an ethyl group; Sulfamoyl group; C1-C6 alkylsulfonyl groups, such as a methylsulfonyl group; C1-C6 alkoxycarbonyl groups, such as a methoxycarbonyl group, etc. are mentioned. As an m-valent aromatic group, group specifically, represented by a following formula is mentioned. In the following formula, * represents a bonding hand.

As A, for example, an aromatic hydrocarbon group represented by the following formula (E-I) is preferable.

[In formula (EI), R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.]

R ⁵¹ to R ⁵⁴ are each independently a hydrogen atom, a methyl group or an ethyl group from the viewpoint of ease of synthesis.

D is an aromatic group which may be substituted and connects a cationized carbon atom and an N atom as shown in Formula (A-V). The aromatic group of D includes, for example, an aromatic heterocyclic substituent having a sulfur atom such as a thiazolyl group, an oxazolyl group, an imidazolyl group, a pyridyl group, an oxygen atom, a nitrogen atom, and an aromatic hydrocarbon group such as a phenyl group or a naphthyl group do. As for carbon number of an aromatic group, 6-20 are preferable, for example, More preferably, it is 6-16, More preferably, it is 6-12.

As a substituent of an aromatic hydrocarbon group, halogen atoms, such as a fluorine atom, a chlorine atom, and iodine, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a SO ₃ ^- group, and a methyl group Sulfonyl group, dialkylamino group, phenylamino group, and the like, wherein the phenylamino group is an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a hydroxy group, a SO ₃ ^- group, a methylsulfonyl group, a dialkylamino group, or the like. It may be substituted.

As a substituent of a hetero aromatic group, a phenyl group, a phenylamino group, etc. are mentioned, The said phenylamino group may be substituted by the C1-C4 alkyl group etc ..

As a specific example of the aromatic group which may be substituted, group represented by a following formula is mentioned. In the following formula, * represents a bond with a cationized carbon atom, and ** represents a bond with an N atom.

In the above formula, R ⁵⁵ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group which may be substituted, and an oxygen atom may be inserted between the methylene groups constituting the alkyl group in R ⁵⁵ . X ¹ is a halogen atom. X ¹ is more preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.

Examples of the alkyl group in R ⁵⁵ include an alkyl group having 1 to 10 carbon atoms in R ^1A to R ^20A , respectively.

Examples of the alkyl group having 1 to 10 carbon atoms in R ⁵⁵ are methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, etc. Linear alkyl groups; Branched alkyl groups such as isopropyl group, sec-butyl group, tert-butyl group, isopentyl group, 1-methylpentyl group and 1-propylbutyl group; Cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group; These etc. are mentioned, The group represented by a following formula is mentioned. In the following formula, * represents a bonding hand. Especially, a C1-C8 alkyl group is preferable, a C1-C6 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.

Examples of the group in which an oxygen atom is inserted between the methylene groups constituting the alkyl group in R ⁵⁵ include a group represented by the following formula. In the following formula, * represents a bonding hand.

A phenyl group, a naphthyl group, etc. are mentioned as an aromatic hydrocarbon group in R <^55> , A phenyl group is preferable.

As a substituent of an aromatic hydrocarbon group in R <^55> , Halogen atoms, such as a fluorine atom, a chlorine atom, and iodine; Haloalkyl groups having 1 to 6 carbon atoms such as a chloromethyl group and a trifluoromethyl group; Alkoxy groups having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; Hydroxyl group; C1-C6 alkyl groups, such as a methyl group and an ethyl group; Sulfamoyl group; C1-C6 alkylsulfonyl groups, such as a methylsulfonyl group; C1-C6 alkoxycarbonyl groups, such as a methoxycarbonyl group, etc. are mentioned. Specific examples of the aromatic hydrocarbon group which may be substituted include groups represented by the following formulas. In the following formula, * represents a bonding hand.

R ⁵⁵ is preferably an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group which may be substituted, and more preferably an alkyl group having 1 to 8 carbon atoms or a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, and carbon atoms. It is an aromatic hydrocarbon group which may be substituted by the alkoxy group of 1-4, a hydroxyl group, a C1-C4 alkyl group, or a methylsulfonyl group, More preferably, it is an aromatic hydrocarbon group represented by a following formula. In the following formula, * represents a bonding hand.

It is preferable that the compound represented by Formula (A-V) is a compound represented by Formula (A-I) (henceforth a compound (A-I).). Compounds represented by the formula (A-I) also include tautomers thereof.

[In formula (A-I), Y represents p-valent anion.

R ⁴⁶ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group which may be substituted. In R ⁴⁶ , an oxygen atom may be inserted between the methylene groups constituting the alkyl group.

X represents O, S or NH.

A represents the m-valent organic group which may be substituted.

m represents the integer of 2-6.

n represents the integer of 1-6.

p represents the integer of 1-6.

q represents an integer of 1 to 6.]

In formulas (A-V) and (A-I), n is determined according to the charge m of the cation and the charge p of the anion, and is generally adjusted so that the charges of the whole of the formulas (A-V) and (A-I) become zero. Usually, n is a value obtained by dividing the least common multiple of m and p by m, and in the present invention, n is preferably 1 to 6, more preferably 1 to 3.

The cationic moieties of formulas (A-V) and (A-I) are represented by formulas (A-V-2) and (A-I-3), respectively.

(In the formula, R ^9A ~ R ^20A , R ⁴⁶ , R ⁵⁵ , A and m are the same as the above formula.)

Specifically, cation 1-cation 198 etc. which have a substituent shown to the following table in (A-I-3) are mentioned.

Each substituent in the table is as follows.

Especially, as a cation part represented by Formula (A-I-3), cation 1-cation 102 is preferable, cation 55-cation 102 is more preferable, cation 55-cation 66 is further more preferable.

Y in Formula (AV) represents p-valent anion. [Y] ^p- may include a known anion, but at least one element and oxygen selected from the group consisting of boron-containing anions, aluminum-containing anions, fluorine-containing anions, and tungsten, molybdenum, silicon and phosphorus in terms of heat resistance Anion which contains as an essential element is preferable.

As an boron containing anion and aluminum containing anion, the anion represented by following formula (4) is mentioned.

[In formula (4), W <^1> , W <^2> respectively independently represents the group which has two substituents formed by releasing proton from monovalent proton donor substituent. M represents boron or aluminum.]

Groups having two substituents formed by releasing protons from monovalent proton donor substituents include two proton donor substituents in a compound having at least two monovalent proton donor substituents (e.g., hydroxy, carboxylic acid, etc.) The group in which the proton is released is mentioned. Examples of the compound include catechol which may have a substituent, 2,3-dihydroxynaphthalene which may have a substituent, 2,2'-biphenol which may have a substituent, and 3-hydroxy-2 which may have a substituent. -Naphthoic acid, 2-hydroxy-1-naphthoic acid which may have a substituent, 1-hydroxy-2-naphthoic acid which may have a substituent, vinaphthol which may have a substituent, salicylic acid which may have a substituent Benzylic acid which may have or mandelic acid which may have a substituent is preferable.

In the compounds exemplified above, examples of the substituent include a saturated hydrocarbon group (eg, an alkyl group, a cycloalkyl group, etc.), a halogen atom, a haloalkyl group, a hydroxy group, an amino group, a nitro group, and an alkoxy group.

Examples of salicylic acid which may have a substituent include salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-methoxysalicylic acid, 3-nitrosalicylic acid, 4-trifluoromethylsalicylic acid, 3,5-di-tert-butyl Monoamino salicylic acid, such as salicylic acid, 3-aminosalicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, and 6-aminosalicylic acid; 3-hydroxysalicylic acid (2,3-dihydroxybenzoic acid), 4-hydroxysalicylic acid (2 4-hydroxybenzoic acid), 5-hydroxysalicylic acid (2,5-dihydroxybenzoic acid), 6-hydroxy Monohydroxysalicylic acids such as salicylic acid (2,6-dihydroxybenzoic acid); Dihydroxysalicylic acid, such as 4,5-dihydroxysalicylic acid and 4,6-dihydroxysalicylic acid; Monohalo salicylic acid, such as 3-chlorosalicylic acid, 4-chlorosalicylic acid, 5-chlorosalicylic acid, 6-chlorosalicylic acid, 3-bromosalicylic acid, 4-bromosalicylic acid, 5-bromosalicylic acid, and 6-bromosalicylic acid; Dihalosalicylic acid, such as 3,5-dichlorosalicylic acid, 3,5-dibromosalicylic acid, and 3,5-diiosalicylic acid; Trihalo salicylic acid such as 3,5,6-trichlorosalicylic acid; Etc. can be mentioned.

As the benzyl acid which may have a substituent

In mandelic acid which may have a substituent

Etc. can be mentioned.

Preferred anions among the anions represented by the formula (4) are anions represented by the following formulas, and have an anion (BC-1) to an anion (BC-24) having a substituent shown in the table, and a formula (BC-25), The anion (BC-25)-anion (BC-28) etc. which were represented by Formula (BC-26), Formula (BC-27), and Formula (BC-28) are mentioned.

Anions represented by formula (4) include anion (BC-1), anion (BC-2), anion (BC-3), anion (BC-25), anion (BC-26), anion (BC -27 ), Anion (BC-1), anion (BC-2) and anion (BC-25) are more preferred, and anion (BC-1) and anion (BC-2) are even more preferred. Salts formed by any of these anions and ions represented by formula (A-V-2) or formula (A-I-3) tend to have excellent solubility in organic solvents.

Examples of the fluorine-containing anion include groups represented by the following formulas (6), (7), (8) and (9).

[Formula (6) of the W ^3, and W ⁴ each independently represent a fluorinated alkyl group having a fluorine atom or a group having from 1 to 4 carbon atoms, W ³ and W ⁴ are shown with a fluoride alkanediyl group having a carbon number of 1 to 4.]

[Formula (7) of the W ⁵ ~ W ⁷ represents a fluorinated alkyl group having a fluorine atom or a group having from 1 to 4 carbon atoms each independently;

[In formula (8), Y <^1> represents a C1-C4 fluorinated alkanediyl group.]

[In formula (9), Y <^2> represents a C1-C4 alkyl fluoride group.]

In the formulas (6) and (7), a perfluoroalkyl group is preferable as the fluorinated alkyl group having 1 to 4 carbon atoms. As the perfluoroalkyl group, -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF (CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF (CF ₃ ), and the _2, -C (CF _{₃₎ 3.}

In formula (6) as seen fluoride alkanediyl group having from 1 to 4 carbon atoms is preferably a perfluoroalkyl roal alkanediyl group, and _{_{_{-CF 2 -, -CF 2 CF 2}}} -, -CF 2 CF 2 CF 2 -, -C (CF ₃ ) _2- , -CF ₂ CF ₂ CF ₂ CF ₂ -and the like.

In Formula (8), a perfluoro alkanediyl group is preferable as a C1-C4 fluorinated alkanediyl group. Examples of the perfluoroalkanediyl group include -CF _2- , -CF ₂ CF _2- , -CF ₂ CF ₂ CF _2- , -C (CF ₃ ) _2- , -CF ₂ CF ₂ CF ₂ CF ₂ -and the like. Can be.

In formula (9), a perfluoroalkyl group is preferable as the fluorinated alkyl group having 1 to 4 carbon atoms. Perfluoroalkyl groups include -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF (CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF (CF ₃ ) ₂ , -C (CF ₃ ) ₃ , and the like.

The anion represented by the formula (6) (hereinafter also referred to as "anion (6)") is an anion represented by the formulas (6-1) to (6-6), respectively (hereinafter referred to as "anion (6-1)" And " anion (6-6) ").

The anion represented by the formula (7) (hereinafter also referred to as "anion (7)") includes an anion (7-1) represented by the following formula.

The anion represented by the formula (8) (hereinafter also referred to as "anion (8)") is an anion represented by the formulas (8-1) to (8-4), respectively (hereinafter referred to as "anion (8-1)"). And " anion (8-4) ").

The anion represented by formula (9) (hereinafter also referred to as "anion (9)") is an anion represented by formulas (9-1) to (9-4), respectively (hereinafter referred to as "anion (9-1)"). And " anion (9-4) ").

At least one anion selected from the group consisting of an anion (6), an anion (7), an anion (8) and an anion (9) (i.e., a fluorine-containing anion, hereinafter referred to as anion (6) to (9)). It is possible to improve the solubility of the ions represented by the formula (AV-2) or the formula (AI-3) and the salt formed by the anion with respect to the organic solvent. Especially, anion (6-1), anion (6-2), and anion (7-1) are preferable, and anion (6-2) is especially preferable.

Anion which forms a salt with an ion represented by formula (AV-2) or formula (AI-3), and an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as an essential element And anions of heteropoly acid and isopoly acid containing tungsten as essential elements are preferable, and anions of phosphorous tungstic acid, silicon tungstic acid and tungsten-based isopoly acid are preferable.

An anion of a heteropoly acid or isophthalic acid polyester containing such a tungsten, as essential elements, for example, Kane ginhyeong of tungstate ion _{_{^{α- [PW 12 O 40] 3-}}} , Dawson type of tungstate ion α- [P ₂ W ₁₈ O ₆₂ ] ^6- , β- [P ₂ W ₁₈ O ₆₂ ] ^6- , Keggin-type silica tungstate ions α- [SiW ₁₂ O ₄₀ ] ^4- , β- [SiW ₁₂ O ₄₀ ] ^4- , γ- [ SiW ₁₂ O ₄₀ ] ^4- , other [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ W ₃₀ O ₁₁₀ ] ^14- , α- [SiW ₉ O ₃₄ ] ^10- , γ- [SiW ₁₀ O ₃₆ ] ^8- , α- [SiW ₁₁ O ₃₉ ] ^8- , β- [SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^2- and the like.

In addition, among the anions other than the anion of heteropoly acid or isopoly acid containing tungsten as an essential element, an anion composed of oxygen and at least one element selected from the group consisting of silicon and phosphorus is preferable.

Examples of the anion consisting of oxygen and at least one element selected from the group consisting of silicon and phosphorus include SiO ₃ ² ^- and PO ₄ ^3- .

Particularly, in view of ease of synthesis and post-treatment, heteropoly acid anions such as Keggin phosphotungstate ions, Dawson type phosphotungstate ions, and Keggin silicate tungstate ions, and isopolyacid anions such as [W ₁₀ O ₃₂ ] ^4- are preferred. Do.

p is 1-14 normally, Preferably it is 1-12, More preferably, it is 1-10, More preferably, it is 1-6, Especially preferably, it is 1-4.

In formulas (A-V) and (A-I) q is determined by the charge m of the cation and the charge p of the anion, and is generally adjusted so that the total charge of formulas (A-V) and (A-I) can be zero. Usually, q is a value obtained by dividing the least common multiple of m and p by p, and in the present invention, q is preferably 1 to 6, more preferably 1 to 3.

Examples of the compound (AV) include any one of the cations 1 to 198, anions (BC-1) to (BC-28), anions (6-1) to (6-6), and anions (7-1). , A combination of any one of anions (8-1) to (8-4), and anions (9-1) to (9-4), and anions of any three of the above cations 1 to 198 Combination with α- [PW ₁₂ O ₄₀ ] ^3- , any six of the cations 1 to 198 with a combination of anions α- [P ₂ W ₁₈ O ₆₂ ] ^6- , and any four of the cations 1 to 198 one may be positive and negative ions α- [SiW ₁₂ O _40] ^4- or [W ₁₀ O _32] ^4-, etc. with the combination. In the present invention, in particular, a combination of cations 1 to 198 and anion α- [PW ₁₂ O ₄₀ ] ^3- is preferable in that heat resistance is improved.

Compound (AV) can be prepared by mixing a salt comprising the cation (ie, formula (AV-2)) portion of compound (AV) with an anion [Y] ^p- alkali metal salt or an amphoteric asset. Salts containing cationic moieties include, for example, hydrochloride, phosphate, sulfate, benzenesulfonate, naphthalenesulfonate, perchlorate, BF ₄ salt, PF ₆ salt and the like. Moreover, lithium, sodium, potassium, etc. are mentioned as alkali metal.

The amount of the alkali metal salt or positive asset of the anion [Y] ^{p- for} the compound (AV-2) is added in accordance with the stoichiometric ratio so that the charge of the cation of the compound (AV-2) and the anion [Y] ^p- is balanced. Although what is necessary, it is preferably 0.5 mol or more and 8 mol or less, more preferably 1 mol or more and 3 mol or less with respect to 1 mol of compound (AV-2).

Mixing of the compound (AV-2) and an anionic [Y] ^{p- with} an alkali metal salt or an amphoteric asset may be carried out by dissolving both in the above solvent or without dissolving it.

Solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, ethyl acetate, toluene, methanol, ethanol, isopropanol, acetone, tetrahydrofuran, Dioxane, water and chloroform.

Among them, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, methanol, ethanol, isopropanol and water are preferable. In the case of such a solvent, there exists a tendency for the solubility of the alkali metal salt of a compound (AV-2) and an anion [Y] ^p- to become high.

The usage-amount of a solvent becomes like this. Preferably it is 1 mass part or more and 30 mass parts or less with respect to 1 mass part of compound (A-V-2), More preferably, it is 2 mass parts or more and 20 mass parts or less.

When the solvent is water, an acid such as acetic acid or hydrochloric acid may be added.

The mixing temperature of the compound (AV-2) and the alkali metal salt of the anion [Y] ^p- is preferably 0 to 150 ° C, more preferably 10 to 120 ° C, still more preferably 20 to 100 ° C. The mixing time is preferably 1 hour to 72 hours, more preferably 2 hours to 24 hours, even more preferably 3 hours to 12 hours.

In the case of using a solvent which is not compatible with water, the compound (A-V) can be obtained by mixing the solution, stirring for an additional 1 to 3 hours if necessary, and then obtaining a precipitate by filtration. If necessary, the obtained compound (A-V) may be washed with ion-exchanged water.

In the case of using a solvent which is not compatible with water, the reaction mixture and the ion-exchanged water are mixed and stirred for an additional 1 to 3 hours as necessary, and then the organic layer is obtained by separating the solution to obtain a solution containing the compound (AV). Can be. If necessary, the solution may be washed with ion-exchanged water. Compound (A-V) can be obtained by removing a solvent from the solution containing compound (A-V).

Compound (AV-2) can be produced, for example, by reacting a compound represented by the formula (B-IX) with a compound represented by the formula (CI), and in particular, a compound (AI-3) in which D is a thiazolyl group. Can be produced by reacting a compound represented by the formula (BI) with a compound represented by the formula (CI). The reaction may be carried out in the presence of an organic solvent or in a solvent-free manner.

[In formula (B-IX), (BI), and formula (CI), R <^1A> -R <^20A> , R <^46> , R <^55> , D, A, and m respectively represent the same meaning as the above.

In addition, the compound (AV-2) can be produced, for example, by reacting the compound represented by the formula (BX) with the compound represented by the formula (C-II) and the formula (C-III), in particular D is The compound (AI-3) which is a thiazolyl group can be produced by reacting the compound represented by the formula (B-II) with the compound represented by the formula (C-II) and formula (C-III). The reaction may be carried out in the presence of an organic solvent or in a solvent-free manner.

[In formula (BX), (B-II), (C-II), and (C-III), R <^1A> -R <^20A> , R <^46> , R <^55> , D, A, and m show the same meaning as the above. ]

The amount of the compound represented by the formula (CI) is preferably 0.5 mol or more and 10 mol or less, and more preferably 1 mol or more and 4 mol or less with respect to 1 mol of the compound represented by the formula (B-IX) or (BI). to be.

The total amount of the compound represented by the formula (C-II) and the compound represented by the formula (C-III) is preferably 0.5 moles or more and 20 moles per mole of the compound represented by the formula (BX) or (B-II). It is mol or less, More preferably, it is 1 mol or more and 10 mol or less.

30-180 degreeC is preferable and, as for reaction temperature, 80-130 degreeC is more preferable. 1 hour-12 hours are preferable, and, as for reaction time, 1 hour-8 hours are more preferable.

Any reaction is preferably carried out in an organic solvent in terms of yield. As an organic solvent, Hydrocarbon solvent, such as toluene and xylene; Halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform; Alcohol solvents such as methanol, ethanol, isopropanol and butanol; Nitrohydrocarbon solvents such as nitrobenzene; Ketone solvents such as methyl isobutyl ketone; Amide solvents such as 1-methyl-2-pyrrolidone; Etc. can be mentioned. The usage-amount of an organic solvent is 1 mass part or more and 20 mass parts or less with respect to 1 mass part of compounds represented by Formula (B-IX), (BI), (BX), and (B-II), More preferably, Preferably it is 2 mass parts or more and 10 mass parts or less.

The reaction is preferably carried out in the presence of a condensing agent in terms of yield. Phosphoric acid, polyphosphoric acid, phosphorus oxychloride, sulfuric acid, thionyl chloride, etc. are mentioned as a condensing agent.

The amount of the condensing agent used is preferably 0.1 part by mass or more and 20 parts by mass or less with respect to 1 part by mass of the compound represented by formula (B-IX), (BI), (BX), or (B-II). Is 0.2 mass part or more and 10 mass parts or less.

The method for obtaining the compound (A-V-2) from the reaction mixture is not particularly limited, and various known methods can be adopted. For example, the method of mixing a reaction mixture with solvents, such as alcohol (for example, methanol), and filtering and obtaining the precipitated crystal | crystallization is mentioned. It is preferable to add a reaction mixture to solvents, such as the said alcohol. The temperature at the time of adding a reaction mixture becomes like this. Preferably it is -100 or more and 50 or less, More preferably, it is -80 or more and 0 or less. Moreover, after that, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystals obtained by filtration are preferably washed with water or the like and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization as needed.

As a manufacturing method of a compound (B-I) and a compound (B-II), various well-known methods, for example, the method described in West German patent application P3928243.0 are mentioned.

Specifically compound (B-I) can be prepared by reacting compound (B-III) with an alkylating agent.

[In formula (B-III), R ⁵⁵ , A and m represent the same meaning as described above.]

As the alkylating agent, known alkylating agents such as alkyl halides and sulfuric acid esters can be used. In particular, alkyl halides are preferable in view of availability, and primary alkyl iodide is particularly preferable in view of ease of synthesis.

Specific examples of the alkylating agent include methyl iodide, ethyl iodide, normal butyl iodide, ethyl bromide, normal butyl bromide, 1,2-diiodineethane, 1,4-diiodobutane, 1,6-diiodinehexane, 1 , 8-diiooctane, 1,2-dibromoethane, 1,4-dibromobutane, 1,6-dibromohexane, 1,8-dibromooctane, 1,4-bis (bro Mother methyl) benzene, dimethyl sulfuric acid, diethyl sulfuric acid, etc. are mentioned.

For the compound represented by the formula (B-III), the amount of the alkylating agent used is preferably 2 moles or more and 6 moles or less, more preferably 2 moles or more and 4 moles to 1 mole of the compound represented by the formula (B-III). It is below moles.

20-180 degreeC is preferable and 30-50 degreeC of reaction temperature is more preferable. The reaction time is preferably 10 minutes to 10 hours, more preferably 30 minutes to 2 hours.

This reaction is preferably carried out in an organic solvent in terms of yield. As an organic solvent, Hydrocarbon solvent, such as toluene and xylene; Halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform; Alcohol solvents such as methanol, ethanol, isopropanol and butanol; Nitrohydrocarbon solvents such as nitrobenzene; Ketone solvents such as methyl isobutyl ketone; Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and 1-methyl-2-pyrrolidone; Etc. can be mentioned. The usage-amount of an organic solvent becomes like this. Preferably it is 1 mass part or more and 20 mass parts or less, More preferably, it is 2 mass parts or more and 10 mass parts or less with respect to 1 mass part of compounds represented by Formula (B-III).

The reaction is preferably carried out in the presence of a basic substance in terms of yield. Examples of the basic substance include sodium hydride, LDA, DIBAL, t-butoxy potassium and the like.

The usage-amount of a basic substance becomes like this. Preferably it is 2 mol or more and 6 mol or less, More preferably, it is 2 mol or more and 4 mol or less with respect to 1 mol of compounds represented by Formula (B-III).

In addition, compound (BI) can be manufactured even if the compound represented by Formula (B-IV) reacts with the coupling agent in which the bond (*) of the m-valent organic group which may be substituted mentioned above was substituted by the halogen atom. .

[In Formula (B-IV), R ⁴⁶ and R ⁵⁵ each represent the same meaning as described above.]

As a halogen atom in a coupling agent, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example, The halogen atom in one coupling agent molecule may be same or different, respectively. As a specific example of a coupling agent, the compound in which the bond (*) was substituted by the halogen atom in the organic group represented by a following formula is preferable, and the compound in which the bond (*) was substituted by the chlorine atom or the bromine atom is more preferable.

The amount of the linking agent used for the compound represented by the formula (B-IV) is preferably 0.1 mol or more and 2 mol or less, more preferably 0.2 mol or more and 1.2 mol, per 1 mol of the compound represented by the formula (B-IV). It is below moles.

20-180 degreeC is preferable and 40-100 degreeC of reaction temperature is more preferable. 30 minutes-20 hours are preferable, and, as for reaction time, 2 hours-12 hours are more preferable.

This reaction is preferably carried out in an organic solvent in terms of yield. As an organic solvent, Hydrocarbon solvent, such as toluene and xylene; Halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform; Alcohol solvents such as methanol, ethanol, isopropanol and butanol; Nitrohydrocarbon solvents such as nitrobenzene; Ketone solvents such as methyl isobutyl ketone; Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and 1-methyl-2-pyrrolidone; Etc. can be mentioned. The usage-amount of an organic solvent becomes like this. Preferably it is 1 mass part or more and 20 mass parts or less, More preferably, it is 2 mass parts or more and 10 mass parts or less with respect to 1 mass part of compounds represented by Formula (B-IV).

The reaction is preferably carried out in the presence of a basic substance in terms of yield. Examples of the basic substance include sodium hydride, potassium carbonate, LDA, DIBAL, t-butoxy potassium and the like.

The amount of the basic substance used is preferably 2 moles or more and 6 moles or less, more preferably 2 moles or more and 4 moles or less with respect to 1 mole of the compound represented by formula (B-IV).

The method for obtaining the compound represented by the formula (B-III) or the formula (B-IV) from the reaction mixture is not particularly limited, and various known methods can be employed. For example, the method of filtering and obtaining the crystal | crystallization which mixed the reaction mixture with alcohol (for example, methanol etc.) and precipitated is mentioned. The reaction mixture is preferably added to the alcohol. The temperature at the time of adding a reaction mixture becomes like this. Preferably it is -100 or more and 50 or less, More preferably, it is -80 or more and 0 or less. Moreover, after that, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystals obtained by filtration are preferably dried after washing with water or the like. Moreover, you may refine | purify further by well-known methods, such as recrystallization as needed.

Methods for preparing compounds represented by formula (B-III) or (B-IV) include Tetrahedron, 2008, vol. 64, p. 5019-5022, or European Journal of Medicinal Chemistry, 2014, vol. 72, p There are various known methods, such as those described in .26-34.

Specifically, the compound represented by formula (B-III) can be produced by reacting compound (B-V) and compound (B-VII).

Equation (BV) and the formula (B-VII) of the R ^55, A and m are the same meaning as above.]

The manufacturing method of the compound represented by Formula (B-VII) has various well-known methods, such as the method described in Synthesis, 1988, vol. 6, p.456-559.

In addition, the compound represented by a formula (B-IV) can be manufactured by making compound (B-V) and a compound (B-VI) react.

[In formula (BV) and (B-VI), R ⁴⁶ and R ⁵⁵ each represent the same meaning as described above. X ² represents a halogen atom.]

Formula (BV) with respect to the compound represented by formula (B-IV) Or the usage-amount of the compound represented by Formula (B-VI) is 1 mol or more and 5 mol or less with respect to 1 mol of compounds represented by Formula (B-IV), More preferably, they are 1 mol or more and 3 mol or less. .

20-180 degreeC is preferable and 30-100 degreeC of reaction temperature is more preferable. The reaction time is preferably 10 minutes to 10 hours, more preferably 30 minutes to 2 hours.

This reaction is preferably carried out in an organic solvent in terms of yield. As an organic solvent, Hydrocarbon solvent, such as toluene and xylene; Halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform; Alcohol solvents such as methanol, ethanol, isopropanol and butanol; Nitrohydrocarbon solvents such as nitrobenzene; Ketone solvents such as methyl isobutyl ketone; Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and 1-methyl-2-pyrrolidone; Etc. can be mentioned. The amount of the organic solvent used is preferably 1 part by mass or more and 20 parts by mass or less, and more preferably 2 parts by mass or more and 10 parts by mass or less based on 1 part by mass of the compound represented by the formula (B-V).

The manufacturing method of a compound (C-II) and (C-III) can mention various well-known methods, such as the method described in international publication 2012/053211.

Wherein R ^1A to R ^20A are the same as above. R ^1B is the same as R ^9A , R ^10A , R ^2B is the same as R ^11A , R ^13A , R ^3B is the same as R ^12A , R ^14A , and R ^4B is R ^15A , R ^18A , R ^5B is the same as R ^16A , R ^19A , R ^6B is the same as R ^17A , R ^20A . R ^7B , R ^8B are halogen atoms.)

As the alkylating agent, known alkylating agents such as alkyl halides and sulfate esters can be used. In particular, alkyl halides are preferred in view of availability, and primary alkyl iodide is particularly preferred in view of ease of synthesis. As the aralkylating agent, benzyl halide or the like can be used.

Examples of the alkylating agent include methyl iodide, ethyl iodide, normal butyl iodide, ethyl bromide, normal butyl bromide, dimethyl sulfuric acid and diethyl sulfuric acid. Examples of the aralkylating agent include benzyl iodide, benzyl bromide and the like.

The amount of the alkylating agent or aralkylating agent used is preferably 2 mol or more and 6 mol or less, and more preferably 2 mol or more and 4 mol or less, with respect to 1 mol of the compound represented by formula (C-IV).

20-180 degreeC is preferable and 30-50 degreeC of reaction temperature is more preferable. 10 minutes-10 hours are preferable, and, as for reaction time, 30 minutes-2 hours are more preferable.

Both reactions are preferably carried out in organic solvents in terms of yield. As an organic solvent, Hydrocarbon solvent, such as toluene and xylene; Halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform; Alcohol solvents such as methanol, ethanol, isopropanol and butanol; Nitrohydrocarbon solvents such as nitrobenzene; Ketone solvents such as methyl isobutyl ketone; Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and 1-methyl-2-pyrrolidone; Etc. can be mentioned. The usage-amount of an organic solvent becomes like this. Preferably it is 1 mass part or more and 20 mass parts or less, More preferably, it is 2 mass parts or more and 10 mass parts or less with respect to 1 mass part of compounds represented by Formula (C-IV).

The reaction is preferably carried out in the presence of a basic compound in terms of yield. Examples of the basic compound include sodium hydride, LDA, DIBAL, t-butoxy potassium and the like.

The use amount of the basic compound is preferably 2 mol or more and 6 mol or less, and more preferably 2 mol or more and 4 mol or less, with respect to 1 mol of the compound represented by the formula (C-IV).

The method for obtaining the compound (C-IV) from the reaction mixture is not particularly limited, and various known methods can be adopted. For example, the method of mixing a reaction mixture with solvents, such as alcohol (for example, methanol), and filtering the precipitated crystal | crystallization is mentioned. It is preferable to add a reaction mixture to solvents, such as the said alcohol. The temperature at the time of adding a reaction mixture becomes like this. Preferably it is -100 or more and 50 or less, More preferably, it is -80 or more and 0 or less. Moreover, after that, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystals obtained by filtration are preferably dried after washing with water or the like. Moreover, you may refine | purify further by well-known methods, such as recrystallization as needed.

The compound (C-IV) can be prepared by reacting the compound (C-V) with the compound (C-VI) as described above. Moreover, the said compound (C-I) can also be manufactured by making compound (C-V) and compound (C-VI) react as mentioned above.

^Examples of the halogen atoms represented by R ^7B and R ^8B in the formula (C-VI) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. From the viewpoint of availability of raw materials, a fluorine atom and a chlorine atom are preferable.

The use amount of the compound (C-V) is preferably 2 mol or more and 5 mol or less, more preferably 2 mol or more and 3 mol or less, per 1 mol of the compound (C-VI).

Both reactions are preferably carried out in organic solvents in terms of yield. As an organic solvent, Hydrocarbon solvent, such as toluene and xylene; Halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform; Alcohol solvents such as methanol, ethanol, isopropanol and butanol; Nitro hydrocarbon solvents such as nitrobenzene; Ketone solvents such as methyl isobutyl ketone; Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and 1-methyl-2-pyrrolidone; Etc. can be mentioned. The usage-amount of an organic solvent is 1 mass part or more and 20 mass parts or less with respect to 1 mass part of compounds represented by a formula (C-VI), More preferably, they are 2 mass parts or more and 10 mass parts or less.

In view of yield, the reaction is preferably carried out in the presence of a palladium compound, a phosphine compound and a basic compound.

Examples of palladium compounds include palladium acetate (II), palladium chloride (II), palladium bromide (II), bis (2,4-pentanedioato) palladium (II), bis (dibenzilideneacetone) palladium (0) and tris (Dibenzylidene acetone) dipalladium (0) etc. are mentioned.

The use amount of the palladium compound is preferably 0.0001 mol or more and 0.5 mol or less, and more preferably 0.001 mol or more and 0.1 mol or less, with respect to 1 mol of the compound (C-VI).

Examples of the phosphine compounds include dppf, Xantphos, BINAP, XPhos, SPhos, MePhos and the like.

The use amount of the phosphine compound is preferably 0.001 mol or more and 0.5 mol or less, and more preferably 0.003 mol or more and 0.1 mol or less, per 1 mol of the compound (C-VI).

Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, t-butoxy sodium and t-butoxy potassium.

The amount of the basic compound used is preferably 1 mol or more and 5 mol or less, more preferably 1 mol or more and 3 mol or less, per 1 mol of the compound (C-VI).

The method for obtaining the compound (C-IV) from the reaction mixture is not particularly limited, and various known methods can be adopted. For example, the method of mixing a reaction mixture with alcohol (for example, methanol, etc.), and filtering the precipitated crystal | crystallization is mentioned. The reaction mixture is preferably added to the alcohol. The temperature at the time of adding a reaction mixture becomes like this. Preferably it is -100 or more and 50 or less, More preferably, it is -80 or more and 0 or less. Moreover, after that, it is preferable to stir at the same temperature for 0.5 to 2 hours. The crystals obtained by filtration are preferably dried after washing with water or the like. Moreover, you may refine | purify further by well-known methods, such as recrystallization as needed.

The alkali metal salt of the anion represented by Formula (4) may use a commercial item, for example, Unexamined-Japanese-Patent No. 4097704 or 4341251 and Journal of The Electrochemical Society, Vol. 148, 1st, 2001 . It can manufacture by the method as described in.

The alkali metal salt of the anion represented by Formula (6), Formula (7), Formula (8) or Formula (9) may use a commercial item, the method described in international application 2008/075672 or JP2010-280586, etc. It can be prepared by.

The alkali metal salt of the anion containing at least one element selected from the group consisting of tungsten, silicon, and phosphorus and oxygen as an essential element may be produced by a known method, but a commercial item may be used as it is. As such a compound, the corresponding heteropoly acid salt, isopoly acid salt, silicate, phosphate, etc. are mentioned. As these various salts, since monovalent metal salts, such as sodium, lithium, and potassium, are excellent in water solubility, since synthesis and post-processing become easy, it is preferable.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following Examples, and of course, the present invention may be appropriately modified and implemented within a range suitable for the purpose of the present invention. These are all included in the technical scope of the present invention. In addition, unless otherwise indicated, "part" means a "mass part" and "%" means the "mass%."

In the following, the structure of the compound was confirmed by mass spectrometry (LC; 1200 manufactured by Agilent, MASS; LC / MSD manufactured by Agilent), and UV-VIS (Japanese spectrometer V-650).

Synthesis Example 1

The following reaction was carried out under a nitrogen atmosphere. 15 parts of 2'-fluoroacetophenone (Tokyo Chemical Co., Ltd.), 105 parts of ethyl acetate, 0.15 part of 48% hydrobromic acid were dripped at the flask with a cooling tube and the stirring apparatus, and 17.9 parts of bromine were dripped at room temperature. Then, it reacted at room temperature for 30 minutes. The reaction solution was washed with about 1% aqueous sodium sulfite solution followed by about 7% aqueous sodium hydrogen carbonate solution to separate the organic layer. The organic layer was washed with water, 10% brine and concentrated under reduced pressure to obtain 2-bromo-2'-fluoroacetophenone in the form of a pale yellow liquid.

And the following reaction was performed in nitrogen atmosphere. 17.2 parts of torylthiourea (manufactured by Tokyo Chemical Co., Ltd.) and 105 parts of methanol were placed in a flask equipped with a cooling tube and a stirring device, and the total amount of 2-bromo-2'-fluoroacetophenone prepared therein was added dropwise at room temperature. After reacting as it is at room temperature for 1 hour, 100 parts of ion-exchange water was dripped, and 30% sodium hydroxide aqueous solution was added, and it adjusted to pH = 5-6. The slurry was filtered, and the obtained cake was washed with water and dried to obtain 27.0 parts of the compound represented by the formula (B-IV-1) in the form of white crystals. Yield 91.9%

The following reaction was carried out under a nitrogen atmosphere. 10 parts of the compound represented by the formula (B-IV-1), 4.6 parts of α, α'-dibromo-p-xylene (manufactured by Tokyo Chemical Co., Ltd.) and 5.8 parts of potassium carbonate in a flask equipped with a cooling tube and a stirring device. And 36.7 parts of dimethylacetamide were reacted at 70 for 6 hours. The reaction solution was poured into a mixed solution of 46 parts of acetonitrile and 31 parts of ion-exchanged water to crystallize. The cake obtained by filtration at room temperature was washed with ion-exchanged water and acetonitrile and dried to obtain a crude crystal of the compound represented by the formula (B-I-1). The crude crystals were suspended in 100 parts of acetonitrile, stirred at 80 for 20 minutes, cooled to room temperature, and filtered. The obtained cake was washed with acetonitrile and dried to obtain 9.6 parts of the compound represented by the formula (B-I-1) in the form of white crystals. Yield 81.8%

The following reaction was carried out under a nitrogen atmosphere. 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Co., Ltd.) and 60 parts of N, N-dimethylformamide were added to a flask equipped with a cooling tube and a stirring device, and the mixed solution was cooled under ice conditions. Under ice-cooling conditions, 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Co., Ltd.) was added little by little over 30 minutes, followed by stirring for 1 hour while raising the temperature to room temperature. 10.4 parts of 4,4'-difluorobenzophenone (Tokyo Chemical Co., Ltd. product) was added little by little to the reaction liquid, and it stirred at room temperature for 24 hours. The reaction solution was added to 200 parts of ice water little by little, left at room temperature for 15 hours, and water was separated and removed by decantation to obtain a viscous solid as a residue. 60 parts of methanol was added to this viscous solid, followed by stirring at room temperature for 15 hours. The precipitated solid was filtered off and purified by column chromatography. The purified pale yellow solid was dried under reduced pressure at 60 to obtain 9.8 parts of the compound represented by the formula (C-I-1). Yield 53%

The following reaction was carried out under a nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 3.0 parts of the compound represented by the formula (BI-1), 3.51 parts of the compound represented by the formula (CI-1) and 14 parts of toluene were placed and heated to 100, followed by oxychloride. 2.1 parts of phosphorus (made by Wako Pure Chemical Industries, Ltd.) was dripped at 100-110, and it was made to react at 110 for 5 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and 10.5 parts of methanol was added dropwise. The reaction solution was poured into a separatory funnel containing 30 parts of 20% saline solution and 21 parts of toluene while washing with 15 parts of isopropanol. After stirring at room temperature, the organic layer was separated and washed twice with 30 parts of 20% saline solution and then concentrated. To this concentrated residue, 33 parts of ethyl acetate was added to crystallize and filtered. In addition, 6.2 parts of compounds represented by Formula (A-II-1) which are blue individuals were obtained by repeating suspension washing with 30 parts of ethyl acetate three times, and drying. Yield 92.8%

The following reaction was performed in nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 1.00 parts of the compound represented by the formula (A-II-1), 1.61 parts of phosphotungstic acid n-hydrate (Aldrich) and 5.3 parts of dimethyl sulfoxide were added thereto. Stir for 1 hour. Subsequently, the reaction mixture was cooled to room temperature and then dropwise added to 150.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The suspension obtained was filtered to give a blue violet solid. In addition, the obtained blue-purple solid was suspended and washed with ion-exchanged water and methanol and purified. The purified blue-purple solid was dried under the reduced pressure of 60, and 0.67 parts of compounds of formula (A-I-1) were obtained. Yield 29.9%

Identification of the compound represented by formula (A-I-1) (UV-VIS):

0.10 g of the compound represented by formula (AI-1) was dissolved in N and N-dimethylformamide to a volume of 100 cm ³ , of which 2 cm ³ was diluted with N and N-dimethylformamide to a volume of 250 cm ³ . (Concentration: 0.008 g / L) and the absorption spectrum was measured using the spectrophotometer (quartz cell, optical path length; 1 cm). This compound showed an absorbance of 0.2 (arbitrary unit) at λ max = 630 nm.

Synthesis Example 2

The following reaction was carried out under a nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 2.5 parts of potassium thiocyanate (manufactured by Wako Pure Chemical Industries, Ltd.) and 15 parts of tetrahydrofuran were placed, and 3.0 parts of benzoyl chloride (manufactured by Tokyo Chemical Co., Ltd.) was added dropwise thereto. After stirring for 30 minutes at room temperature, 2.17 parts of 4,4'-diamino-3,3'-dimethyldiphenylmethane (made by Tokyo Chemical Co., Ltd.) were thrown in at room temperature. Then, it was made to react at room temperature for 2 hours, and 30 parts of ion-exchange water was dripped, and it crystallized. The obtained crystal was filtered and washed with ion exchanged water to obtain a crude crystal of the compound represented by formula (B-VIII-2). This crude crystal was further suspended and purified in methanol to obtain 6.5 parts of the compound represented by the formula (B-VIII-2) as a wet cake.

The following reaction was carried out under a nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 6.5 parts of compounds represented by the formula (B-VIII-2) and 15 parts of methanol were placed, and 4.3 parts of 30% aqueous sodium hydroxide solution was added dropwise at room temperature, followed by heating to 60. In the meantime, 15 parts of additional methanol was added and the reaction was continued. The reaction time was 1.5 hours. Thereafter, 30 parts of ion-exchanged water was added dropwise to crystallize. The obtained crystals were filtered, washed with ion-exchanged water, and dried to obtain 3.05 parts of the compound represented by the formula (B-VII-2) in a white crystal state. Yield 92.1%

The following reaction was carried out under a nitrogen atmosphere. A flask equipped with a cooling tube and a stirring device was equipped with 4.0 parts of the compound represented by the formula (B-VII-2) and 20 parts of methanol, and 5.9 parts of 2-bromo-2'-fluoroacetophenone (manufactured by Aldrich). It dripped at room temperature. In the meantime, 40 parts of methanol was further added, and the reaction temperature was raised to 35. The reaction time was 1 hour. Thereafter, after cooling to room temperature, 20 parts of ion-exchanged water was added dropwise, and 30% sodium hydroxide aqueous solution was further added to adjust the pH to 7-6. The slurry obtained by filtering this slurry was washed with ion exchanged water, and then dried to obtain 6.4 parts of the compound represented by the formula (B-III-2) in a white crystal state. Yield 94.4%

The following reaction was carried out under a nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 5.93 parts of the compound represented by the formula (B-III-2) and 20 parts of N and N-dimethylformamide were placed therein, and 60% sodium hydride (manufactured by Tokyo Chemical Co., Ltd.) 0.86 Part was added at room temperature. After stirring at room temperature for 5 minutes, 3.34 parts of ethyl iodide (made by Wako Pure Chemical Industries, Ltd.) was dripped similarly at room temperature. After reacting at room temperature for 1 hour, 100 parts of ion-exchanged water and 32 parts of ethyl acetate were separated, and the organic phase was washed with 100 parts of saturated brine, dried over anhydrous magnesium sulfate (available from Wako Pure Chemical Industries, Ltd.), and concentrated. After adding 21 parts of methanol to crystallization and crystallizing, the obtained crystals were filtered, washed with methanol, and dried to obtain a crude crystal of the compound represented by the formula (B-I-2). The crude crystals were suspended in 15 parts of acetonitrile, stirred at 60 to 30 minutes, cooled to room temperature and filtered. The obtained crystal was washed with acetonitrile and dried to obtain 5.6 parts of the compound represented by the formula (B-I-2) in the form of white crystals. Yield 86.2%

The following reaction was carried out under a nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 4.46 parts of the compound represented by the formula (B-I-2), 5.5 parts of the compound represented by the formula (C-I-1) and 16.5 parts of toluene were placed and heated to 100. 3.22 parts of phosphorus oxychloride (made by Wako Pure Chemical Industries, Ltd.) was dripped at this solution at 100-110, and it reacted at 110-7 hours. It cooled to room temperature after completion | finish of reaction, and 10 parts of acetonitrile, then 19 parts of methanol were dripped. The reaction solution was poured into 975 parts of isopropanol in a separatory funnel containing 275 parts of 20% saline solution and 55 parts of toluene. After stirring at room temperature, the organic layer was separated, washed three times with 275 parts of 20% brine and concentrated. This concentrated residue was dissolved in 20 parts of acetone, and added dropwise to 275 parts of ethyl acetate to crystallize. The obtained crystals were filtered, washed with ethyl acetate and dried to obtain 10.0 parts of the compound represented by the formula (A-II-2) in a blue individual state. Yield 97.8%

Identification of the compound represented by formula (A-II-2) (mass spectrometry):

Ionization mode = ESI +: m / z = 693.3 [(M-2Cl) / 2] ⁺

Exact Mass: 1456.5

The following reaction was carried out under a nitrogen atmosphere. Into a flask equipped with a cooling tube and a stirring device, 0.86 parts of a compound represented by formula (A-II-2), 1.41 parts of phosphotungstic acid n-hydrate (manufactured by Aldrich) and 4.7 parts of dimethyl sulfoxide were added thereto. Stirred for 1 hour. Subsequently, the reaction mixture was cooled to room temperature and then dropwise added to 150.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The suspension obtained was filtered to yield a blue violet solid. Thereafter, the obtained blue-purple solid was suspended and purified in ion-exchanged water and methanol. The purified blue-purple solid was dried at 60 under reduced pressure, and 0.73 parts of compounds of formula (A-I-2) were obtained. Yield 37.5%

Identification of compound represented by formula (A-I-2) (UV-VIS):

0.10 g of the compound represented by formula (AI-2) was dissolved in N and N-dimethylformamide to a volume of 100 cm ³ , of which 2 cm ³ was diluted with N and N-dimethylformamide to a volume of 250 cm ³ . (Concentration: 0.008 g / L), the absorption spectrum was measured using the spectrophotometer (quartz cell, optical path length; 1 cm). This compound showed an absorbance of 0.2 (arbitrary unit) at λ max = 627 nm.

합성예Synthesis Example 3 3

The following reaction was performed in nitrogen atmosphere. Into a flask equipped with a cooling tube and a stirring device, 1.00 parts of Victoria Pure Blue BOH conc (product of Hodogaya Chemical), 2.33 parts of phosphotungstic acid n-hydrate (Aldrich), and 15.4 parts of dimethyl sulfoxide were added thereto. Stirred for 1 hour. Subsequently, the reaction mixture was cooled to room temperature and then added dropwise with stirring for 30 hours to 300.0 parts of tap water to obtain a dark blue suspension. The suspension obtained was filtered to give a turquoise solid. Then, the obtained turquoise solid was purified by column chromatography. The purified cyan solid was dried under reduced pressure at 60 to obtain 2.8 parts of the compound represented by the formula (A-III-1). Yield 100%

Identification of compound represented by formula (A-III-1) (UV-VIS):

0.10 g of the compound represented by the formula (A-III-1) was dissolved in N and N-dimethylformamide to a volume of 100 cm ³ , of which 2 cm ³ was diluted with N and N-dimethylformamide to a volume of 250 cm. ^The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm) at ³ (concentration: 0.008 g / L). This compound exhibited an absorbance of 0.2 (arbitrary unit) at λ max = 626 nm.

(분해 온도의 측정)(Measurement of decomposition temperature)

Differential scanning calorimetry of the compounds obtained in Synthesis Examples 1 to 3 was carried out using a differential thermal gravimetric simultaneous measurement apparatus (manufactured by S-I Nano Technology, TG / DTA6200R). The sample amount used for one measurement was 5 mg. The measurements were started at 25 and raised to 600 at a rate of 10 per minute. The extrapolation temperature of the peak of the obtained TG curve was made into decomposition temperature. The measurement was performed twice in the presence of air under a nitrogen atmosphere. The decomposition temperature can be said to be an index indicating heat resistance.

By using the compound excellent in heat resistance of this invention, the color filter excellent in heat resistance can be provided. The color filter is useful as a color filter that can be used in a liquid crystal display and a solid state image pickup device.

Claims

A compound characterized by the following formula (A-V):

[Formula 1]

[In formula (A-V), Y represents p-valent anion.

R 1A , R 2A , R 3A , R 4A , R 5A , R 6A , R 7A and R 8A each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R 9A and R 10A each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, optionally substituted aromatic hydrocarbon group, or which may be substituted represents an aralkyl group.

R 11A to R 14A each independently represent a hydrogen atom, a halogen atom and an alkyl group having 1 to 10 carbon atoms.

R 15A, R 16A, R 17A , R 18A, R 19A and R 20A represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms independently.

In the R 1A ~ R 20A wherein the alkyl group is an oxygen atom may be inserted between methylene groups constituting.

R 46 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group which may be substituted, and an oxygen atom may be inserted between the methylene groups constituting the alkyl group in R 46 .

D represents an aromatic group which may be substituted.

A represents the m-valent organic group which may be substituted.

m represents the integer of 2-6.

n represents the integer of 1-6.

p represents the integer of 1-6.

q represents an integer of 1 to 6.]
A compound characterized by the following formula (A-I):

[Formula 2]

[In formula (A-I), Y represents p-valent anion.

R 1A , R 2A , R 3A , R 4A , R 5A , R 6A , R 7A and R 8A each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R 9A and R 10A each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, optionally substituted aromatic hydrocarbon group, or which may be substituted represents an aralkyl group.

R 11A to R 14A each independently represent a hydrogen atom, a halogen atom and an alkyl group having 1 to 10 carbon atoms.

R 15A, R 16A, R 17A , R 18A, R 19A and R 20A represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms independently.

In the R 1A ~ R 20A wherein the alkyl group is an oxygen atom may be inserted between methylene groups constituting.

R 46 is an oxygen atom may be inserted between the methylene group to a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or represents an optionally substituted aromatic hydrocarbon good, in the configuration R 46 is the alkyl group.

R 55 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group which may be substituted, and an oxygen atom may be inserted between the methylene groups constituting the alkyl group in R 55 .

X represents O, S or NH.

A represents the m-valent organic group which may be substituted.

m represents the integer of 2-6.

n represents the integer of 1-6.

p represents the integer of 1-6.

q represents an integer of 1 to 6.]
The method according to claim 1 or 2,

A counter ion is a compound characterized in that it is an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as an essential element.
A compound characterized by the following formula (B-1):

[Formula 3]

[In formula (B-I),

R 46 is an oxygen atom may be inserted between the methylene group to a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or represents an optionally substituted aromatic hydrocarbon good, in the configuration R 46 is the alkyl group.

R 55 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group which may be substituted, and an oxygen atom may be inserted between the methylene groups constituting the alkyl group in R 55 .

X represents O, S or NH.

A represents the m-valent organic group which may be substituted.

m represents an integer of 2 to 6.]