Triarylmethane pigment, coloring composition containing same, colorant for color filter, and color filter

Abstract

The present invention relates to a triarylmethane pigment, a coloring composition containing the pigment, a colorant for a color filter, and a color filter, and provides a triarylmethane pigment having excellent heat resistance, and a colorant for a color filter having good color characteristics by using the coloring composition of the pigment. A triarylmethane dye represented by general formula (1); a coloring composition containing the pigment; a colorant for a color filter; and a color filter. In formula (1), R1-R4 represent H, an alkyl group, or an aromatic hydrocarbon group, R5 and R6 represent H, a halogen atom, OH, CF3, NO2, CN, an alkyl group, an alkoxy group, or an aryloxy group, AH represents a heterocyclic group, An represents an anion, and m represents a natural number. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a triarylmethane dye, a coloring composition containing the dye, a colorant for a color filter containing the dye or the coloring composition, and a color filter using the colorant. Background Art

[0002] Color filters are used in solid-state imaging elements such as liquid crystal display devices, organic electroluminescent (organic EL) display devices, CCDs, and CMOS sensors, and have red pixels (R), green pixels (G), and blue pixels (B). Colorants used in color filters include pigments and dyes, which are exposed to high temperatures of 200°C or above, ultraviolet radiation, and other conditions when manufacturing color filters. Therefore, pigments with better heat resistance and light resistance than dyes are generally used. For example, as a blue pigment for forming a blue pixel portion, an ε-type copper phthalocyanine pigment (CI Pigment Blue 15:6) is generally used, and a small amount of a purple dioxazine violet pigment (CI Pigment Violet 23) is used in combination for color matching as needed.

[0003] As a recent trend, image display devices are being pursued for energy savings. To improve backlight efficiency, there is a growing demand for higher-brightness color filters. In particular, backlight efficiency in blue pixels is relatively low compared to red and green pixels, and this improvement is desired.

[0004] Pigments are generally insoluble in solvents and therefore exist as fine particles in color filters made of resins, etc. Consequently, it is known that color filters using pigments reflect and scatter transmitted light at the surface of the pigment particles, thereby reducing brightness and affecting color purity. Furthermore, depolarization due to reflection reduces the contrast ratio of color displays.

[0005] In order to improve the problem of brightness and contrast ratio reduction, not only the pigments that have always been used as colorants have been studied, but also the situation of using only dyes (such as patent document 1). Since dyes are soluble in solvents, the depolarization effect of the color filter using dyes is suppressed compared with the situation of using only pigments as colorants, and the spectral characteristics are excellent, and it is expected that brightness, contrast, etc. will be improved. For this reason, especially for the color filter of the blue pixel portion, the use of dyes that are generally more soluble than pigments has attracted much attention.

[0006] In particular, triarylmethane dyes have excellent spectral properties. For example, Patent Documents 2 to 5 describe attempts to use triarylmethane dyes as colorants for color filters. Furthermore, Patent Documents 3, 4, and 6, as well as Non-Patent Document 1, describe triarylmethane dyes having a heterocyclic skeleton. These dyes exhibit excellent spectral properties and high stability, and therefore have attracted considerable attention.

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 6-75375

[0008] Patent Document 2: Japanese Patent Application Laid-Open No. 2008-304766

[0009] Patent Document 3: International Publication No. 2012 / 128318

[0010] Patent Document 4: Japanese Patent Application Laid-Open No. 2015-28121

[0011] Patent Document 5: Japanese Patent Application Laid-Open No. 2012-83652

[0012] Patent Document 6: Japanese Patent Application Laid-Open No. 2003-165918

[0013] Non-patent literature

[0014] Non-patent document 1: Helvetica, (USA), February 13, 1985, Vol. 68, Issue 1, pp. 64-71

[0015] Non-Patent Document 2: Hiroshi Horiguchi, "A Comprehensive Discussion of Synthetic Dyes," Sankyo Publishing Co., Ltd., July 15, 1969, pp. 79-109 Summary of the Invention

[0016] However, when using triarylmethane dyes with known structures to manufacture color filters, as described in Patent Documents 1 to 3, there is a problem that the hue easily changes due to the thermal history during the manufacturing process. High heat resistance is an important characteristic required of colorants for color filters. Although triarylmethane dyes with specific structures are described in Patent Documents 4 and 5 as colorants for color filters with excellent heat resistance, their heat resistance is insufficient and further improvement of heat resistance is needed. Patent Documents 3 and 6 and Non-Patent Document 1 disclose triarylmethane dyes with excellent solvent resistance and light resistance, but there is no description of heat resistance.

[0017] The present invention aims to provide a dye having superior heat resistance compared to conventional triarylmethane dyes. Another object of the present invention is to provide a colorant for a color filter having good color characteristics (color gamut, brightness, contrast ratio, etc.) by using a coloring composition using the dye.

[0018] Intensive studies have been conducted to solve the above-mentioned problems, and as a result, the present invention has been developed, the gist of which is as follows.

[0019] 1. A triarylmethane dye represented by the following general formula (1).

[0020]

Chemical Formula 1

[0021]

[0022] [In formula (1), R 1 ~R 4 Each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent;

[0023] R 5 、R 6 Each independently represents a hydrogen atom, a halogen atom, -OH, -CF3, -NO2, -CN, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms which may have a substituent, or an aryloxy group having 6 to 20 carbon atoms which may have a substituent;

[0024] A H represents a heterocyclic group represented by the following general formula (2);

[0025] An represents an anion, and m represents a natural number.]

[0026]

Chemical Formula 2

[0027]

[0028] [In formula (2), X 1 represents nitrogen atom, CR 9 or NR 10 ;

[0029] X 2 Indicates CR 9 or NR 10 ;

[0030] X 1 and X 2 At least one of the NR 10 ;

[0031] R 7 ~R 9 Independently represent:

[0032] Hydrogen atoms, halogen atoms,

[0033] ―OH, ―CF3, ―NO2, ―CN,

[0034] a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, a linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms which may have a substituent,

[0035] a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms which may have a substituent,

[0036] an aryloxy group having 6 to 20 carbon atoms which may have a substituent,

[0037] an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,

[0038] a heterocyclic group having 5 to 20 ring atoms which may have a substituent,

[0039] ―NR 11 R 12 、

[0040] an acyl group having 1 to 20 carbon atoms which may have a substituent,

[0041] a linear, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms which may have a substituent, or an aryloxycarbonyl group having 7 to 20 carbon atoms which may have a substituent;

[0042] R 10 express:

[0043] a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, a linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or

[0044] a heterocyclic group having 5 to 20 ring atoms which may have a substituent;

[0045] R 11 and R 12 Independently represent:

[0046] a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent,

[0047] an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent or

[0048] a heterocyclic group having 5 to 20 ring atoms which may have a substituent;

[0049] R 7 ~R 12 Adjacent groups can be bonded to each other via single bonds, double bonds, substituted or unsubstituted methylene groups, oxygen atoms, or sulfur atoms to form a ring;

[0050] The dotted line portion represents the bonding portion with the general formula (1).]

[0051] 2. The triarylmethane dye according to 1. above, wherein in the general formula (1), A H It is a heterocyclic group represented by any one of the following general formulae (2-1) to (2-4).

[0052]

Chemical Formula 3

[0053]

[0054] [In formula (2-1), R 7 ~R 10 Indicates that R in the general formula (2) 7 ~R 10 The same group, adjacent R 7 and R 9 and R 8 and R 9 can be independently bonded to each other via a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring;

[0055] The dotted line portion represents the bonding portion with the general formula (1).]

[0056]

Chemical Formula 4

[0057]

[0058] [In formula (2-2), R 7 ~R 10 Indicates that R in the general formula (2) 7 ~R 10 The same group, adjacent R 7 and R 9 can be bonded to each other via single bonds, double bonds, substituted or unsubstituted methylene groups, oxygen atoms or sulfur atoms to form a ring;

[0059] The dotted line portion represents the bonding portion with the general formula (1).]

[0060]

Chemical Formula 5

[0061]

[0062] [In formula (2-3), R 7 、R 8 and R 10 Indicates that R in the general formula (2) 7 、R 8 and R 10 The dotted line portion represents the bonding portion with the general formula (1).]

[0063]

Chemical Formula 6

[0064]

[0065] [In formula (2-4), R 13 and R 15 ~R 18Indicates that R in the general formula (2) 7 ~R 9 The same group, R 14 represents a hydrogen atom, and the dotted line portion represents the bonding portion with the general formula (1).]

[0066] 3. The triarylmethane dye according to 2. above, wherein in the general formula (1), A H is a heterocyclic group represented by the above general formula (2-1), wherein R 7 、R 8 and R 10 are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, R 9 A hydrogen atom.

[0067] 4. The triarylmethane dye according to 2. above, wherein in the general formula (1), A H is a heterocyclic group represented by the above general formula (2-1), wherein R 7 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, R 8 and R 10 are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, R 9 It is an acyl group having 1 to 10 carbon atoms which may have a substituent, a linear, branched or cyclic alkoxycarbonyl group having 2 to 10 carbon atoms which may have a substituent, or an aryloxycarbonyl group having 7 to 10 carbon atoms which may have a substituent.

[0068] 5. The triarylmethane dye according to 2. above, wherein in the general formula (1), A H is a heterocyclic group represented by the above general formula (2-1), wherein R 7 is an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, R 8 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, R 9 is a hydrogen atom, R 10 It is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

[0069] 6. The triarylmethane dye according to 2. above, wherein in the general formula (1), A H is a heterocyclic group represented by the above general formula (2-2), wherein R 7 and R 9are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, R 8 and R 10 Each independently represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

[0070] 7. The triarylmethane dye according to 2. above, wherein in the general formula (1), A H is a heterocyclic group represented by the above general formula (2-3), R 7 NR 11 R 12 , R 8 and R 10 are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, 11 and R 12 Each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

[0071] 8. The triarylmethane dye according to 2. above, wherein in the general formula (1), A H is a heterocyclic group represented by the above general formula (2-4), wherein R 13 It is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

[0072] 9. The triarylmethane dye according to 1. above, wherein in the general formula (1), R 1 and R 2 are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, R 3 and R 4 Each independently represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

[0073] 10. The triarylmethane dye according to 1. above, wherein in the general formula (1), An is a perfluoroalkylsulfonate anion, a perfluoroalkylsulfonylimide anion, a tris(trifluoromethanesulfonyl)methide anion, or a heteropolyacid anion.

[0074] 11. The triarylmethane dye according to 1. above, wherein the maximum absorption wavelength of the absorption band in the ultraviolet-visible absorption spectrum (wavelength range of 350 to 800 nm) measured at 23 to 27° C. using a propylene glycol monomethyl ether (PGME) solution of the triarylmethane dye is within a wavelength range of 570 nm to 640 nm.

[0075] 12. A colored composition comprising the triarylmethane dye according to any one of 1. to 11. above.

[0076] 13. A colorant for color filters, comprising the coloring composition according to 12. above.

[0077] 14. A color filter using the colorant for color filter according to 13. above.

[0078] The triarylmethane dye of the present invention is excellent in spectral characteristics and heat resistance, and a coloring composition containing the dye is useful as a colorant for color filters. DETAILED DESCRIPTION

[0079] Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist thereof. First, the triarylmethane dye represented by the above-mentioned general formula (1) will be described.

[0080] In the general formula (1) and the general formula (2), as R 1 ~R 12The “straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent” in the above-mentioned “straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms” specifically includes straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl; isopropyl, isobutyl, sec-butyl, tert-butyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-methylpentyl, 2 ... Branched-chain alkyl groups such as 1-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethyl-1-methylpropyl, isooctyl, and 2-ethylhexyl; cyclic alkyl groups (cycloalkyl groups) such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2-ethylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl; and norbornyl, 1-adamantyl, 2-adamantyl, and bicyclo[4.3.0]nonyl. The lower limit of the number of carbon atoms in a "branched or cyclic alkyl group" is the number of carbon atoms that allows for a branched or cyclic structure (i.e., 3 carbon atoms), as will be understood by those skilled in the art.

[0081] In the general formula (1) and the general formula (2), as R 1 ~R 4 and R 7 ~R 12 Specific examples of the "aromatic hydrocarbon group having 6 to 20 carbon atoms" in the "aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent" include aromatic hydrocarbon groups such as phenyl, biphenyl, terphenyl, naphthyl, azulenyl, anthracenyl, phenanthrenyl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthenyl, and triphenylenyl. The "aromatic hydrocarbon group" in the present invention also includes an aryl group or a condensed polycyclic aromatic group.

[0082] In the general formula (1) and the general formula (2), as R 5 ~R 10 The "halogen atom" represented by includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. As the "halogen atom", a fluorine atom or a chlorine atom is preferred.

[0083] In the general formula (1) and the general formula (2), as R 5 ~R 9Specifically, the “straight-chain, branched or cyclic alkoxy group having 1 to 20 carbon atoms which may have a substituent” includes: straight-chain alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy and decyloxy; branched-chain alkoxy groups such as isopropoxy, isobutoxy, sec-butoxy, tert-butoxy and isooctyloxy; cyclic alkoxy groups (cycloalkoxy groups) such as cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclononyloxy and cyclodecyloxy; 1-adamantyloxy and 2-adamantyloxy;

[0084] In the general formula (1) and the general formula (2), as R 5 ~R 9 Specific examples of the "aryloxy group having 6 to 20 carbon atoms" in the "aryloxy group having 6 to 20 carbon atoms which may have a substituent" include phenoxy, tolyloxy, biphenyloxy, naphthyloxy, anthryloxy, and phenanthrenoxy.

[0085] In the general formula (2), R 7 ~R 10 Specifically, the “straight-chain, branched-chain or cyclic alkenyl group having 2 to 20 carbon atoms which may have a substituent” includes alkenyl groups such as vinyl, allyl, 1-propenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 1-hexenyl, isopropenyl, and isobutenyl.

[0086] In the general formula (2), R 7 ~R 12Specific examples of the “heterocyclic group having 5 to 20 ring atoms” in the “heterocyclic group having 5 to 20 ring atoms which may have a substituent” include pyridyl, pyrimidinyl, quinolyl, isoquinolyl, pyrazinyl, triazinyl, acridinyl, phenanthrolinyl, carbolinyl, purinyl, naphthyridinyl, phthalazinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, phenanthridinyl, perimidinyl, pyrido[2,3-b][1,8]naphthyridinyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, dihydropyrrolopyrrolyl, indolyl, isoindolyl, indolizinyl, indazolyl, and benzimidazolyl. , benzotriazolyl, carbazolyl, azaindolyl, azaindazolyl, pyrazolopyrimidinyl, adenylyl, guanidino, phenazinyl, furyl, thienyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, dibenzofuranyl, dibenzothienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, furopyrrolyl, thienopyrrolyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, benzisothiazolyl, benzothiadiazolyl, phenoxathiyl, imidazopyridyl, oxazolopyridyl, oxazolopyrazinyl, benzo[1,2-b:4,5-b']dithienyl, bipyridyl and other heterocyclic groups (or heteroaromatic hydrocarbon groups). The "heterocyclic group" in the present invention includes a heteroaryl group and a condensed polycyclic aromatic heterocyclic group.

[0087] In the general formula (2), R 7 ~R 9 "-NR" 11 R 12 " means "with R 11 and R 12 amino group", "with R 11 and R 12 The term "amino group" refers to "an unsubstituted amino group or a mono-substituted or di-substituted amino group having 1 to 20 carbon atoms which may have a substituent".

[0088] The "monosubstituted amino group" in the "optionally substituted monosubstituted amino group or disubstituted amino group having 1 to 20 carbon atoms" means the group in which "-NR 11 R 12 "R" 11 and R 12 "" is a hydrogen atom and the other is an amino group other than a hydrogen atom, and "disubstituted amino group" means that "-NR 11 R 12 "R" 11 and R 12 " are each independently an amino group other than a hydrogen atom. In "a monosubstituted or disubstituted amino group having 1 to 20 carbon atoms which may have a substituent", "may have a substituent" means "-NR11 R 12 "R" 11 and R 12 " may have a substituent, "R 11 and R 12 The term "substituent" in the formula "substituent" is applicable to the substituents represented by R 7 ~R 9 The "substituent" in each group represented is the same group.

[0089] Specific examples of the monosubstituted amino group include ethylamino, butylamino, acetylamino, and phenylamino. Specific examples of the disubstituted amino group include dialkylamino groups having 2 to 20 carbon atoms, such as dimethylamino, diethylamino, dipropylamino, dibutylamino, dihexylamino, and bis(2-methoxyethyl)amino; diallylamino groups having 4 to 20 carbon atoms, such as diallylamino; and diphenylamino, N-acetyl-N-phenylamino, and (n-butyl)-N-phenylamino.

[0090] In the general formula (2), R 7 ~R 9 The "acyl group having 1 to 20 carbon atoms" in the "acyl group having 1 to 20 carbon atoms which may have a substituent" is represented by "-(C=O)-R 19 " represents a group. 19 Applications with R 11 and R 12 The same groups. Specific examples of the "acyl group having 1 to 20 carbon atoms" include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, hexanoyl, octanoyl, chloroacetyl, trifluoroacetyl, cyclopentanecarbonyl, cyclohexanecarbonyl, benzoyl, methoxybenzoyl, chlorobenzoyl, nicotinoyl, furanyl, and thiophenecarbonyl.

[0091] In the general formula (1), R 7 ~R 9 The “straight-chain, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms which may have a substituent” or “aryloxycarbonyl group having 7 to 20 carbon atoms which may have a substituent” in the above-mentioned “straight-chain, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms which may have a substituent” or “aryloxycarbonyl group having 7 to 20 carbon atoms which may have a substituent” means a group consisting of “—(C═O)—O—R 19 " represents a group. 19As defined above. Specific examples of the "aryloxycarbonyl group having 7 to 20 carbon atoms" include oxycarbonyl groups (ester groups) such as carboxyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, isopropyloxycarbonyl, isobutyloxycarbonyl, sec-butyloxycarbonyl, tert-butyloxycarbonyl, isooctyloxycarbonyl, cyclopropyloxycarbonyl, cyclobutyloxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cycloheptyloxycarbonyl, cyclooctyloxycarbonyl, cyclononyloxycarbonyl, cyclodecyloxycarbonyl, 1-adamantyloxycarbonyl, 2-adamantyloxycarbonyl, phenoxycarbonyl, naphthyloxycarbonyl, pyridyloxycarbonyl, and benzyloxycarbonyl.

[0092] In the general formula (1) and the general formula (2), as R 1 ~R 12 Specific examples of the “substituent” in the “straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent,” “straight-chain, branched or cyclic alkenyl group having 2 to 20 carbon atoms which may have a substituent,” “aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,” “heterocyclic group having 2 to 20 carbon atoms which may have a substituent,” “straight-chain, branched or cyclic alkoxy group having 1 to 20 carbon atoms which may have a substituent,” “aryloxy group having 6 to 20 carbon atoms which may have a substituent,” “mono- or di-substituted amino group having 1 to 20 carbon atoms which may have a substituent,” “acyl group having 1 to 20 carbon atoms which may have a substituent,” “straight-chain, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms which may have a substituent,” or “aryloxycarbonyl group having 7 to 20 carbon atoms which may have a substituent” represented by any of the following include:

[0093] Deuterium atom, hydroxyl group (―OH), thiol group (―SH), cyano group (―CN), nitro group (―NO2), trifluoromethyl group (―CF3), carbonyl group (―(C=O)―);

[0094] Halogen atoms such as fluorine, chlorine, bromine, and iodine;

[0095] a linear or branched alkyl group having 1 to 20 carbon atoms;

[0096] a cycloalkyl group having 3 to 20 carbon atoms;

[0097] a linear or branched alkenyl group having 2 to 20 carbon atoms;

[0098] a straight-chain or branched alkynyl group having 2 to 20 carbon atoms;

[0099] a linear or branched alkoxy group having 1 to 20 carbon atoms;

[0100] a cycloalkoxy group having 3 to 20 carbon atoms, or a 1-adamantyloxy group or a 2-adamantyloxy group;

[0101] An aromatic hydrocarbon group or a condensed polycyclic aromatic group having 6 to 20 carbon atoms;

[0102] a heterocyclic group having 2 to 20 carbon atoms;

[0103] an aryloxy group having 6 to 20 carbon atoms;

[0104] Unsubstituted amino group; mono- or di-substituted amino group having 1 to 20 carbon atoms;

[0105] -COOH, -COOM, an acyl group having 1 to 20 carbon atoms which may have a substituent;

[0106] an alkoxycarbonyl group having 2 to 20 carbon atoms;

[0107] an aryloxycarbonyl group having 7 to 20 carbon atoms;

[0108] an amide group (carbamoyl group) having 1 to 20 carbon atoms;

[0109] -SO3H, -SO3M, or a sulfonyl group or sulfonamide group (aminosulfonyl group) having 0 to 20 carbon atoms which may have a substituent (wherein M represents an inorganic cation or an organic cation), etc.

[0110] These "substituents" may contain only one or more, and in the case of containing more than one, they may be the same or different from each other. In addition, in the groups having these "substituents", regarding the bonding position of the "substituent", for example, when considering the presence of multiple bonding positions such as any one of the four carbon atoms of an n-butyl group, the para position, meta position, or ortho position of a phenyl group, substitution may be performed at any of the positions, and when considering the presence of multiple positions for forming chemical bonds such as a pyridyl group or a naphthyl group, bonding may be performed at any of the positions. In addition, these "substituents" may further have the substituents exemplified above. Therefore, these “substituents” can be represented by, for example, “a linear or branched unsubstituted or substituted alkyl group having 1 to 20 carbon atoms,” “an unsubstituted or substituted cycloalkyl group having 3 to 20 carbon atoms,” “a linear or branched unsubstituted or substituted alkenyl group having 2 to 20 carbon atoms,” “a linear or branched alkynyl group having 2 to 20 carbon atoms,” “an unsubstituted or substituted cycloalkoxy group having 3 to 20 carbon atoms,” “an unsubstituted or substituted aryloxy group having 6 to 20 carbon atoms,” “an unsubstituted or substituted amino group having 0 to 20 carbon atoms,” “an unsubstituted or substituted amide group having 1 to 20 carbon atoms,” “an unsubstituted or substituted ammonium group having 0 to 20 carbon atoms,” “an unsubstituted or substituted phenyl group having 6 to 20 carbon atoms,” “an unsubstituted or substituted phenoxy group having 6 to 20 carbon atoms,” “a phenyl group having 6 to 20 carbon atoms substituted by a linear or branched alkyl group having 1 to 20 carbon atoms substituted by a halogen atom,” and the like. When a "substituent" contains carbon atoms, the carbon atoms are included in the above-mentioned "1 to 20 carbon atoms," "2 to 20 carbon atoms," "6 to 20 carbon atoms," and "7 to 20 carbon atoms." Furthermore, these substituents may be bonded to each other via a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.

[0111] In general formula (1) and general formula (2), as R 1 ~R 12Among the various “groups” having “substituents” mentioned above, “straight-chain or branched alkyl groups having 1 to 20 carbon atoms,” “cycloalkyl groups having 3 to 20 carbon atoms,” “straight-chain or branched alkenyl groups having 2 to 20 carbon atoms,” “straight-chain or branched alkynyl groups having 2 to 20 carbon atoms,” “straight-chain or branched alkoxy groups having 1 to 20 carbon atoms,” “cycloalkoxy groups having 3 to 20 carbon atoms,” “straight-chain or branched alkyl groups having 6 to 20 carbon atoms,” “cycloalkyl groups having 6 to 20 carbon atoms,” “straight-chain or branched alkynyl groups having 2 to 20 carbon atoms,” “straight-chain or branched alkoxy groups having 1 to 20 carbon atoms,” “cycloalkyl groups having 3 to 20 carbon atoms,” “straight-chain or branched alkyl groups having 6 to 20 carbon atoms,” “cycloalkyl groups having 3 to 20 carbon atoms,” “straight-chain or branched alkoxy groups having 3 ... , an aromatic hydrocarbon group or a condensed polycyclic aromatic group having 2 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a monosubstituted or disubstituted amino group having 1 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, or a sulfonamide group having 0 to 20 carbon atoms. Specific examples include:

[0112] Straight-chain or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, heptyl, octyl, isooctyl, nonyl, and decyl;

[0113] Cycloalkyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclononyl, and cyclodecyl;

[0114] an alkenyl group such as vinyl, 1-propenyl, allyl, 1-butenyl, 2-butenyl, 1-pentenyl, 1-hexenyl, isopropenyl, or isobutenyl, or a linear or branched alkenyl group in which a plurality of these groups are bonded;

[0115] Alkynyl groups such as ethynyl, propargyl, butynyl, or linear or branched alkynyl groups in which a plurality of these groups are bonded; mixed groups of alkenyl and alkynyl groups such as pent-3-en-1-ynyl and hex-2-en-4-ynyl;

[0116] Linear or branched alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, and isooctyloxy;

[0117] Cycloalkyloxy groups having 3 to 20 carbon atoms, such as cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclononyloxy, and cyclodecyloxy;

[0118] Aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as phenyl, biphenyl, terphenyl, naphthyl, anthryl, naphthyl, phenanthrenyl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthenyl, and triphenylenyl;

[0119] Heterocyclic groups such as thienyl, furanyl, pyrrolyl, thiazolyl, oxazolyl, imidazolyl, pyrazolyl, triazolyl, benzothienyl, benzofuranyl, indolyl, isoindolyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzotriazolyl, purinyl, carbazolyl, dibenzothienyl, dibenzofuranyl, pyridyl, pyrimidinyl, triazinyl, quinolyl, isoquinolyl, naphthyridinyl, acridinyl, phenanthrolinyl, naphthyridinyl, and carbolinyl;

[0120] Aryloxy groups such as phenoxy, tolyloxy, biphenyloxy, naphthoxy, anthryloxy, and phenanthrenoxy;

[0121] a linear or branched alkyl group, a cycloalkyl group, or a mono- or di-substituted amino group having an aromatic hydrocarbon group, such as methylamino, dimethylamino, diethylamino, ethylmethylamino, dipropylamino, dibutylamino, di(2-ethylhexyl)amino, di-tert-butylamino, or diphenylamino;

[0122] Acyl groups such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, hexanoyl, octanoyl, chloroacetyl, trifluoroacetyl, cyclopentanecarbonyl, cyclohexanecarbonyl, benzoyl, methoxybenzoyl, chlorobenzoyl, nicotinoyl, furancarbonyl, and thiophenecarbonyl;

[0123] Oxycarbonyl (alkoxycarbonyl or aryloxycarbonyl) such as carboxyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, isopropyloxycarbonyl, isobutyloxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, isooctyloxycarbonyl, cyclopropyloxycarbonyl, cyclobutyloxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cycloheptyloxycarbonyl, cyclooctyloxycarbonyl, cyclononyloxycarbonyl, cyclodecyloxycarbonyl, 1-adamantyloxycarbonyl, 2-adamantyloxycarbonyl, phenoxycarbonyl, naphthyloxycarbonyl, pyridyloxycarbonyl, benzyloxycarbonyl, etc.;

[0124] Amide groups such as unsubstituted amide group, N-methylamide group, N-ethylamide group, N-n-propylamide group, N-isopropylamide group, N-hexylamide group, N-phenylamide group, N-naphthylamide group, N,N-dimethylamide group, N,N-diethylamide group, N-methyl-N-(2-hydroxyethyl)amide group, N-methyl-N-phenylamide group, N-ethyl-N-phenylamide group, N-propyl-N-naphthylamide group, N-methyl-N-(4-methylphenyl)amide group, and diphenylamide group;

[0125] Sulfonamides (aminosulfonyl groups) such as unsubstituted sulfonamide, N-methylsulfonamide, N-ethylsulfonamide, N-n-propylsulfonamide, N-isopropylsulfonamide, N-hexylsulfonamide, N-phenylsulfonamide, N-naphthylsulfonamide, N,N-dimethylsulfonamide, N,N-diethylsulfonamide, N,N-bis(2-hydroxyethyl)sulfonamide, N-methyl-N-phenylsulfonamide, N-ethyl-N-phenylsulfonamide, N-propyl-N-naphthylsulfonamide, N-methyl-N-(4-methylphenyl)sulfonamide, and diphenylsulfonamide.

[0126] In the general formula (1), when an "inorganic cation" or "organic cation" represented by "M" is present, examples of the "organic cation" include those represented by R 20 R 21 R 22 R 23 N + The ammonium ion represented by the formula, R 20 ~R 23 Each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and they may be bonded to each other to form a ring. 20 ~R 23 The details of the "substituent", "linear or branched alkyl group having 1 to 20 carbon atoms" and "aromatic hydrocarbon group having 6 to 20 carbon atoms" in R 1 ~R 12 The same applies. Examples of "inorganic cations" include alkali metal ions such as lithium and sodium ions, and alkaline earth metal ions such as magnesium, calcium, and barium ions. M is preferably an alkali metal ion.

[0127] In the general formula (1), the presence of an "amide group having 1 to 20 carbon atoms which may have a substituent" refers to the group consisting of "-(C=O)-NR 11 R 12 " represents a group. Here, R 11 and R 12 As shown in the above definition.

[0128] In the general formula (1), the presence of "a sulfonyl group or a sulfonamide group having 0 to 20 carbon atoms which may have a substituent" means the presence of "-SO2-R 19 ” (or “―S(=O)2―R 19 ”) or “―S(=O)2―NR 11 R 12 "-SO2-R 19 ” (or “―S(=O)2―R19 ”) 19 , “―S(=O)2―NR 11 R 12 R in " 11 and R 12 As shown in the above definition.

[0129] In the general formula (1), An is not particularly limited, and examples thereof include halide ions and organic anions. Specifically, examples thereof include:

[0130] Cl - Br - , I - ;(CF3SO2)2N - (or Tf2N - ),

[0131] (CF3SO2)3C - (or Tf3C - ),

[0132] (C2F5SO2)2N - 、(C4F9SO2)2N - 、(C6F5SO2)2N - 、

[0133] (C2F5)3F3P - 、

[0134] (CN)2N - 、(CN)3C - 、NC-S - 、;

[0135] (C6H4SO3 - )O(C6H3(C 12 H 25 )(SO3 - ))、

[0136] C6H4(C 12 H 25 )(SO3 - );PF6 - 、BF4 - ;

[0137] (PW 12 O 40 ) 3- 、(P2W 18 O 62 ) 6- 、

[0138] (SiW 12 O 40 )4- 、(PMo 12 O 40 ) 3- 、(SiMo 12 O 40 ) 3- 、

[0139] (PW 12-x Mo x O 40 ) 3- 、(SiW 12-x Mo x O 40 ) 4- 、

[0140] (P2W 18-y Mo y O 40 ) 6- (x represents an integer of 1 to 11, y represents an integer of 1 to 17) heteropolyacid anions;

[0141] or anions represented by the following structural formulas (Z-1) to (Z-16).

[0142]

Chemical Formula 7

[0143]

[0144]

Chemical Formula 8

[0145]

[0146]

Chemical Formula 9

[0147]

[0148]

Chemical Formula 10

[0149]

[0150] In the general formula (1), An may be a single species or a combination of two or more different species. It is preferably a single species or a combination of two or three species selected from the anions exemplified above. It is further preferably a single species or a combination of two or three species selected from perfluoroalkylsulfonate anions (more preferably perfluoroalkylsulfonate anions having 1 to 24 carbon atoms), perfluoroalkylsulfonimide anions (more preferably perfluoroalkylsulfonimide anions having 1 to 24 carbon atoms), tris(trifluoromethanesulfonyl)methide anions, or heteropolyacid anions. Therefore, "m" in the general formula (1) can be selected from any natural number based on the valence of [An] in the formula (1) as a whole and the valence of the cation of the triarylmethane skeleton structure within [] so that the molecule of the formula (1) exhibits electrical neutrality as a whole. From the viewpoint of molecular design, An is preferably a single species, preferably a perfluoroalkylsulfonyl imide anion or a heteropolyacid anion, more preferably a trifluoromethanesulfonyl imide anion or a phosphotungstate anion (PW 12 O 40 3- ).

[0151] In the general formulas (2-1) to (2-4), R 7 ~R 9 、R 13 and R 15 ~R 18 Indicates that R in the general formula (2) 7 ~R 9 For the same groups, refer to the above general formula (2) for R 7 ~R 9 Description and specific examples.

[0152] In the general formulas (2-1) to (2-3), R 10 Indicates that R in the general formula (2) 10 For the same groups, refer to the above general formula (2) for R 10 Description and specific examples.

[0153] In the general formulas (2-1) to (2-4), R 11 and R 12 Indicates that R in the general formula (2) 11 and R 12 For the same groups, refer to the above general formula (2) for R 11 and R 12 Description and specific examples.

[0154] Specific examples of preferred compounds of the triarylmethane dye of the present invention represented by general formula (1) are shown below, but the present invention is not limited to these compounds. The following formulas (B-1) to (B-87) represent the triarylmethane dye portion of the above general formula (1), with the anion portion represented by [An] omitted. In the following structural formulas, some hydrogen atoms are omitted, and all possible stereoisomers and tautomers are included, and the planar structural formula is described.

[0155]

Chemical Formula 11

[0156]

[0157]

Chemical Formula 12

[0158]

[0159]

Chemical Formula 13

[0160]

[0161]

Chemical Formula 14

[0162]

[0163]

Chemical Formula 15

[0164]

[0165]

Chemical Formula 16

[0166]

[0167]

Chemical Formula 17

[0168]

[0169]

Chemical Formula 18

[0170]

[0171]

Chemical Formula 19

[0172]

[0173]

Chemical Formula 20

[0174]

[0175]

Chemical Formula 21

[0176]

[0177]

Chemical Formula 22

[0178]

[0179]

Chemical Formula 23

[0180]

[0181]

Chemical Formula 24

[0182]

[0183]

Chemical Formula 25

[0184]

[0185]

Chemical Formula 26

[0186]

[0187]

Chemical Formula 27

[0188]

[0189]

Chemical Formula 28

[0190]

[0191]

Chemical Formula 29

[0192]

[0193]

Chemical Formula 30

[0194]

[0195]

Chemical Formula 31

[0196]

[0197]

Chemical Formula 32

[0198]

[0199]

Chemical Formula 33

[0200]

[0201]

Chemical Formula 34

[0202]

[0203]

Chemical Formula 35

[0204]

[0205]

Chemical Formula 36

[0206]

[0207]

Chemical Formula 37

[0208]

[0209]

Chemical Formula 38

[0210]

[0211]

Chemical Formula 39

[0212]

[0213] As R in the general formula (1) 1 ~R 4 , preferably "a hydrogen atom", "a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent", or "an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent". 1 and R 3 Any one of them is preferably a "linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent", and the other is more preferably a "linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent" or an "aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent". R 2 and R 4 Any one of them is preferably a "linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent", and the other is preferably a "linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent" or an "aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent". 1 and R 3 At least one of them is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, and R 2 and R 4 At least one of them is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent. 1 ~R 4 Examples of the group include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isobutyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a methylphenyl group, a methoxyphenyl group, a difluorophenyl group, a dichlorophenyl group, a dimethylphenyl group, a mesityl group (2,4,6-trimethylphenyl group), a 1-naphthyl group, and a 2-naphthyl group.

[0214] As R in the general formula (1) 5 and R 6, preferably "hydrogen atom", "halogen atom" or "linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent", more preferably "hydrogen atom", "fluorine atom", "chlorine atom" or "linear, branched or cyclic alkyl group having 1 to 4 carbon atoms which may have a substituent". Preferred R 5 and R 6 Examples of R include hydrogen, fluorine, chlorine, methyl, ethyl, n-propyl, and isopropyl. 5 and R 6 The same groups are preferred.

[0215] As R in the general formula (2) 7 and R 8 , preferably "a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent", "a linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms which may have a substituent", "an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent", or "-NR 11 R 12 More preferably, it is "a branched alkyl group having 1 to 10 carbon atoms which may have a substituent", "an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent", or "-NR 11 R 12 As the preferred R 7 and R 8 Examples of the group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, vinyl, propenyl, phenyl, fluorophenyl, chlorophenyl, methylphenyl, methoxyphenyl, dichlorophenyl, dimethylphenyl, mesityl, naphthyl, methylamino, ethylamino, phenylamino, dimethylamino, diethylamino, dipropylamino, N-ethyl-phenylamino, N-ethyl-(4-fluorophenyl)amino, and N-ethyl-(2-methylphenyl)amino.

[0216] In the general formula (2), R 9 , preferably "a hydrogen atom", "a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent", or "an alkoxycarbonyl group having 2 to 20 carbon atoms which may have a substituent". Preferred R 9 Examples of the group include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a methoxycarbonyl group, an ethoxycarbonyl group, and a benzyloxycarbonyl group.

[0217] In the general formula (2), R 10, preferably "a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent" or "an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent". 10 Examples of the group include methyl, ethyl, n-propyl, n-butyl, isobutyl, phenyl, fluorophenyl, chlorophenyl, methylphenyl, methoxyphenyl, difluorophenyl, dichlorophenyl, dimethylphenyl, and mesityl.

[0218] In the general formula (2), R 11 and R 12 , preferably "a hydrogen atom", "a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent", or "an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent". 11 and R 12 Examples of the group include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isobutyl group, a phenyl group, a fluorophenyl group, a chlorophenyl group, a methylphenyl group, a methoxyphenyl group, a difluorophenyl group, a dichlorophenyl group, a dimethylphenyl group, and a mesityl group.

[0219] In the general formula (1), A H , preferably a heterocyclic group represented by the general formula (2-1) to (2-4). In the general formula (2-1) to (2-3), the preferred R 7 ~R 12 For example, please refer to the general formula (2) for R 7 ~R 12 In the general formula (2-4), the preferred R 13 ~R 18 For example, please refer to the general formula (2) for R 7 ~R 12 Description and specific examples.

[0220] In the general formula (1), A H In the case of a heterocyclic group represented by the general formula (2-1), R 7 and R 8 Preferably, it is "a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent", "an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent", or "-NR 11 R 12 More preferably, it is "a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent" or "an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent". 7 and R 8 At least one of them is particularly preferably an "aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent". 9Preferred are "hydrogen atom", "linear, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms which may have a substituent", or "aryloxycarbonyl group having 7 to 20 carbon atoms which may have a substituent", and more preferred are "hydrogen atom", "linear, branched or cyclic alkoxycarbonyl group having 2 to 10 carbon atoms which may have a substituent", and from the viewpoint of heat resistance, "linear, branched or cyclic alkoxycarbonyl group having 2 to 10 carbon atoms which may have a substituent" is preferred. 10 Preferably, it is a "linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent" or an "aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent", and more preferably an "aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent". 7 ~R 12 For a preferred specific example, please refer to the formula (2) for R 7 ~R 12 Description and specific examples.

[0221] In the general formula (1), A H In the case of a heterocyclic group represented by the general formula (2-2), R 7 ~R 10 Preferably, R is a "hydrogen atom", "a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent", or "an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent". 7 ~R 10 For a preferred specific example, please refer to the formula (2) for R 7 ~R 10 Description and specific examples.

[0222] In the general formula (1), A H In the case of a heterocyclic group represented by the general formula (2-3), R 7 Preferably "-NR 11 R 12 ”. 8 and R 10 ~R 12 Preferably, it is a "linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent" or an "aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent", and more preferably a "linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent" or an "aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent". R 11 and R 12 At least one of them is preferably an "aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent", and from the viewpoint of molecular design, it is preferred that R 11 and R 12At least one of them is related to R 10 Same as R 8 and R 10 ~R 12 The "substituent" in the "linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent" or the "aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent" represented by any of the above is preferably a deuterium atom, a hydroxyl group (-OH), a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, a condensed polycyclic aromatic group or a heterocyclic group having 2 to 10 carbon atoms, and more preferably a fluorine atom, a chlorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. As R 7 ~R 12 For a preferred specific example, please refer to the formula (2) for R 7 ~R 12 Description and specific examples.

[0223] In the general formula (1), A H In the case of a heterocyclic group represented by the general formula (2-4), R 13 Preferably, it is "a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent" or "an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent". 14 Preferably it is a "hydrogen atom". 15 ~R 18 Preferred are "hydrogen atom", "halogen atom", "-OH", "-CF3", "-NO2", "-CN", "a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent", "an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent", or "a heterocyclic group having 5 to 20 ring atoms which may have a substituent", and more preferred are "hydrogen atom", "halogen atom", "a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent", or "an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent". 13 and R 15 ~R 18 For a preferred specific example, please refer to the formula (2) for R 7 ~R 12 Description and specific examples.

[0224] The method for producing the triarylmethane pigment compound represented by the general formula (1) is not particularly limited, and can be produced by applying a known method (e.g., non-patent document 2) using reagents having various corresponding groups of the general formula (1) and the general formula (2), or other appropriate reagents. One embodiment of the method for producing the compound of the present invention is described below. However, the present invention is not limited thereto.

[0225] The triarylmethane dye represented by the general formula (1) can be obtained by condensing a benzophenone derivative having a corresponding substituent with a heterocyclic compound having a corresponding substituent. Furthermore, the triarylmethane dye represented by the general formula (1) can be produced by salt exchange with a salt having a corresponding structure, as needed. The chemical reaction in this production can be carried out in the presence of an aqueous solvent or an organic solvent, or can be carried out in the absence of a solvent.

[0226] The separation and purification of each product in the production method of the present invention can be carried out by appropriately combining methods used in conventional organic synthesis, such as purification based on column chromatography, adsorption purification based on silica gel, activated carbon, activated clay, etc., recrystallization based on solvents, crystallization methods, and other known methods. In addition, in the identification, analysis, optical properties, thermal properties, and other physical property evaluations of these compounds, nuclear magnetic resonance analysis (NMR), spectrophotometric absorbance measurement, ultraviolet-visible absorption spectroscopy (UV-Vis) measurement, thermogravimetric measurement-differential thermal analysis (TG-DTA), etc. can be performed. These analytical methods can also be used to evaluate the solubility, color, and heat resistance of the obtained compounds.

[0227] The triarylmethane pigment of the present invention may be used alone or in combination (e.g., a mixture) of two or more triarylmethane pigments having different molecular structures. When two or more triarylmethane pigments are used, the mass concentration ratio of the least triarylmethane pigment in the total mass concentration ratio of the triarylmethane pigment is 0.1 to 50% by mass. The triarylmethane pigments are preferably used in combination of one or two types.

[0228] The triarylmethane dye of the present invention, a coloring composition containing the dye, and a color filter colorant containing the dye or the coloring composition need to be well dissolved or dispersed in an organic solvent containing a resin or the like during the production process of the colorant and the color filter. Therefore, they preferably have high solubility and dispersibility in organic solvents. The organic solvent is not particularly limited, and specific examples include: aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as propylene glycol monomethyl ether acetate (PGMEA), methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether (PGME); ketones such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, and 3-heptanone; alcohols such as methanol, ethanol, 2-propanol, and propylene glycol; esters such as methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, ethyl acetate, butyl acetate, and methyl 3-methoxypropionate; diacetone alcohol (DAA); amides such as N,N-dimethylformamide (DMF) and N-methylpyrrolidone (NMP); and dimethyl sulfoxide (DMSO). PGME, PGMEA, cyclohexanone, or DAA is preferred. From the perspective of achieving both the solubility of the resin and the solubility of the triarylmethane dye, PGME or PGMEA is particularly preferred. These solvents may be used alone or in combination of two or more.

[0229] The triarylmethane dye of the present invention has excellent solubility in organic solvents, particularly in PGMEA. The solubility in PGMEA is preferably 1% by mass or greater, more preferably 3% by mass or greater, and particularly preferably 5% by mass or greater. Considering application in high-contrast ratio color filters, the higher the solubility, the better.

[0230] Use the solution prepared by dissolving the triarylmethane pigment of the present invention in an organic solvent, in the visible light region (for example, the wavelength range of 350 to 800 nm) of the ultraviolet-visible absorption spectrum measured near room temperature (for example, 23 to 27 ° C), a maximum absorption wavelength showing maximum absorbance is observed. In the present invention, the maximum absorption wavelength in the PGME solution is preferably in the wavelength range of 550 to 650 nm, more preferably in the wavelength range of 570 to 640 nm. In addition, the pigment concentration is preferably 0.005 to 0.02 mmol / L. As long as the solvent is a solvent that dissolves the pigment, it is not limited, and preferably a solvent that does not significantly shift the absorption wavelength of the ultraviolet-visible absorption spectrum due to the dissolution conditions is preferably PGME.

[0231] The triarylmethane pigment of the present invention can be mixed with various resin solutions and coated on a glass substrate to produce a coating film. The obtained coating film is measured using a spectrophotometer to obtain the color value of the coating film, which can be used for color evaluation. Color values ​​are generally measured using CIE L * a * b *Color system, etc. Specifically, the color value L of the film sample is measured. * 、a * 、b * , based on the color difference (ΔE ＊ ab ), heat resistance can be judged. In the case of application to color filters, the color difference at a temperature of around 230°C can be used as an indicator of heat resistance. * ab The smaller the value, the less discoloration due to thermal decomposition and the higher the heat resistance. It is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less. In addition, as a method for comparing the heat resistance of pigments, it can be evaluated by thermogravimetric measurement. For example, by measuring the 5% mass loss temperature by thermogravimetric measurement in an inert gas atmosphere such as nitrogen, the higher the decomposition temperature, the better.

[0232] The colorant for color filters of the present invention comprises: a triarylmethane pigment represented by the general formula (1) or a coloring composition containing at least one triarylmethane pigment; and components commonly used in the manufacture of color filters. Conventional color filters can be obtained, for example, by the following method: in the case of a method utilizing a photolithography process, a liquid prepared by mixing a pigment such as a dye or pigment with a resin component (including monomers and oligomers) and a solvent is applied to a substrate such as glass or resin, and photopolymerized using a photomask to produce a coloring pattern of a pigment-resin composite film that is soluble / insoluble in the solvent, and then heated after washing. In addition, in the electroplating method and the printing method, a mixture of a pigment, a resin, and other components is also used to produce a coloring pattern. Therefore, as specific components in the colorant for color filters of the present invention, at least one triarylmethane pigment represented by the general formula (1), other pigments such as dyes and pigments, a resin component, an organic solvent, and other additives such as a photopolymerization initiator can be cited. In addition, it is possible to select from these components, and it is also possible to add other components as needed.

[0233] When the triarylmethane dye of the present invention or a coloring composition containing the triarylmethane dye is used as a colorant for color filters, it can be used for color filters of various colors, but is preferably used as a colorant for blue or green color filters.

[0234] The colorant for color filter of the present invention may be used alone or in combination with two or more triarylmethane dyes. In order to adjust the hue, that is, to adjust the spectral characteristics, other known dyes such as dyes and pigments described below may be further mixed.

[0235] When used as a colorant for a blue color filter, there are no particular limitations, and examples thereof include basic dyes such as CI Basic Blue 3, CI Basic Blue 7, CI Basic Blue 9, CI Basic Blue 54, CI Basic Blue 65, CI Basic Blue 75, CI Basic Blue 77, CI Basic Blue 99, CI Basic Blue 129, and CI Basic Violet 10; acid dyes such as CI Acid Blue 9, CI Acid Blue 74, CI Acid Red 52, and CI Acid Red 289; disperse dyes such as Disperse Blue 3, Disperse Blue 7, and Disperse Blue 377; Spilon dyes; cyanine-based, indigo-based, phthalocyanine-based, anthraquinone-based, methine-based, triarylmethane-based, indanthrene-based, oxazine-based, dioxazine-based, azo-based, and xanthene-based pigments; and other blue lake pigments and other blue or red dyes or pigments.

[0236] When used as a colorant for a green color filter, there are no particular limitations, and examples thereof include green pigments such as CI Pigment Green 7, CI Pigment Green 10, CI Pigment Green 36, CI Pigment Green 47, CI Pigment Green 58, CI Pigment Green 59, CI Pigment Green 62, and CI Pigment Green 63; yellow pigments such as CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, and CI Pigment Yellow 185; Spilon dyes; cyanine-based, indigo-based, phthalocyanine-based, anthraquinone-based, methine-based, triarylmethane-based, indanthrene-based, oxazine-based, dioxazine-based, azo-based, xanthene-based, isoindoline-based, and quinophthalone-based pigments; and blue, yellow, or green dyes or pigments such as other lake pigments.

[0237] In the present invention, the pigments mixed for adjusting hue are preferably triarylmethane pigments not included in the present invention, such as CI Basic Blue 7, or xanthene pigments, such as CI Basic Violet 10, CI Acid Red 52, and CI Acid Red 289, when used as colorants for blue color filters. When used as colorants for green color filters, quinophthalone pigments, such as CI Pigment Yellow 138, isoindoline pigments, such as CI Pigment Yellow 139, or azo pigments are preferred. By using these pigments in combination with the triarylmethane pigments included in the present invention, a blue or green color filter having excellent brightness and contrast ratio can be obtained.

[0238] The pigment may be subjected to rosin treatment, surface treatment using a pigment derivative having an acidic or basic group introduced therein, grafting treatment on the pigment surface using a polymer compound, micronization treatment using a sulfuric acid micronization method, or washing treatment using an organic solvent or water to remove impurities, or removal of ionic impurities using an ion exchange method. The pigments preferably have uniform particle sizes.

[0239] The mixing ratio of other pigments in the color filter colorant of the present invention relative to the triarylmethane pigment (the total of these pigments when there are two or more) is preferably 5 to 2000 mass%, more preferably 10 to 1000 mass%. The mixing ratio of pigment components such as dyes in the liquid color filter colorant relative to the entire colorant is preferably 0.5 to 70 mass%, more preferably 1 to 50 mass%.

[0240] As the resin component in the colorant for color filter of the present invention, as long as it has the properties required for the production method of the color filter resin film formed by using them and the properties required when used, known resin components can be used. Specifically, for example, acrylic resins, olefin resins, styrene resins, polyimide resins, polyurethane resins, polyester resins, epoxy resins, vinyl ether resins, phenolic (varnish) resins, other transparent resins, photocurable resins or thermosetting resins can be mentioned, and they can be used in appropriate combination with their monomers or oligomer components. In addition, copolymers of these resins can also be used in combination. In the case of liquid colorants, the content of the resin in these color filter colorants is preferably 5 to 95% by mass, more preferably 10 to 50% by mass.

[0241] To improve the performance of the colorant for color filters, the coloring composition of the present invention may contain surfactants, dispersants, defoamers, leveling agents, antioxidants, ultraviolet absorbers, and other additives mixed during the production of the colorant for color filters as other components of the compound. The content of these additives in the coloring composition is preferably an appropriate amount, preferably within a range that does not reduce or increase the solubility of the coloring composition of the present invention in the solvent beyond the required level, and does not affect the effects of other similar additives used during the production of the color filter. These additives can be added at any time during the preparation of the coloring composition.

[0242] Other additives in the colorant for color filters of the present invention include components required for polymerization and curing of the resin, such as photopolymerization initiators and crosslinking agents. In addition, surfactants and dispersants required to stabilize the properties of the components in the liquid colorant for color filters can be mentioned. These can be known substances used for the manufacture of color filters and are not particularly limited. The total amount of these additives is preferably mixed in the solid content of the colorant for color filters in a ratio of 5 to 60% by mass, more preferably 10 to 40% by mass.

[0243] [Example]

[0244] Hereinafter, the embodiments of the present invention will be specifically described using examples, but the present invention is not limited to the following examples. The reagents described in the synthesis examples are manufactured by Tokyo Chemical Industry Co., Ltd., Sigma Aldrich Co., Ltd., Alfa Aesar Co., Ltd., Duksan Co., Ltd., Daejung Co., Ltd., etc. In addition, unless otherwise specified, the reactions in the synthesis examples are carried out in a reaction vessel equipped with a condenser, a stirring device, and a thermometer under a nitrogen gas stream. In addition, the identification of the compounds in the following synthesis examples is carried out by 1 H-NMR analysis (NMR instrument manufactured by BRUKER: Ascend TM 400MHz).

[0245] [Synthesis Example 1] Synthesis of Compound (C-1)

[0246] The following reaction was carried out under air flow. 35.7 g (333 mmol) of p-toluidine, 40.0 g (333 mmol) of acetophenone, 27.6 g (166 mmol) of potassium iodide, 21.1 g (83.2 mmol) of iodine, and 650 mL of chlorobenzene were added to a reaction vessel and stirred at 120°C for 5 days. The reaction solution was cooled to room temperature, filtered under reduced pressure, and the solvent in the filtrate was removed by vacuum distillation. 600 mL of a 5% aqueous sodium thiosulfate solution and 600 mL of ethyl acetate were added to the resulting residue, stirred at room temperature (23-28°C), and the organic layer was extracted. After drying over anhydrous magnesium sulfate, the mixture was filtered under reduced pressure, and the solvent in the filtrate was removed by vacuum distillation. The residue was purified by column chromatography (support: silica gel, solvent: n-heptane), and the solvent was removed by vacuum distillation. The residue was dried under reduced pressure to obtain the following (Intermediate 100) (15.8 g, 32% yield).

[0247]

Chemical Formula 40

[0248]

[0249] Next, the following reaction was carried out under a nitrogen stream. 35.0 g (139 mmol) of 4,4'-dichlorobenzophenone, 33.8 g (279 mmol) of 2,6-dimethylaniline, 37.5 g (390 mmol) of sodium tert-butoxide, and 280 mL of xylene were added to the reaction vessel, and while stirring at room temperature, 1.56 g (6.97 mmol) of palladium acetate and 6.64 g (13.9 mmol) of 2-dicyclohexylphosphino-2',4',6',-triisopropylbiphenyl (XPhos) were added, and stirred at 110°C for 3 hours. After the reaction solution was cooled to room temperature, 200 mL of water and 50 mL of isopropanol were added, stirred, and the solid was filtered out. The obtained solid was suspended and washed with 200 mL of water, and then the solid was filtered out. The obtained solid was dried under reduced pressure at 80°C to obtain the following (Intermediate 101) (55.0 g, yield 94%).

[0250]

Chemical Formula 41

[0251]

[0252] Next, 150 g (357 mmol) of the above-mentioned (intermediate 105) and 530 mL of dimethylformamide were added to the reaction vessel and cooled to 5°C while stirring. After slowly adding 120 g (1.07 mol) of potassium tert-butoxide to the solution, 167 g (1.07 mol) of iodoethane was added dropwise while maintaining the temperature at 5°C. After the addition, the temperature was raised to 35°C and stirred for 3 hours. The reaction solution was added dropwise to 3.0 L of a 10% sodium chloride aqueous solution, and the precipitated solid was filtered out. The obtained solid was suspended and washed in 1.5 L of water, and the solid was filtered out. The obtained solid was suspended and washed in a mixed solvent of 500 mL of water and 1.0 L of methanol, and the solid was filtered out. The obtained solid was dried under reduced pressure at 80°C to obtain the following (intermediate 102) (152 g, yield 90%).

[0253]

Chemical Formula 42

[0254]

[0255] Next, 23.1 g (48.5 mmol) of the above-mentioned (intermediate 102) and 100 mL of toluene were added to the reaction vessel and stirred at room temperature (23-28°C). 11.9 g (77.6 mmol) of phosphorus oxychloride was added dropwise thereto and stirred at room temperature (23-28°C) for 1 hour. 15.0 g (48.5 mmol) of the above-mentioned (intermediate 100) was further added to the solution and stirred at 100°C for 5 hours. After the reaction solution was cooled to room temperature, 300 mL of dichloromethane and 100 mL of water were added to extract the organic layer. Anhydrous magnesium sulfate was added, the organic layer was dried, filtered, and the filtrate was concentrated under reduced pressure. The resulting residue was purified by column chromatography (carrier: silica gel, solvent: dichloromethane / methanol = 100 / 1 to 10 / 1 (volume ratio)), and the solvent was distilled off under reduced pressure. To the residue was added 90 mL of methanol and stirred to dissolve the solid. Then, 17.4 g (60.6 mmol) of lithium bis(trifluoromethanesulfonyl)imide (LiN(SO₂CF₃)₂) was added. After stirring at 45°C for 1 hour, the mixture was cooled and the precipitated solid was collected by filtration. The resulting solid was dried under reduced pressure at 80°C to obtain the target compound (C-1) (48.5 g, 95% yield) as a brown solid.

[0256] The obtained brown solid was subjected to NMR measurement, and the following 54 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-1).

[0257] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.58 (1H), 7.35-6.70 (26H), 5.72 (2H), 3.70 (4H), 2.14 (3H), 2.08-1.75 (12H), 1.13 (6H).

[0258]

Chemical Formula 43

[0259]

[0260] [Synthesis Example 2] Synthesis of Compound (C-2)

[0261] 18.0 g (17.2 mmol) of the above-mentioned (C-1) and 680 mL of methanol were added to a reaction vessel. After dissolving the solid, a solution prepared by dissolving 25.1 g of phosphotungstic acid hydrate in 230 mL of methanol was added dropwise. The solution was stirred at room temperature (23-28°C) for 1 hour, and the reaction liquid was filtered. The resulting solid was suspended and washed in 200 mL of methanol, filtered, and dried under reduced pressure at 80°C to obtain the target compound (C-2) (26.6 g, 90% yield) as a blue solid.

[0262] The obtained blue solid was subjected to NMR measurement, and the following 162 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-2).

[0263] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.58 (3H), 7.35-6.70 (78H), 5.72 (6H), 3.70 (12H), 2.14 (9H), 2.08-1.75 (36H), 1.13 (18H).

[0264]

Chemical Formula 44

[0265]

[0266] [Synthesis Example 3] Synthesis of Compound (C-3)

[0267] The following (Intermediate 103) (3.99 g, yield 46%) was obtained by the same method as in Synthesis Example 1 (Intermediate 100) except that acetophenone was changed to 4'-fluoroacetophenone.

[0268]

Chemical Formula 45

[0269]

[0270] Next, in the synthesis of compound (C-1) of Synthesis Example 1, except that (Intermediate 100) was changed to the above-mentioned (Intermediate 103), the target compound (C-3) (4.26 g, yield 68%) was obtained as a brown solid using the same method.

[0271] The obtained brown solid was subjected to NMR measurement, and the following 52 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-3).

[0272] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.55 (1H), 7.35-6.70 (24H), 5.72 (2H), 3.70 (4H), 2.14 (3H), 2.08-1.75 (12H), 1.14 (6H).

[0273]

Chemical Formula 46

[0274]

[0275] [Synthesis Example 4] Synthesis of Compound (C-4)

[0276] The following reaction was carried out under air flow. A reaction vessel was charged with 1.89 g (17.6 mmol) of p-toluidine, 4.00 g (23.5 mmol) of 1'-acetonaphthone, 0.98 g (5.88 mmol) of potassium iodide, 0.60 g (2.35 mmol) of iodine, and 40 mL of 1,1,2,2-tetrachloroethane, and stirred at 120°C for 18 hours. The reaction mixture was cooled to room temperature, and 30 mL of a 5% aqueous sodium thiosulfate solution was added. After stirring at room temperature (23-28°C), 50 mL of dichloromethane was added to extract the organic layer. After drying over anhydrous magnesium sulfate, the mixture was filtered under reduced pressure, and the solvent in the filtrate was removed by vacuum distillation. The residue was purified by column chromatography (support: silica gel, solvent: n-heptane / ethyl acetate = 100 / 1 (volume ratio)), and the solvent was removed by vacuum distillation. The residue was dried under reduced pressure to obtain the following (Intermediate 104) (2.00 g, 42% yield).

[0277]

Chemical Formula 47

[0278]

[0279] Next, in the synthesis of compound (C-1) in Synthesis Example 1, except that (Intermediate 100) was changed to the above-mentioned (Intermediate 104), the target compound (C-4) (4.80 g, yield 86%) was obtained as a brown solid using the same method.

[0280] The obtained brown solid was subjected to NMR measurement, and the following 58 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-4).

[0281] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 8.50-6.10 (31H), 5.54 (2H), 3.63 (4H), 2.20-1.40 (15H), 1.06 (6H).

[0282]

Chemical Formula 48

[0283]

[0284] [Synthesis Example 5] Synthesis of Compound (C-5)

[0285] The following (Intermediate 105) (2.23 g, yield 59%) was obtained by the same method as in Synthesis Example 4 (Intermediate 104) except that 1'-acetonaphthone was replaced with 2'-methylacetophenone.

[0286]

Chemical Formula 49

[0287]

[0288] Next, in the synthesis of compound (C-1) in Synthesis Example 1, the target compound (C-5) (5.58 g, yield 79%) was obtained as a brown solid using the same method except that (Intermediate 100) was changed to the above-mentioned (Intermediate 105).

[0289] The obtained brown solid was subjected to NMR measurement, and the following 58 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-5).

[0290] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.60 (1H), 7.40-6.70 (24H), 5.80-5.60 (2H), 3.70 (4H), 2.35-1.80 (21H), 1.16 (6H).

[0291]

Chemical Formula 50

[0292]

[0293] [Synthesis Example 6] Synthesis of Compound (C-6)

[0294] The following (Intermediate 106) (1.90 g, yield 39%) was obtained by the same method as in Synthesis Example 4 (Intermediate 104) except that 1'-acetonaphthone was replaced with 2'-chloroacetophenone.

[0295]

Chemical Formula 51

[0296]

[0297] Next, in the synthesis of compound (C-1) of Synthesis Example 1, except that (Intermediate 100) was changed to the above-mentioned (Intermediate 106), the target compound (C-6) (4.01 g, yield 71%) was obtained as a brown solid using the same method.

[0298] The obtained brown solid was subjected to NMR measurement, and the following 52 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-6).

[0299] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.63-6.65 (25H), 5.83-5.65 (2H), 3.71 (4H), 2.06 (3H), 2.01-1.85 (12H), 1.15 (6H).

[0300]

Chemical Formula 52

[0301]

[0302] [Synthesis Example 7] Synthesis of Compound (C-7)

[0303] The following (Intermediate 107) (3.00 g, yield 51%) was obtained by the same method as in Synthesis Example 4 (Intermediate 104) except that 1'-acetonaphthone was replaced with 2',4'-dichloroacetophenone.

[0304]

Chemical Formula 53

[0305]

[0306] Next, in the synthesis of compound (C-1) of Synthesis Example 1, except that (Intermediate 100) was changed to the above-mentioned (Intermediate 107), the target compound (C-7) (6.35 g, yield 85%) was obtained as a brown solid using the same method.

[0307] The obtained brown solid was subjected to NMR measurement, and the following 50 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-7).

[0308] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.73-6.72(23H), 5.83-5.65(2H), 3.74(4H), 2.07(3H), 2.01-1.85(12H), 1.16(6H).

[0309]

Chemical Formula 54

[0310]

[0311] [Synthesis Example 8] Synthesis of Compound (C-8)

[0312] Add 30 mL of tetrahydrofuran to a reaction vessel and stir at 0°C. Add 4.17 g (0.104 mol) of sodium hydride (60% dispersion in liquid paraffin) to the reaction solution, and dropwise add a solution of 3.00 g (26.1 mmol) of 3,3'-dimethylbutane-2-one oxime in 7 mL of tetrahydrofuran. Furthermore, add a solution of 4.97 g (26.1 mmol) of p-toluenesulfonyl chloride in 7 mL of tetrahydrofuran, and stir at room temperature (23-28°C) for 1 hour. Add 3.91 g (26.1 mmol) of 4'-methoxyacetophenone, stir at room temperature (23-28°C) for 1 hour, then raise the temperature to 50°C and stir for 44 hours. Add 30 mL of dichloromethane to the reaction solution, and then wash the solution with 200 mL of water. Extract the organic layer, dry it over anhydrous magnesium sulfate, and filter it. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (support: silica gel, solvent: toluene). The solvent was distilled off under reduced pressure to obtain the following (Intermediate 108) (2.46 g, yield 41%).

[0313]

Chemical Formula 55

[0314]

[0315] Next, 2.00 g (8.72 mmol) of the above-mentioned (intermediate 108), 0.35 g (8.72 mmol) of sodium hydride (60%, dispersed in liquid paraffin), and 6 mL of dimethylformamide were added to the reaction vessel and stirred at room temperature (23-28°C) for 30 minutes. 1.06 g (8.72 mmol) of 4-trifluorobenzonitrile was further added, and the mixture was stirred at room temperature (23-28°C) for 30 minutes. The temperature was then raised to 70°C and stirred for 1 hour. After the reaction solution was cooled to room temperature, 50 mL of ethyl acetate was added, and the solution was washed with 20 mL of water. After extraction of the organic layer, it was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (carrier: silica gel, solvent: ethyl acetate / n-heptane = 100 / 1 to 10 / 1 (volume ratio)). The solvent was removed by distillation under reduced pressure. The resulting residue was dispersed and washed with 10 mL of methanol. The solution was filtered, and the obtained solid was dried under reduced pressure to obtain the following (Intermediate 109) (2.07 g, yield 72%).

[0316]

Chemical Formula 56

[0317]

[0318] Next, in the synthesis of compound (C-1) of Synthesis Example 1, except that (Intermediate 100) was changed to the above-mentioned (Intermediate 109), the target compound (C-8) (2.44 g, yield 38%) was obtained as a blue solid using the same method.

[0319] The obtained blue solid was subjected to NMR measurement, and the following 57 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-8).

[0320] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.58-6.75 (21H), 6.00-5.83 (2H), 3.93-3.65 (7H), 2.13-1.85 (12H), 1.25-0.90 (15H).

[0321]

Chemical Formula 57

[0322]

[0323] [Synthesis Example 9] Synthesis of Compound (C-9)

[0324] 5.00 g (47.1 mmol) of benzaldehyde, 4.39 g (47.1 mmol) of aniline, 6.13 g (47.1 mmol) of ethyl acetoacetate, 2.23 g (9.42 mmol) of 1-butyl-3-methylimidazolium hydrogen sulfate, and 47 mL of nitromethane were added to a reaction vessel and stirred at 90°C for 3 hours. After the reaction solution was cooled to room temperature, 300 mL of ethyl acetate was added to the reaction solution, and then the solution was washed with 300 mL of water. After extraction of the organic layer, it was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (carrier: silica gel, solvent: toluene). The solvent was removed by distillation under reduced pressure to obtain the following (Intermediate 110) (5.51 g, yield 38%).

[0325]

Chemical Formula 58

[0326]

[0327] Next, in the synthesis of compound (C-1) of Synthesis Example 1, the target compound (C-9) (0.60 g, yield 18%) was obtained as a blue solid using the same method except that (Intermediate 100) was changed to the above-mentioned (Intermediate 110).

[0328] The obtained blue solid was subjected to NMR measurement, and the following 54 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-9).

[0329] 1H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.60 (1H), 7.45-6.65 (21H), 5.84-5.55 ( 2H), 4.05(2H), 3.75(4H), 3.42(3H), 2.13-1.85(12H), 1.16(6H), 1.02(3H).

[0330]

Chemical Formula 59

[0331]

[0332] [Synthesis Example 10] Synthesis of Compound (C-10)

[0333] To a reaction vessel were added 3.82 g (38.9 mmol) of cyclohexanone, 3.20 g (38.9 mmol) of pyrrolidine, and 76 mL of toluene, and the mixture was stirred at 100° C. for 15 hours. The solvent was distilled off under reduced pressure to obtain the following (Intermediate 111) (2.80 g, yield 48%).

[0334]

Chemical Formula 60

[0335]

[0336] Next, 0.70 g (3.24 mmol) of the above-mentioned (intermediate 111), 0.81 g (5.37 mmol) of sodium iodide, and 25 mL of N-methyl-2-pyrrolidone were added to the reaction vessel and stirred at room temperature (23-28°C) for 30 minutes. 5.12 g (25.7 mmol) of bromoacetophenone was further dissolved in 43 mL of N-methyl-2-pyrrolidone, and the solution was added dropwise to the reaction vessel over 60 minutes. After stirring the reaction solution at room temperature (23-28°C) for 10 hours, 112 mL of water was added and stirred for a further 11 hours. The solution was extracted twice with ethyl acetate and water, and the organic layer was further washed with water three times. After the organic layer was extracted, it was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (carrier: silica gel, solvent: ethyl acetate / n-heptane = 20 / 1 (volume ratio)). The solvent was distilled off under reduced pressure to obtain the following (Intermediate 112) (0.70 g, yield 18%).

[0337]

Chemical Formula 61

[0338]

[0339] Next, 0.70 g (3.24 mmol) of the above-mentioned (intermediate 112), 0.30 g (3.24 mmol) of aniline, and 7 mL of glacial acetic acid were added to the reaction vessel and stirred at 110°C for 3 hours. After the reaction solution was cooled to room temperature, 12 mL of water was added, and the suspension was stirred at room temperature (23-28°C) for 18 hours. 50 mL of ethyl acetate was added, and the solution was washed with 20 mL of water. After extraction of the organic layer, it was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (carrier: silica gel, solvent: ethyl acetate / n-heptane = 20 / 1 (volume ratio)). The solvent was removed by distillation under reduced pressure to obtain the following (intermediate 113) (0.50 g, yield 57%).

[0340]

Chemical Formula 62

[0341]

[0342] Next, in the synthesis of compound (C-1) of Synthesis Example 1, except that (Intermediate 100) was changed to the above-mentioned (Intermediate 113), the target compound (C-10) (0.60 g, yield 32%) was obtained as a blue solid using the same method.

[0343] The obtained blue solid was subjected to NMR measurement, and the following 54 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-10).

[0344] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 8.00-6.75 (22H), 5.86 (2H), 3.75 (4H), 2.38 (2H), 2.02 (14H), 1.75 (2H), 1.61 (2H), 1.15 (6H).

[0345]

Chemical Formula 63

[0346]

[0347] [Synthesis Example 11] Synthesis of Compound (C-11)

[0348] To a reaction vessel, 19.9 g (100 mmol) of bromoacetophenone, 9.31 g (100 mmol) of 2-methylpyridine, and 500 mL of acetone were added, and the mixture was stirred at 60°C for 5 hours. The reaction mixture was filtered, and the residue was dissolved in 200 mL of water, followed by stirring at 60°C for 10 minutes. To this solution, 13.8 g of potassium carbonate was added, and the mixture was stirred at 60°C for 1 hour. The reaction mixture was filtered, and the residue was washed with 50 mL of methanol. The resulting solid was dried under reduced pressure to obtain the following (Intermediate 114) (10.2 g, 53% yield).

[0349]

Chemical Formula 64

[0350]

[0351] Next, in the synthesis of compound (C-1) of Synthesis Example 1, except that (Intermediate 100) was changed to the above-mentioned (Intermediate 114), the target compound (C-11) (8.95 g, yield 93%) was obtained as a blue solid using the same method.

[0352] The obtained blue solid was subjected to NMR measurement, and the following 46 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-11).

[0353] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.83 (2H), 7.50-6.70 (20H), 5.84 (2H), 3.74 (4H), 2.19-1.83 (12H), 1.15 (6H).

[0354]

Chemical Formula 65

[0355]

[0356] [Synthesis Example 12] Synthesis of Compound (C-12)

[0357] The target compound (C-12) (3.5 g, 65% yield) was obtained as a purple solid by the same method except that (Intermediate 102) was changed to 4,4'-bis(diethylamino)benzophenone in the synthesis of compound (C-1) in Synthesis Example 1.

[0358] The obtained purple solid was subjected to NMR measurement, and the following 46 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-12).

[0359] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.50-6.95 (15H), 6.95-6.55 (8H), 3.53 (8H), 2.12 (3H), 1.13 (12H).

[0360]

Chemical Formula 66

[0361]

[0362] [Synthesis Example 13] Synthesis of Compound (C-13)

[0363] 2.50 g (10.9 mmol) of the above-mentioned (intermediate 108), 0.48 g (12.0 mol) of sodium hydride (60%, dispersed in liquid paraffin), and 27 mL of dimethylformamide were added to a reaction vessel, and the mixture was stirred at 5°C for 20 minutes. 1.96 g (12.5 mmol) of iodoethane was further added, and the mixture was stirred at room temperature (23-28°C) for 1.5 hours. 100 mL of ethyl acetate was added to the reaction solution, and the solution was washed with 20 mL of water. After extraction of the organic layer, it was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (carrier: silica gel, solvent: ethyl acetate / n-heptane = 1 / 10 (volume ratio)). The solvent was removed by distillation under reduced pressure. The obtained residue was dried under reduced pressure to obtain the following (intermediate 115) (1.94 g, yield 69%).

[0364]

Chemical Formula 67

[0365]

[0366] Next, in the synthesis of compound (C-1) of Synthesis Example 1, except that (Intermediate 100) was changed to the above-mentioned (Intermediate 115), the target compound (C-13) (3.70 g, yield 63%) was obtained as a blue solid using the same method.

[0367] The obtained blue solid was subjected to NMR measurement, and the following 58 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-13).

[0368] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.85-6.95 (16H), 6.70-6.53 (1H), 6.20-6.05 (2H) , 4.00-3.70(7H), 3.45(2H), 2.19-1.83(12H), 1.21(6H), 1.08-0.83(9H), 0.65(3H).

[0369]

Chemical Formula 68

[0370]

[0371] [Synthesis Example 14] Synthesis of Compound (C-14)

[0372] To a reaction vessel, 23.1 g (166 mmol) of choline chloride and 19.9 g (331 mmol) of urea were added, and the mixture was stirred at 80°C for 30 minutes. Furthermore, 6.50 g (30.8 mmol) of 1,3-diphenylguanidine, 3.66 g (23.7 mmol) of 2-chloroacetophenone, and 3.30 mL (23.7 mmol) of triethylamine were added, and the mixture was stirred at 80°C for 2 hours. 50 mL of water was added to the reaction solution, which was filtered and the residue was washed with 50 mL of ethyl acetate / n-heptane = 1 / 5 (volume ratio). The resulting solid was dried under reduced pressure to obtain the following (Intermediate 116) (4.00 g, 54% yield).

[0373]

Chemical Formula 69

[0374]

[0375] Next, 4.00 g (12.9 mmol) of the above-mentioned (intermediate 116), 0.57 g (14.1 mol) of sodium hydride (60%, dispersed in liquid paraffin), and 32 mL of dimethylformamide were added to the reaction vessel, and the mixture was stirred at 5°C for 20 minutes. 2.80 g (14.8 mmol) of iodoethane was further added, and the mixture was stirred at room temperature (23-28°C) for 1 hour. 200 mL of ethyl acetate was added to the reaction solution, and the solution was washed with 50 mL of water. After extracting the organic layer, it was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (carrier: silica gel, solvent: ethyl acetate / n-heptane = 1 / 10 (volume ratio)). The solvent was removed by distillation under reduced pressure. The obtained residue was dried under reduced pressure to obtain the following (intermediate 117) (3.10 g, yield 71%).

[0376]

Chemical Formula 70

[0377]

[0378] Next, in the synthesis of compound (C-1) of Synthesis Example 1, except that (Intermediate 100) was changed to the above-mentioned (Intermediate 117), the target compound (C-14) (9.28 g, yield 97%) was obtained as a blue solid using the same method.

[0379] The obtained blue solid was subjected to NMR measurement, and the following 56 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-14).

[0380] 1H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.77-6.55 (27H), 5.70 (2H), 3.97 (2H), 3.68 (4H), 2.14-1.73 (12H), 1.17 (3H), 1.10 (6H).

[0381]

Chemical Formula 71

[0382]

[0383] [Synthesis Example 15] Synthesis of Compound (C-15)

[0384] To the reaction vessel, 61.3 g (439 mmol) of choline chloride and 80.8 g (877 mmol) of glycerol were added, and the mixture was stirred at 70°C for 10 minutes. 15.0 g (62.7 mmol) of 1,3-di-o-tolylguanidine, 9.69 g (62.7 mmol) of 2-chloroacetophenone, and 8.74 mL (62.7 mmol) of triethylamine were further added, and the mixture was stirred at 80°C for 2 hours. 300 mL of ethyl acetate was added to the reaction solution, and the solution was washed with 100 mL of water. After extraction of the organic layer, it was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the residue was washed with 100 mL of diethyl ether / n-heptane = 1 / 4 (volume ratio). The obtained solid was dried under reduced pressure to obtain the following (Intermediate 118) (14.0 g, yield 66%).

[0385]

Chemical Formula 72

[0386]

[0387] Next, 15.0 g (44.2 mmol) of the above-mentioned (intermediate 118), 1.94 g (48.6 mol) of sodium hydride (60%, dispersed in liquid paraffin), and 100 mL of dimethylformamide were added to the reaction vessel, and the mixture was stirred at 5°C for 20 minutes. 7.93 g (50.8 mmol) of iodoethane was further added, and the mixture was stirred at room temperature (23-28°C) for 1 hour. 300 mL of ethyl acetate was added to the reaction solution, and the solution was washed with 100 mL of water. After extracting the organic layer, it was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the residue was washed with 50 mL of methanol. The obtained solid was dried under reduced pressure to obtain the following (intermediate 119) (14.7 g, yield 91%).

[0388]

Chemical Formula 73

[0389]

[0390] Next, in the synthesis of compound (C-1) of Synthesis Example 1, except that (Intermediate 100) was changed to the above-mentioned (Intermediate 119), the target compound (C-15) (26.6 g, yield 81%) was obtained as a blue solid using the same method.

[0391] The obtained blue solid was subjected to NMR measurement, and the following 60 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-15).

[0392] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.77-5.42 (27H), 4.18-3.50 (6H), 2.15-1.60 (18H), 1.29 (3H), 1.20-0.99 (6H).

[0393]

Chemical Formula 74

[0394]

[0395] [Synthesis Example 16] Synthesis of Compound (C-16)

[0396] To a reaction vessel were added 6.50 g (30.8 mmol) of 1,3-diphenylguanidine, 5.29 g (23.7 mmol) of 2,2',4'-trichloroacetophenone, 3.3 mL (23.7 mmol) of triethylamine, and 40 mL of tetrahydrofuran, and the mixture was stirred at 65°C for 15 hours. 200 mL of ethyl acetate was added to the reaction solution, and the solution was washed with 50 mL of water. The organic layer was extracted, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (support: silica gel, solvent: ethyl acetate / n-heptane = 1 / 6 (volume ratio)). The solvent was removed by distillation under reduced pressure. The residue was washed with 50 mL of diethyl ether / n-heptane = 1 / 50 (volume ratio). The resulting solid was dried under reduced pressure to obtain the following (Intermediate 120) (5.34 g, 59% yield).

[0397]

Chemical Formula 75

[0398]

[0399] Next, 3.00 g (8.84 mmol) of the above-mentioned (intermediate 120), 0.39 g (9.72 mol) of sodium hydride (60%, dispersed in liquid paraffin), and 22 mL of dimethylformamide were added to the reaction vessel, and the mixture was stirred at 5°C for 30 minutes. 1.59 g (10.2 mmol) of iodoethane was further added, and the mixture was stirred at room temperature (23-28°C) for 30 minutes. 50 mL of ethyl acetate was added to the reaction solution, and the solution was washed with 20 mL of water. After extracting the organic layer, it was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the residue was washed with 50 mL of methanol / water = 4 / 1 (volume ratio). The obtained solid was dried under reduced pressure to obtain the following (intermediate 121) (3.17 g, yield 98%).

[0400]

Chemical Formula 76

[0401]

[0402] Next, in the synthesis of compound (C-1) of Synthesis Example 1, except that (Intermediate 100) was changed to the above-mentioned (Intermediate 121), the target compound (C-16) (4.41 g, yield 73%) was obtained as a purple solid using the same method.

[0403] The obtained purple solid was subjected to NMR measurement, and the following 54 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-16).

[0404] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.76 (1H), 7.54-6.63 (24H), 5.80-5.57 (2H), 4.40-3.82 (6H), 2.14-1.73 (12H), 1.28-1.00 (9H).

[0405]

Chemical Formula 77

[0406]

[0407] [Synthesis Example 17] Synthesis of Compound (C-17)

[0408] In the synthesis of compound (C-2) in Synthesis Example 2, except that compound (C-1) was changed to compound (C-15), the target compound (C-17) (20.4 g, yield 99%) was obtained as a blue solid using the same method.

[0409] The obtained blue solid was subjected to NMR measurement, and the following 180 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-17).

[0410] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.77-5.42 (81H), 4.18-3.50 (18H), 2.15-1.60 (54H), 1.29 (9H), 1.20-0.99 (18H).

[0411]

Chemical Formula 78

[0412]

[0413] [Synthesis Example 18] Synthesis of Compound (C-18)

[0414] In the synthesis of compound (C-1) of Synthesis Example 1, except that (Intermediate 100) was changed to (Intermediate 119), and (Intermediate 102) was changed to 4,4'-bis(diethylamino)benzophenone, the target compound (C-18) (11.3 g, yield 87%) was obtained as a purple solid using the same method.

[0415] The obtained purple solid was subjected to NMR measurement, and the following 52 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-18).

[0416] 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=7.62-6.03(21H), 3.95-3.65(2H), 3.60-3.25(8H), 1.92(3H), 1.84(3H), 1.32(3H), 1.21-0.90(12H).

[0417]

Chemical Formula 79

[0418]

[0419] [Synthesis Example 19] Synthesis of Compound (C-19)

[0420] In the synthesis of compound (C-1) of Synthesis Example 1, except that (Intermediate 100) was changed to (Intermediate 121) and (Intermediate 102) was changed to 4,4'-bis(diethylamino)benzophenone, the target compound (C-19) (4.53 g, yield 62%) was obtained as a purple solid using the same method.

[0421] The obtained purple solid was subjected to NMR measurement, and the following 46 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-19).

[0422] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.62-6.50 (21H), 3.89 (2H), 3.51 (8H), 1.19-1.00 (15H).

[0423]

Chemical Formula 80

[0424]

[0425] [Synthesis Example 20] Synthesis of Compound (C-20)

[0426] To a reaction vessel, 8.09 g (57.9 mmol) of choline chloride and 10.67 g (116.9 mmol) of glycerol were added, and the mixture was stirred at 70°C for 10 minutes. Furthermore, 7.63 g (31.9 mmol) of 1,3-di-o-tolylguanidine, 5.00 g (29.0 mmol) of 4'-fluoroacetophenone, and 4.0 mL (29.0 mmol) of triethylamine were added, and the mixture was stirred at 80°C for 1 hour. 10 mL of water was added to the reaction solution, and the precipitated solid was filtered and washed with 50 mL of water. The filtrate was further suspended and washed with 10 mL of methanol, and the solid was filtered and dried under reduced pressure at 80°C to obtain the following (Intermediate 122) (7.50 g, 72% yield).

[0427]

Chemical Formula 81

[0428]

[0429] Next, 7.00 g (19.6 mmol) of the above-mentioned (intermediate 122), 2.64 g (23.5 mol) of potassium tert-butoxide, and 16 mL of dimethylformamide were added to the reaction vessel, and the mixture was stirred at 5°C for 10 minutes. 3.67 g (23.5 mol) of iodoethane was further added, and the mixture was stirred at room temperature (23-28°C) for 30 minutes. 10 mL of water was added to the reaction solution, and the precipitated solid was filtered. The filtrate was further suspended and washed with 20 mL of methanol, and the solid was filtered and dried under reduced pressure at 80°C to obtain the following (intermediate 123) (6.76 g, yield 90%).

[0430]

Chemical Formula 82

[0431]

[0432] Next, the target compound (C-20) (8.49 g, yield 97%) was obtained as a purple solid by the same method except that (Intermediate 100) was changed to (Intermediate 123) in the synthesis of compound (C-1) of Synthesis Example 1.

[0433] The obtained purple solid was subjected to NMR measurement, and the following 59 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-20).

[0434] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.85-6.94 (24H), 5.77 (1H), 5.56 (1H), 4.08-3.65 (6H), 2.20-1.62 (18H), 1.42-0.95 (9H).

[0435]

Chemical Formula 83

[0436]

[0437] [Synthesis Example 21] Synthesis of Compound (C-21)

[0438] In the synthesis of compound (C-1) of Synthesis Example 1, except that (Intermediate 100) was changed to (Intermediate 123) and (Intermediate 102) was changed to 4,4'-bis(diethylamino)benzophenone, the target compound (C-21) (6.34 g, yield 84%) was obtained as a purple solid using the same method.

[0439] The obtained purple solid was subjected to NMR measurement, and the following 51 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-21).

[0440] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.62-6.36 (18H), 6.33 (1H), 6.20 (1H), 3.95 -3.80(2H), 3.58-3.34(8H), 1.92(3H), 1.84(3H), 1.32(3H), 1.18-0.95(12H).

[0441]

Chemical Formula 84

[0442]

[0443] [Synthesis Example 22] Synthesis of Compound (C-22)

[0444] In the synthesis of compound (C-1) of Synthesis Example 1, except that (Intermediate 100) was changed to (Intermediate 118) and (Intermediate 102) was changed to 4,4'-bis(diethylamino)benzophenone, the target compound (C-22) (1.67 g, yield 20%) was obtained as a purple solid using the same method.

[0445] The obtained purple solid was subjected to NMR measurement, and the following 48 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-22).

[0446] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 8.47 (1H), 7.62-6.23 (21H), 3.58-3.34 (8H), 2.22 (3H), 2.15 (3H), 1.18-0.95 (12H).

[0447]

Chemical Formula 85

[0448]

[0449] [Synthesis Example 23] Synthesis of Compound (C-23)

[0450] In the synthesis of compound (C-1) of Synthesis Example 1, except that (Intermediate 100) was changed to (Intermediate 117) and (Intermediate 102) was changed to 4,4'-bis(diethylamino)benzophenone, the target compound (C-23) (11.5 g, yield 84%) was obtained as a purple solid using the same method.

[0451] The obtained purple solid was subjected to NMR measurement, and the following 48 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-23).

[0452] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.70-6.55 (23H), 3.87 (2H), 3.61-3.28 (8H), 1.22-0.98 (15H).

[0453]

Chemical Formula 86

[0454]

[0455] [Synthesis Example 24] Synthesis of Compound (C-24)

[0456] 3.00 g (8.84 mmol) of the above-mentioned (Intermediate 118), 1.19 g (10.6 mol) of potassium tert-butoxide, and 9 mL of dimethylformamide were added to a reaction vessel, and the mixture was stirred at 5°C for 10 minutes. 1.81 g (10.6 mol) of benzyl bromide was further added, and the mixture was stirred at room temperature (23-28°C) for 2 hours. 50 mL of ethyl acetate was added to the reaction solution, and the solution was washed with 50 mL of water. After extraction of the organic layer, it was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (carrier: silica gel, solvent: ethyl acetate / n-heptane = 1 / 10 (volume ratio)). The solvent was removed by distillation under reduced pressure. The obtained residue was dried under reduced pressure to obtain the following (Intermediate 124) (3.50 g, yield 92%).

[0457]

Chemical Formula 87

[0458]

[0459] Next, the target compound (C-24) (8.58 g, 90% yield) was obtained as a purple solid by the same method except that (Intermediate 100) was changed to (Intermediate 124) in the synthesis of compound (C-1) of Synthesis Example 1.

[0460] The obtained purple solid was subjected to NMR measurement, and the following 62 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-24).

[0461] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.75-5.95 (30H), 5.77 (1H), 5.55 (1H), 5.25-4.91 (2H), 3.67 (4H), 2.28-1.55 (18H), 1.29-0.90 (6H).

[0462]

Chemical Formula 88

[0463]

[0464] [Synthesis Example 25] Synthesis of Compound (C-25)

[0465] In the synthesis of compound (C-2) in Synthesis Example 2, except that compound (C-1) was changed to compound (C-23), the target compound (C-25) (20.0 g, yield 100%) was obtained as a blue solid using the same method.

[0466] The obtained blue solid was subjected to NMR measurement, and the following 144 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-25).

[0467] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.70-6.55 (69H), 3.87 (6H), 3.61-3.28 (24H), 1.22-0.98 (45H).

[0468]

Chemical Formula 89

[0469]

[0470] [Synthesis Example 26] Synthesis of Compound (C-26)

[0471] In the synthesis of compound (C-2) in Synthesis Example 2, except that compound (C-1) was changed to compound (C-23), the target compound (C-26) (19.3 g, yield 100%) was obtained as a blue solid using the same method.

[0472] The obtained blue solid was subjected to NMR measurement, and the following 168 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-26).

[0473] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.77-6.55 (81H), 5.70 (6H), 3.97 (6H), 3.68 (12H), 2.14-1.73 (36H), 1.85-1.89 (27H).

[0474]

Chemical Formula 90

[0475]

[0476] [Synthesis Example 27] Synthesis of Compound (C-27)

[0477] To a reaction vessel were added 2.50 g (8.03 mmol) of the above-mentioned (Intermediate 116), 1.08 g (9.63 mol) of potassium tert-butoxide, and 8 mL of dimethylformamide, and the mixture was stirred at 5°C for 30 minutes. Benzyl bromide (1.65 g (9.63 mol)) was further added, and the mixture was stirred at room temperature (23-28°C) for 1 hour. 20 mL of water was added to the reaction solution, and the precipitated solid was filtered. The filtrate was further suspended and washed in 20 mL of methanol, and the solid was filtered and dried under reduced pressure at 80°C to obtain the following (Intermediate 125) (2.90 g, 90% yield).

[0478]

Chemical Formula 91

[0479]

[0480] Next, in the synthesis of compound (C-1) of Synthesis Example 1, except that (Intermediate 100) was changed to (Intermediate 125) and (Intermediate 102) was changed to 4,4'-bis(diethylamino)benzophenone, the target compound (C-27) (4.00 g, yield 81%) was obtained as a purple solid using the same method.

[0481] The obtained purple solid was subjected to NMR measurement, and the following 50 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-27).

[0482] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.70-6.55 (28H), 5.05 (2H), 3.54 (8H), 1.15 (12H).

[0483]

Chemical Formula 92

[0484]

[0485] [Synthesis Example 28] Synthesis of Compound (C-28)

[0486] To a reaction vessel, 2.50 g (8.03 mmol) of the above-mentioned (intermediate 116), 1.08 g (13.6 mmol) of potassium tert-butoxide, and 8 mL of dimethylformamide were added, and the mixture was stirred at 5°C for 30 minutes. 1.65 g (13.2 mol) of 2-iodopropane was further added, and the mixture was stirred at room temperature (23-28°C) for 1 hour. 20 mL of water was added to the reaction solution, and the precipitated solid was filtered. The filtrate was further suspended and washed with 20 mL of methanol, and the solid was filtered out and dried under reduced pressure at 80°C to obtain the following (intermediate 126) (2.32 g, yield 82%).

[0487]

Chemical Formula 93

[0488]

[0489] Next, in the synthesis of compound (C-1) of Synthesis Example 1, except that (Intermediate 100) was changed to (Intermediate 126) and (Intermediate 102) was changed to 4,4'-bis(diethylamino)benzophenone, the target compound (C-28) (4.60 g, yield 86%) was obtained as a purple solid using the same method.

[0490] The obtained purple solid was subjected to NMR measurement, and the following 50 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-28).

[0491] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.70-6.62 (21H), 5.32 (2H), 4.62 (1H), 2.51 (8H), 1.24 (6H), 1.11 (12H).

[0492]

Chemical Formula 94

[0493]

[0494] [Synthesis Example 29] Synthesis of Compound (C-29)

[0495] 5.00 g (14.7 mmol) of the above-mentioned (Intermediate 118), 1.98 g (17.7 mmol) of potassium tert-butoxide, and 15 mL of dimethylformamide were added to a reaction vessel, and the mixture was stirred at 5°C for 20 minutes. 3.27 g (17.7 mol) of 2-methylbenzyl bromide was further added, and the mixture was stirred at room temperature (23-28°C) for 1 hour. 40 mL of ethyl acetate was added to the reaction solution, and the solution was washed with 100 mL of water. After extraction of the organic layer, it was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (support: silica gel, solvent: ethyl acetate / n-heptane = 1 / 10 (volume ratio)). The solvent was removed by distillation under reduced pressure. The resulting residue was dried under reduced pressure to obtain the following (Intermediate 127) (5.01 g, yield 77%).

[0496]

Chemical Formula 95

[0497]

[0498] Next, in the synthesis of compound (C-1) in Synthesis Example 1, the target compound (C-29) (4.66 g, yield 85%) was obtained as a purple solid using the same method except that (Intermediate 100) was changed to (Intermediate 127).

[0499] The obtained purple solid was subjected to NMR measurement, and the following 64 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-29).

[0500] 1H-NMR (400MHz, DMSO-d6): δ(ppm)=7.76-6.00(29H), 5.80(1H), 5.55(1H), 5.33(1H), 4.97(1H), 3.65(4H), 2.21-1.52(21H), 1.26-0.92(6H).

[0501]

Chemical Formula 96

[0502]

[0503] [Synthesis Example 30] Synthesis of Compound (C-30)

[0504] To a reaction vessel, 5.00 g (14.7 mmol) of the above-mentioned (intermediate 118), 1.98 g (17.7 mmol) of potassium tert-butoxide, and 15 mL of dimethylformamide were added, and the mixture was stirred at 5°C for 20 minutes. 3.23 g (17.7 mol) of (bromomethyl)cyclohexane was further added, and the mixture was stirred at room temperature (23-28°C) for 1 hour. 40 mL of ethyl acetate was added to the reaction solution, and the solution was washed with 100 mL of water. After extraction of the organic layer, it was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the precipitated solid was filtered out and dried under reduced pressure at 80°C to obtain the following (intermediate 128) (4.61 g, yield 72%).

[0505]

Chemical Formula 97

[0506]

[0507] Next, in the synthesis of compound (C-1) in Synthesis Example 1, the target compound (C-30) (4.53 g, yield 84%) was obtained as a purple solid using the same method except that (Intermediate 100) was changed to (Intermediate 128).

[0508] The obtained purple solid was subjected to NMR measurement, and the following 68 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-30).

[0509] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.85-5.37 (27H), 4.00 (2H), 3.62 (4H), 2.25-1.45 (24H), 1.28-0.90 (11H).

[0510]

Chemical Formula 98

[0511]

[0512] [Synthesis Example 31] Synthesis of Compound (C-31)

[0513] In the synthesis of compound (C-1) of Synthesis Example 1, except that (Intermediate 100) was changed to (Intermediate 128) and (Intermediate 102) was changed to 4,4'-bis(diethylamino)benzophenone, the target compound (C-31) (3.67 g, yield 78%) was obtained as a purple solid using the same method.

[0514] The obtained purple solid was subjected to NMR measurement, and the following 60 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-31).

[0515] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.55-6.36 (19H), 6.30 (1H), 6.01 (1H), 3.97 (2H), 3.58-3.34 (8H), 2.02 (3H), 1.89-1.54 (9H), 1.31-0.95 (17H).

[0516]

Chemical Formula 99

[0517]

[0518] [Synthesis Example 32] Synthesis of Compound (C-32)

[0519] To a reaction vessel were added 5.00 g (14.7 mmol) of the above-mentioned (Intermediate 118), 1.98 g (17.7 mmol) of potassium tert-butoxide, and 15 mL of dimethylformamide, and the mixture was stirred at 5°C for 20 minutes. Furthermore, 4.27 g (1-bromoethyl)benzene (17.7 mol) was added, and the mixture was stirred at room temperature (23-28°C) for 1 hour. 40 mL of ethyl acetate was added to the reaction solution, and the solution was washed with 200 mL of water. The organic layer was extracted, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (support: silica gel, solvent: ethyl acetate / n-hexane = 1 / 10 (volume ratio)). The solvent was removed by distillation under reduced pressure. The resulting residue was washed with 20 mL of n-hexane, and the precipitated solid was filtered and dried under reduced pressure at 80°C to obtain the following (Intermediate 129) (3.57 g, 55% yield).

[0520]

Chemical Formula 100

[0521]

[0522] Next, in the synthesis of compound (C-1) in Synthesis Example 1, the target compound (C-32) (3.08 g, yield 68%) was obtained as a purple solid using the same method except that (Intermediate 100) was changed to (Intermediate 129).

[0523] The obtained purple solid was subjected to NMR measurement, and the following 64 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-32).

[0524] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.85-5.38 (32H), 3.63 (4H), 3.48 (1H), 2.29-1.22 (21H), 1.22-0.92 (6H).

[0525] Chemical Formula 101

[0526]

[0527] [Synthesis Example 33] Synthesis of Compound (C-33)

[0528] To a reaction vessel, 5.00 g (14.7 mmol) of the above-mentioned (intermediate 118), 1.98 g (17.7 mmol) of potassium tert-butoxide, and 15 mL of dimethylformamide were added, and the mixture was stirred at 5°C for 20 minutes. 4.24 g (17.7 mol) of 2,6-dichlorobenzyl bromide was further added, and the mixture was stirred at room temperature (23-28°C) for 1 hour. 40 mL of ethyl acetate was added to the reaction solution, and the solution was washed with 200 mL of water. After extraction of the organic layer, it was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the resulting residue was washed with 20 mL of n-hexane. The precipitated solid was filtered out and dried under reduced pressure at 80°C to obtain the following (intermediate 130) (5.35 g, yield 73%).

[0529]

Chemical Formula 102

[0530]

[0531] Next, in the synthesis of compound (C-1) in Synthesis Example 1, the target compound (C-33) (3.41 g, yield 69%) was obtained as a purple solid using the same method except that (Intermediate 100) was changed to (Intermediate 130).

[0532] The obtained purple solid was subjected to NMR measurement, and the following 60 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-33).

[0533] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.75-4.75 (30H), 3.63 (4H), 3.47 (2H), 2.42-1.20 (18H), 1.20-0.92 (6H).

[0534]

Chemical Formula 103

[0535]

[0536] [Synthesis Example 34] Synthesis of Compound (C-34)

[0537] In the synthesis of compound (C-1) of Synthesis Example 1, except that (Intermediate 100) was changed to (Intermediate 130) and (Intermediate 102) was changed to 4,4'-bis(diethylamino)benzophenone, the target compound (C-34) (2.00 g, yield 46%) was obtained as a purple solid using the same method.

[0538] The obtained purple solid was subjected to NMR measurement, and the following 52 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-34).

[0539] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.65-5.45 (24H), 5.00 (2H), 3.43 (8H), 2.29-1.53 ​​(6H), 1.13-0.97 (12H).

[0540]

Chemical Formula 104

[0541]

[0542] [Synthesis Example 35] Synthesis of Compound (C-35)

[0543] In the synthesis of compound (C-2) in Synthesis Example 2, except that compound (C-1) was changed to compound (C-33), the target compound (C-35) (15.0 g, yield 81%) was obtained as a blue solid using the same method.

[0544] The obtained blue solid was subjected to NMR measurement, and the following 180 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-35).

[0545] 1H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.75-4.75 (90H), 3.63 (12H), 3.47 (6H), 2.42-1.20 (54H), 1.20-0.92 (18H).

[0546]

Chemical Formula 105

[0547]

[0548] [Synthesis Example 36] Synthesis of Compound (C-36)

[0549] To a reaction vessel, 25.0 g (458.3 mmol) of N-methylaniline, 51.4 g (458.3 mmol) of potassium tert-butoxide, and 255 mL of dimethylformamide were added, and the mixture was stirred at 5°C for 20 minutes. A solution of 25.0 g (114.6 mol) of 4,4-difluorobenzophenone in 25 mL of DMF was further added dropwise, and the mixture was stirred at room temperature (23-28°C) for 2 hours. 150 mL of ethyl acetate and 300 mL of water were added to the reaction solution, and the mixture was stirred at room temperature (23-28°C) for 2 hours. The precipitated solid was filtered and dried under reduced pressure at 80°C to obtain the following (Intermediate 131) (39.2 g, 87% yield).

[0550]

Chemical Formula 106

[0551]

[0552] Next, in the synthesis of compound (C-1) of Synthesis Example 1, except that (intermediate 100) was changed to (intermediate 119) and (intermediate 102) was changed to (intermediate 131), the target compound (C-36) (27.6 g, yield 99%) was obtained in the form of a purple solid using the same method.

[0553] The obtained purple solid was subjected to NMR measurement, and the following 48 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-36).

[0554] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.70-6.10 (31H), 3.88 (2H), 3.32 (6H), 1.94 (3H), 1.77 (3H), 1.26 (3H).

[0555]

Chemical Formula 107

[0556]

[0557] [Synthesis Example 37] Synthesis of Compound (C-37)

[0558] In the synthesis of compound (C-2) in Synthesis Example 2, except that compound (C-1) was changed to compound (C-33), the target compound (C-35) (15.0 g, yield 81%) was obtained as a blue solid using the same method.

[0559] The obtained blue solid was subjected to NMR measurement, and the following 144 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-37).

[0560] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.55-6.22 (93H), 3.82 (6H), 3.31 (18H), 1.94 (9H), 1.77 (9H), 1.26 (9H).

[0561]

Chemical Formula 108

[0562]

[0563] [Synthesis Example 38] Synthesis of Compound (C-38)

[0564] 17.1 g (100.8 mmol) of diphenylamine, 13.4 g (119.2 mmol) of potassium tert-butoxide, and 220 mL of dimethylformamide were added to the reaction vessel, and the mixture was stirred at 60°C for 20 minutes. 10.0 g (45.8 mol) of 4,4-difluorobenzophenone was further added, and the mixture was stirred at 110°C for 7 hours. 1500 mL of water and 300 mL of saturated brine were added to the reaction solution, and the precipitated solid was filtered out. The obtained solid was dissolved in 500 mL of chloroform, concentrated, and then 200 mL of methanol was added for recrystallization. After filtering the precipitated solid, it was dried under reduced pressure at 80°C to obtain the following (Intermediate 132) (11.8 g, yield 50%).

[0565]

Chemical Formula 109

[0566]

[0567] Next, in the synthesis of compound (C-1) of Synthesis Example 1, except that (intermediate 100) was changed to (intermediate 119) and (intermediate 102) was changed to (intermediate 132), the target compound (C-38) (4.33 g, yield 69%) was obtained in the form of a purple solid using the same method.

[0568] The obtained purple solid was subjected to NMR measurement, and the following 52 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-38).

[0569] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.70-6.20 (41H), 3.90 (2H), 2.02 (3H), 1.80 (3H), 1.26 (3H).

[0570]

Chemical Formula 110

[0571]

[0572] [Synthesis Example 39] Synthesis of Compound (C-39)

[0573] The target compound (C-39) (6.16 g, yield 38%) was obtained as a purple solid by the same method except that (Intermediate 100) was changed to (Intermediate 118) in the synthesis of compound (C-1) in Synthesis Example 1.

[0574] The obtained purple solid was subjected to NMR measurement, and the following 56 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-39).

[0575] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 8.77 (1H), 7.95-6.35 (25H), 5.60 (2H), 3.56 (4H), 2.45-1.50 (18H), 1.18-0.95 (6H).

[0576]

Chemical Formula 111

[0577]

[0578] [Synthesis Example 40] Synthesis of Compound (C-40)

[0579] To a reaction vessel were added 5.00 g (14.7 mmol) of the above-mentioned (Intermediate 118), 1.98 g (17.7 mmol) of potassium tert-butoxide, and 20 mL of dimethylformamide, and the mixture was stirred at 5°C for 20 minutes. Furthermore, 3.29 g (17.7 mol) of methyl p-toluenesulfonate was added, and the mixture was stirred at room temperature (23-28°C) for 1 hour. 20 mL of water was added to the reaction solution, and the precipitated solid was filtered. The filtrate was further suspended and washed in 20 mL of methanol, and the solid was filtered and dried under reduced pressure at 80°C to obtain the following (Intermediate 133) (4.30 g, yield 83%).

[0580]

Chemical Formula 112

[0581]

[0582] Next, in the synthesis of compound (C-1) in Synthesis Example 1, the target compound (C-40) (5.13 g, yield 80%) was obtained as a purple solid using the same method except that (Intermediate 100) was changed to (Intermediate 133).

[0583] The obtained purple solid was subjected to NMR measurement, and the following 58 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-40).

[0584] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.75-6.04 (25H), 5.95-5.35 (2H), 3.78-3.50 (4H), 3.38 (3H), 2.18-1.52 (18H), 1.23-0.89 (6H).

[0585]

Chemical Formula 113

[0586]

[0587] [Synthesis Example 41] Synthesis of Compound (C-41)

[0588] In the synthesis of compound (C-1) of Synthesis Example 1, except that (Intermediate 100) was changed to (Intermediate 133) and (Intermediate 102) was changed to 4,4'-bis(diethylamino)benzophenone, the target compound (C-41) (4.02 g, yield 48%) was obtained as a purple solid using the same method.

[0589] The obtained purple solid was subjected to NMR measurement, and the following 50 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-41).

[0590] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.55-6.05 (21H), 3.56-3.30 (8H), 3.35 (3H), 1.90 (3H), 1.79 (3H), 1.07 (6H), 1.01 (6H).

[0591]

Chemical Formula 114

[0592]

[0593] [Synthesis Example 42] Synthesis of Compound (C-42)

[0594] In the synthesis of compound (C-2) in Synthesis Example 2, except that compound (C-1) was changed to compound (C-40), the target compound (C-42) (14.7 g, yield 91%) was obtained as a blue solid using the same method.

[0595] The obtained blue solid was subjected to NMR measurement, and the following 174 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-42).

[0596] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.75-6.04 (75H), 5.95-5.35 (6H), 3.78-3.50 (12H), 3.38 (9H), 2.18-1.52 (54H), 1.23-0.89 (18H).

[0597]

Chemical Formula 115

[0598]

[0599] [Synthesis Example 43] Synthesis of Compound (C-43)

[0600] In the synthesis of compound (C-2) in Synthesis Example 2, except that compound (C-1) was changed to compound (C-41), the target compound (C-43) (8.29 g, yield 97%) was obtained as a blue solid using the same method.

[0601] The obtained blue solid was subjected to NMR measurement, and the following 150 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-43).

[0602] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.55-6.05 (63H), 3.56-3.30 (24H), 3.35 (9H), 1.90 (9H), 1.79 (9H), 1.07 (18H), 1.01 (18H).

[0603]

Chemical Formula 116

[0604]

[0605] [Synthesis Example 44] Synthesis of Compound (C-44)

[0606] In the synthesis of compound (C-2) in Synthesis Example 2, except that compound (C-1) was changed to compound (C-18), the target compound (C-44) (6.38 g, yield 75%) was obtained as a blue solid using the same method.

[0607] The obtained blue solid was subjected to NMR measurement, and the following 156 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-44).

[0608] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.50-6.03 (63H), 3.66-3.20 (30H), 1.87 (9H), 1.80 (9H), 1.27 (9H), 1.14-0.95 (36H).

[0609]

Chemical Formula 117

[0610]

[0611] [Synthesis Example 45] Synthesis of Compound (C-45)

[0612] 3.90 g (3.52 mmol) of the above-mentioned (C-15) and 165 mL of methanol were added to a reaction vessel. After dissolving the solid, a solution of 2.63 g of silicotungstic acid hydrate dissolved in 35 mL of methanol was added dropwise. The solution was stirred at room temperature (23-28°C) for 2 hours, and the reaction liquid was filtered. The obtained solid was suspended and washed twice with 75 mL of methanol, and after filtering the solid, it was dried under reduced pressure at 80°C to obtain the target compound (C-45) (3.60 g, yield 74%) as a blue solid.

[0613] The obtained blue solid was subjected to NMR measurement, and the following 240 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-45).

[0614] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.77-5.42 (108H), 4.00-3.55 (24H), 2.15-1.58 (72H), 1.25 (12H), 1.24-0.93 (24H).

[0615]

Chemical Formula 118

[0616]

[0617] [Synthesis Example 46] Synthesis of Compound (C-46)

[0618] To a reaction vessel, 5.00 g (4.52 mmol) of the above-mentioned (C-15) and 215 mL of methanol were added. After dissolving the solid, a solution of 3.03 g of silicomolybdic acid hydrate dissolved in 100 mL of methanol was added dropwise. The solution was stirred at room temperature (23-28°C) for 1.5 hours, and the reaction liquid was filtered. The resulting solid was suspended and washed twice with 400 mL of methanol, filtered, and dried under reduced pressure at 80°C to obtain the target compound (C-46) (3.88 g, yield 67%) as a blue solid.

[0619] The obtained blue solid was subjected to NMR measurement, and the following 240 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-46).

[0620] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.77-5.42 (108H), 4.00-3.73 (8H), 3.72-3.54 (16H), 2.10-1.58 (72H), 1.24 (12H), 1.23-0.93 (24H).

[0621]

Chemical Formula 119

[0622]

[0623] [Synthesis Example 47] Synthesis of Compound (C-47)

[0624] By the method described in paragraph

[0121] of Patent Document 6 (International Patent Publication No. 2019-044096), an inorganic compound (E-1) represented by the following formula was obtained as a yellow solid.

[0625]

Chemical Formula 120

[0626] K6(P2MoW 17 O 62 ) (E-1)

[0627] Next, 7.00 g (6.32 mmol) of (C-15) and 490 mL of methanol were added to a reaction vessel to dissolve the solid. A solution prepared by dissolving 4.88 g of the inorganic compound (E-1) in 100 mL of purified water was then added dropwise. This solution was stirred at 70°C for 1 hour, and the reaction mixture was filtered. The resulting solid was suspended and washed in 500 mL of methanol, filtered, and dried under reduced pressure at 80°C to obtain the target compound (C-47) (26.6 g, 90% yield) as a blue solid.

[0628] The obtained blue solid was subjected to NMR measurement, and the following 360 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (C-47).

[0629] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.77-5.42 (162H), 4.18-3.50 (36H), 2.15-1.60 (108H), 1.29 (18H), 1.20-0.99 (36H).

[0630]

Chemical Formula 121

[0631]

[0632] [Synthesis of Comparative Example Compound (D-1)]

[0633] By the method described in Synthesis Example 1, paragraph

[0058] of Patent Document 5 (Japanese Patent Application Laid-Open No. 2012-83652), a comparative compound (D-1) represented by the following formula was obtained as a brown solid.

[0634] The obtained brown solid was subjected to NMR measurement, and the following 40 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (D-1).

[0635] 1 H-NMR (400MHz, CDCl3): δ (ppm) = 8.01 (1H), 7.54-7.18 (8H), 6.90-6.62 (5H), 6.18 (1H), 3.62-3.51 (10H), 1.47 (3H), 1.30 (12H).

[0636]

Chemical Formula 122

[0637]

[0638] [Synthesis of Comparative Example Compound (D-2)]

[0639] By the method described in paragraphs

[0320] to

[0322] of Patent Document 3, a comparative example compound (D-2) represented by the following formula was obtained as a brown solid.

[0640] The obtained brown solid was subjected to NMR measurement, and the following 40 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (D-2).

[0641] 1H-NMR (400MHz, CDCl3): δ (ppm) = 7.80 (1H), 7.48-7.17 (11H), 6.93 (1H), 6.90-6.66 (4H), 3.85 (3H), 3.55 (8H), 1.15 (12H).

[0642]

Chemical Formula 123

[0643]

[0644] [Synthesis of Comparative Example Compound (D-3)]

[0645] By the method described in Example 1 in paragraphs

[0208] to

[0211] of Patent Document 4, a comparative compound (D-3) represented by the following formula was obtained as a bluish-purple solid.

[0646] The obtained blue-purple solid was subjected to NMR measurement, and the following 45 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (D-3).

[0647] 1 H-NMR (400MHz, CDCl3): δ (ppm) = 7.56-7.41 (4H), 7.40-7.23 (6H), 7.21-7.11 (3H), 6.84-6.72(4H), 4.31(1H), 3.91(1H), 3.50(8H), 2.31(3H), 1.29(3H), 1.11(12H).

[0648]

Chemical Formula 124

[0649]

[0650] [Synthesis of Comparative Example Compound (D-4)]

[0651] In the synthesis of compound (C-1) of Synthesis Example 1, except that (Intermediate 100) was changed to the above-mentioned (Intermediate 108), the comparative example compound (D-4) represented by the following formula was obtained as a bluish purple solid (7.65 g, yield 91%) using the same method.

[0652] The obtained blue-purple solid was subjected to NMR measurement, and the following 54 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (D-4).

[0653] 1H-NMR (400MHz, DMSO-d6): δ (ppm) = 11.83 (1H), 7.87 (2H), 7.60-6.95 (15H), 6.07 (2H), 3.82 (7H), 2.06 (12H), 1.21 (6H), 1.01 (9H).

[0654]

Chemical Formula 125

[0655]

[0656] [Synthesis of Comparative Example Compound (D-5)]

[0657] To the reaction vessel, 1.0 g (1.03 mmol) of the comparative compound (D-4) and 20 mL of methanol were added, and the mixture was stirred at room temperature (23-28° C.) for 30 minutes. 2 mL of a 40% by mass aqueous sodium hydroxide solution was added to the solution, and the mixture was stirred at room temperature for 30 minutes. 100 ml of water was further added, and the mixture was stirred at room temperature for 30 minutes. The reaction solution was filtered under reduced pressure, and the residue was washed with 50 mL of water. The obtained solid was dried under reduced pressure to obtain a comparative compound (D-5) (0.65 g, yield 92%) represented by the following formula as a brown solid.

[0658] The obtained brown solid was subjected to NMR measurement, and the following 53 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (D-5).

[0659] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.81 (2H), 7.25-6.81 (17H), 3.79 (3H), 3.64 (4H), 2.12-2.01 (12H), 1.20-1.12 (6H), 0.95 (9H).

[0660]

Chemical Formula 126

[0661]

[0662] [Synthesis of Comparative Example Compound (D-6)]

[0663] The following (Intermediate 134) (1.40 g, yield 18%) was obtained by the same method as in Synthesis Example 11 (Intermediate 114) except that 2-methylpyridine was replaced with 2-ethylpyridine.

[0664]

Chemical Formula 127

[0665]

[0666] Next, in the synthesis of compound (C-1) of Synthesis Example 1, except that (Intermediate 100) was changed to the above-mentioned (Intermediate 134), the comparative example compound (D-6) represented by the following formula was obtained as a purple solid (5.12 g, yield 80%) using the same method.

[0667] The obtained purple solid was subjected to NMR measurement, and the following 48 hydrogen signals were detected, thereby identifying the structure of the compound represented by the following formula (D-6).

[0668] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 8.66 (1H), 7.59-6.35 (20H), 6.15-5.45 (2H), 3.93-3.40 (4H), 2.51 (3H), 2.19-1.83 (12H), 1.15 (6H).

[0669]

Chemical Formula 128

[0670]

[0671] [Example 1]

[0672] (Determination of maximum absorption wavelength)

[0673] Compound (C-1) obtained in Synthesis Example 1 was dissolved in propylene glycol monomethyl ether (PGME) to prepare a solution with a concentration of 0.01 mmol / L. The UV-visible absorption spectrum (wavelength range of 350 to 800 nm) as a spectral characteristic was measured at room temperature (25°C) using a UV-visible spectrophotometer (manufactured by JASCO Corporation, model: V-650). The maximum absorption wavelength within the measured wavelength range was measured. The measurement results are shown in Table 1.

[0674] (Measurement of 5% mass loss temperature)

[0675] Compound (C-1) obtained in Synthesis Example 1 was subjected to TG-DTA analysis (sample mass: 5.0-6.0 mg, heating rate: 10°C / min) under a nitrogen stream using a thermogravimetric differential thermal analyzer (TG-DTA 2000S, manufactured by MAC Science Co., Ltd.) to measure the 5% mass loss temperature. The results are shown in Table 1.

[0676] (Evaluation of heat resistance)

[0677] 20 mg of the compound (C-1) obtained in Synthesis Example 1 and 5 g of a 25% by mass DMF-PGMEA mixed solution of a copolymer of methacrylic acid, acrylic acid ester, and styrene were added to a sample bottle and stirred for 30 minutes. The obtained colored resin solution was filtered with a syringe filter, and 1 g of the filtrate was applied to a glass substrate (spin coating method, 1000 rpm-6 seconds), and heated and dried at 100°C for 2 minutes to prepare a thin film. The color value of the obtained film was measured using a spectrocolorimeter (CM-5 manufactured by Konica Minolta Co., Ltd.). Thereafter, the color value was measured in the same manner after heating at 230°C for 20 minutes. The color difference (ΔE ＊ ab ) was used as an index of heat resistance, and the results are shown in Table 1.

[0678] [Example 2 to Example 47]

[0679] In Example 1, except that compounds (C-2) to (C-47) obtained in Synthesis Examples 2 to 47 were used instead of Compound (C-1), the maximum absorption wavelength, 5% mass loss temperature, and heat resistance were measured in the same manner as in Example 1. The results are summarized in Table 1.

[0680] [Comparative Examples 1 to 6]

[0681] For comparison, the maximum absorption wavelength, 5% mass loss temperature, and heat resistance evaluation were performed in the same manner as in Example 1, except that the above-described comparative example compounds (D-1) to (D-6), which are not triarylmethane dyes of the present invention, were used instead of the example compound (C-1). The results are summarized in Table 1.

[0682]

Table 1

[0683]

[0684] As shown in Table 1, the triarylmethane dyes of the examples of the present invention were superior to the triarylmethane dyes of the comparative examples in terms of 5% mass loss temperature and heat resistance during film formation.

[0685] The coloring composition containing a triarylmethane dye of the present invention has high heat resistance and can be used as a dye material for various applications such as a colorant for color filters.

Claims

1. A triarylmethane pigment represented by the following general formula (1): 【Chemical Formula 1】 In formula (1), R 1 ~R 4 Independently represent: hydrogen atoms, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent; R 5 、R 6 Independently represent: hydrogen atoms, Halogen atoms, ―OH, ―CF3, ―NO2, ―CN, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, a linear, branched, or cyclic alkoxy group having 1 to 20 carbon atoms which may have a substituent, or an aryloxy group having 6 to 20 carbon atoms which may have a substituent; A H represents a heterocyclic group represented by the following general formula (2); An represents an anion, and m represents a natural number; 【Chemical Formula 2】 In formula (2), X 1 represents nitrogen atom, CR 9 or NR 10 ; X 2 Indicates CR 9 or NR 10 ; X 1 and X 2 At least one of the NR 10 ; R 7 ~R 9 Independently represent: hydrogen atoms, Halogen atoms, ―OH, ―CF3, ―NO2, ―CN, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, a linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms which may have a substituent, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, a heterocyclic group having 5 to 20 ring atoms which may have a substituent, ―NO 11 R 12 、 an acyl group having 1 to 20 carbon atoms which may have a substituent, a linear, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms which may have a substituent; or an aryloxycarbonyl group having 7 to 20 carbon atoms which may have a substituent; R 10 express: a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, a linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a heterocyclic group having 5 to 20 ring atoms which may have a substituent; R 11 and R 12 Independently represent: hydrogen atoms, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a heterocyclic group having 5 to 20 ring atoms which may have a substituent; R 7 ~R 12 Adjacent groups can be bonded to each other via single bonds, double bonds, substituted or unsubstituted methylene groups, oxygen atoms, or sulfur atoms to form a ring; The dotted line portion represents the bonding portion with the general formula (1).

2. The triarylmethane dye according to claim 1, wherein In the general formula (1), A H is a heterocyclic group represented by any one of the following general formulas (2-1) to (2-4); 【Chemical Formula 3】 In formula (2-1), R 7 ~R 10 Indicates that R in the general formula (2) 7 ~R 10 The same group, adjacent R 7 and R 9 and R 8 and R 9 can be independently bonded to each other via a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring; The dotted line portion represents the bonding portion with the general formula (1); 【Chemical Formula 4】 In formula (2-2), R 7 ~R 10 Indicates that R in the general formula (2) 7 ~R 10 The same group, adjacent R 7 and R 9 can be bonded to each other via single bonds, double bonds, substituted or unsubstituted methylene groups, oxygen atoms or sulfur atoms to form a ring; The dotted line portion represents the bonding portion with the general formula (1); 【Chemical Formula 5】 In formula (2-3), R 7 、R 8 and R 10 Indicates that R in the general formula (2) 7 、R 8 and R 10 The same group, the dotted line portion represents the bonding portion with the general formula (1); 【Chemical Formula 6】 In formula (2-4), R 13 and R 15 ~R 18 Indicates that R in the general formula (2) 7 ~R 9 The same group, R 14 represents a hydrogen atom, and the dotted line portion represents a bonding portion with the general formula (1).

3. The triarylmethane dye according to claim 2, wherein In the general formula (1), A H is a heterocyclic group represented by the general formula (2-1), wherein R 7 、R 8 and R 10 are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, R 9 A hydrogen atom.

4. The triarylmethane dye according to claim 2, wherein In the general formula (1), A H is a heterocyclic group represented by the general formula (2-1), wherein R 7 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, R 8 and R 10 are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, R 9 It is an acyl group having 1 to 10 carbon atoms which may have a substituent, a linear, branched or cyclic alkoxycarbonyl group having 2 to 10 carbon atoms which may have a substituent, or an aryloxycarbonyl group having 7 to 10 carbon atoms which may have a substituent.

5. The triarylmethane dye according to claim 2, wherein In the general formula (1), A H is a heterocyclic group represented by the general formula (2-1), wherein R 7 is an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, R 8 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, R 9 is a hydrogen atom, R 10 It is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

6. The triarylmethane dye according to claim 2, wherein In the general formula (1), A H is a heterocyclic group represented by the general formula (2-2), wherein R 7 and R 9 are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, R 8 and R 10 Each independently represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

7. The triarylmethane dye according to claim 2, wherein In the general formula (1), A H is a heterocyclic group represented by the general formula (2-3), R 7 NR 11 R 12 , R 8 and R 10 are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, 11 and R 12 Each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

8. The triarylmethane dye according to claim 2, wherein In the general formula (1), A H is a heterocyclic group represented by the general formula (2-4), wherein R 13 It is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

9. The triarylmethane dye according to claim 1, wherein In the general formula (1), R 1 and R 2 are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, R 3 and R 4 Each independently represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

10. The triarylmethane dye according to claim 1, wherein In the general formula (1), An is a perfluoroalkylsulfonate anion, a perfluoroalkylsulfonimide anion, a tris(trifluoromethanesulfonyl)methide anion, or a heteropolyacid anion.

11. The triarylmethane dye according to claim 1, wherein The maximum absorption wavelength of the absorption band in the ultraviolet-visible absorption spectrum of 350 nm to 800 nm measured at 23° C. to 27° C. using a propylene glycol monomethyl ether (PGME) solution of the triarylmethane dye is in the wavelength range of 570 nm to 640 nm. 12 . A coloring composition comprising the triarylmethane dye according to claim 1 . 13 . A colorant for color filters, comprising the coloring composition according to claim 12 . A color filter using the colorant for color filter according to claim 13 .

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