Pigment compounds

Abstract

To provide a compound that exhibits high absorbance around 400 nm, good light resistance, and is resistant to changes in the waveform of its absorption spectrum due to ultraviolet light. [Solution] A compound represented by the following general formula (1). [C1] JPEG2026114053000031.jpg9156 (In general formula (1), D represents the group shown in general formula (2) or general formula (3), and A represents the group shown in general formula (4).)

Description

[Technical Field]

[0001] This invention relates to compounds that can be used as dyes. [Background technology]

[0002] Ultraviolet and blue light have high energy and can damage the retina, potentially causing eye diseases. Therefore, there is a need for compounds that can be used as UV absorbers or blue light-blocking colorants. Patent Document 1 describes a compound having a methine structure that can be used as an UV absorber. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2018-188565 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] Compounds used as UV absorbers and blue light-blocking colorants are required to have good lightfastness. The compound described in Patent Document 1 has good lightfastness, but it has been found that the waveform of its absorption spectrum changes when exposed to ultraviolet light. Specifically, it was found that the wavelength of absorption maximum shifts slightly and the peak shape becomes somewhat broader in the absorption spectrum. This change in the spectrum due to ultraviolet irradiation is reversible, and the waveform returns to the state before irradiation when not exposed to ultraviolet light, but there is a need for compounds that are less susceptible to such changes in the waveform of the absorption spectrum due to ultraviolet light.

[0005] The main objective of this invention is to provide a compound that has high absorbance around 400 nm, good light resistance, and is less susceptible to changes in the waveform of its absorption spectrum due to ultraviolet light. [Means for solving the problem]

[0006] The inventors conducted diligent research to solve the above problems and found that a merocyanine compound represented by the following general formula (1) has an absorption maximum around 400 nm, high absorbance around 400 nm, is less susceptible to changes in the waveform of its absorption spectrum due to ultraviolet light, and has good light resistance. Based on this finding, the inventors conducted further research and completed the present invention.

[0007] In other words, the present invention relates to the following compounds, dye compositions, blue light shielding molded articles, ultraviolet absorbers, etc., although it is not limited to these. [1] A compound represented by the following general formula (1).

[0008] [ka]

[0009] (In general formula (1), D represents the group shown in general formula (2) or general formula (3), and A represents the group shown in general formula (4).

[0010] [ka]

[0011] (In general formula (2), R 21 R represents an alkyl group which may have substituents or a group represented by general formula (5), 22a , R 22b , R 23a and R 23b (The symbols * represent a hydrogen atom or an alkyl group, either identical or different, and * represents a bonding site with a carbon atom in general formula (1).)

[0012] [ka]

[0013] (In general formula (3), R 31 R represents an alkyl group. 32a , R 32b, R 33a and R 33b are the same or different and each represents a hydrogen atom or an alkyl group, and R 34 represents an alkyl group, and * represents the bonding site with the carbon atom in the general formula (1).)

[0014]

Chemical Formula

[0015] (In the general formula (4), R 45 represents a cyano group, and R 46a , R 46b , R 46c , R 46d and R 46e are the same or different and each represents a hydrogen atom or an alkyl group, and R 47a , R 47b , R 47c , R 47d and R 47e are the same or different and each represents a hydrogen atom or an alkyl group, and * represents the bonding site with the carbon atom in the general formula (1).)

[0016]

Chemical Formula

[0017] (In the general formula (5), R 51 represents an alkylene group, and R 52a , R 52b , R 53a and R 53b are the same or different and each represents a hydrogen atom or an alkyl group, and R 55 represents a cyano group, and R 56a , R 56b , R 56c , R 56d and R 56e are the same or different and each represents a hydrogen atom or an alkyl group, and R 57a , R 57b , R 57c , R 57d and R 57e* represents a hydrogen atom or an alkyl group, either identical or different, and * represents the bonding site with the nitrogen atom in general formula (2). [2] The compound described in [1] above, wherein D represents the group shown in general formula (1). [3] In general formula (2), R 21 R represents an alkyl group having 1 to 6 carbon atoms, which may have substituents. 22a , R 22b , R 23a and R 23b The compound described in [1] or [2] above, which is identical or different in that it represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. [4] In general formula (4), R 46a , R 46b , R 46c , R 46d and R 46e R represents a hydrogen atom. 47a , R 47c and R 47e R represents the same or different hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 47b and R 47d The compound is one of the compounds described in any of [1] to [3] above, which represents a hydrogen atom. [5] In general formula (5), R 51 This represents an alkylene group with 1 to 8 carbon atoms, R 52a , R 52b , R 53a and R 53b R represents a hydrogen atom. 56a , R 56b , R 56c , R 56d and R 56e R represents a hydrogen atom. 57a , R 57c and R 57e R represents the same or different hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 57b and R 57d The compound is one of the compounds described in any of [1] to [4] above, which represents a hydrogen atom. [6] In general formula (3), R 31 R represents an alkyl group having 1 to 3 carbon atoms. 32a , R 32b , R 33a and R33b R represents the same or different hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 34 The compound is one of the compounds described in any of [1] to [5] above, which has an alkyl group having 1 to 3 carbon atoms. [7] A dye composition characterized by containing any of the compounds described in [1] to [6] above. [8] A blue light shielding molded article characterized by containing any of the compounds described in [1] to [6] above. [9] An ultraviolet absorber characterized by containing any of the compounds described in [1] to [6] above. [Effects of the Invention]

[0018] According to the present invention, it is possible to provide a compound that has high absorbance around 400 nm, good light resistance, and is less susceptible to changes in the waveform of its absorption spectrum due to ultraviolet light. [Modes for carrying out the invention]

[0019] The compound of the present invention is a compound represented by the following general formula (1).

[0020] [ka]

[0021] (In general formula (1), D represents the group shown in general formula (2) or general formula (3), and A represents the group shown in general formula (4).

[0022] [ka]

[0023] (In general formula (2), R 21 R represents an alkyl group which may have substituents or a group represented by general formula (5), 22a , R 22b , R 23a and R 23bis the same as or different from and represents a hydrogen atom or an alkyl group, and * represents the bonding site with the carbon atom in general formula (1).)

[0024] [Chemical formula]

[0025] (In general formula (3), R 31 represents an alkyl group, R 32a , R 32b , R 33a and R 33b are the same as or different from and represent a hydrogen atom or an alkyl group, R 34 represents an alkyl group, and * represents the bonding site with the carbon atom in general formula (1).)

[0026] [Chemical formula]

[0027] (In general formula (4), R 45 represents a cyano group, R 46a , R 46b , R 46c , R 46d and R 46e are the same as or different from and represent a hydrogen atom or an alkyl group, R 47a , R 47b , R 47c , R 47d and R 47e are the same as or different from and represent a hydrogen atom or an alkyl group, and * represents the bonding site with the carbon atom in general formula (1).)

[0028] [Chemical formula]

[0029] (In general formula (5), R 51 represents an alkylene group, R 52a , R 52b , R 53a and R 53bR represents a hydrogen atom or an alkyl group, either identical or different. 55 R indicates a cyano group. 56a , R 56b , R 56c , R 56d and R 56e R represents a hydrogen atom or an alkyl group, either identical or different. 57a , R 57b , R 57c , R 57d and R 57e * represents a hydrogen atom or an alkyl group, either identical or different, and * represents the bonding site with the nitrogen atom in general formula (2).

[0030] The compound represented by the above general formula (1) is also referred to as compound (1) in this specification. If geometric isomers exist in compound (1) of the present invention, the present invention encompasses all of those geometric isomers. Furthermore, if compound (1) of the present invention contains one or more chiral carbon atoms, the present invention encompasses compounds in which each chiral carbon atom is in an R configuration, a S configuration, or any combination thereof. Moreover, the present invention also encompasses racemic compounds, racemic mixtures, single enantiomers, and diastereomer mixtures thereof.

[0031] In the above general formula (1), D represents the group shown in general formula (2) or general formula (3). In one embodiment, D preferably represents the group shown in general formula (2).

[0032] In general formula (2), R 21 This represents an alkyl group which may have substituents or a group represented by general formula (5). Examples of alkyl groups that may have substituents include linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms that may have substituents. Preferably, the alkyl group with substituents has 1 to 20 carbon atoms. In this specification, unless otherwise specified, the carbon number of an optionally substituted group refers to the total carbon number of the group including the substituents. Linear alkyl groups include, for example, linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, and n-pentadecyl groups; Isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-methylbutyl group, 1-methylbutyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,2-dimethylbutyl group, 1,1-dimethylbutyl group, 3-ethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, 1,1,2-trimethylpropyl group, 1-ethyl-2-methylpropyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group Branched alkyl groups such as 1-ethylpentyl group, 2,4-dimethylpentyl group, 2-ethylhexyl group, 2,5-dimethylhexyl group, 2,5,5-trimethylpentyl group, 2,4-dimethylhexyl group, 2,2,4-trimethylpentyl group, 1,1-dimethylhexyl group, 1,1,3,3-tetramethylbutyl group, 3,5,5-trimethylhexyl group, 4-ethyloctyl group, 4-ethyl-4,5-dimethylhexyl group, 1,3,5,7-tetramethyloctyl group, 4-butyloctyl group, 6,6-diethyloctyl group, 6-methyl-4-butyloctyl group, 3,5-dimethylheptadecyl group, 2,6-dimethylheptadecyl group, 2,4-dimethylheptadecyl group, and 2,2,5,5-tetramethylhexyl group; Examples include cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, and adamantyl group. In the present invention, the alkyl group is preferably a linear or branched alkyl group.

[0033] The substituents in the alkyl group, which may have substituents, are not particularly limited and include, for example, monocyclic or polycyclic aromatic ring groups having 6 to 10 carbon atoms (phenyl group, naphthyl group, etc.), linear, branched or cyclic alkoxy groups having 1 to 8 carbon atoms, amino groups, mono- or di-alkylamino groups (alkyl groups have 1 to 8 carbon atoms), halogen atoms, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, and alkoxycarbonyl groups having 2 to 8 carbon atoms (preferably 2 to 6 carbon atoms, more preferably carbon atoms). Examples include carbon atoms with 2 to 4 carbon atoms, more preferably 2 to 3 carbon atoms, acyl groups with 2 to 10 carbon atoms (e.g., acetyl group, propionyl group, butyryl group, valeryl group, pivaloyl group, acryloyl group, methacryloyl group, benzoyl group, toluyl group, cinnamoyl group, anisoyl group, naphthoyl group, etc.), acyloxy groups with 2 to 10 carbon atoms, and alkenyl groups with 2 to 10 carbon atoms (e.g., vinyl group, 1-propenyl group, allyl group, butenyl group, styryl group, etc.). Examples of substituents in a cyclic alkyl group that may have substituents include linear or branched alkyl groups having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 2-methylbutyl group, 1-methylbutyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, etc.). When an alkyl group has substituents, if there are two or more substituents, each substituent may be the same or different.

[0034] R 21 The optionally substituted alkyl group in is preferably an optionally substituted alkyl group having 1 to 8 carbon atoms, more preferably an optionally substituted alkyl group having 1 to 6 carbon atoms, even more preferably an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 6 carbon atoms with a substituent, and even more preferably an alkyl group having 1 to 2 carbon atoms or an alkyl group having 2 to 6 carbon atoms with a substituent. 21In this, the substituent in the alkyl group, which may have substituents, is preferably a C2-C4 alkoxycarbonyl group, more preferably a C2-C3 alkoxycarbonyl group, and even more preferably a C3 alkoxycarbonyl group. As the C2-C4 alkoxycarbonyl group, a methoxycarbonyl group and an ethoxycarbonyl group are preferred, and an ethoxycarbonyl group is more preferred. 21 More preferably, the group is a methyl group, an ethyl group, a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group, a methoxycarbonylethyl group, or an ethoxycarbonylethyl group, with the methyl group or an ethoxycarbonylmethyl group being particularly preferred.

[0035] In the above general formula (2), R 22a , R 22b , R 23a and R 23b R represents a hydrogen atom or an alkyl group, either identical or different. 22a , R 22b , R 23a and R 23b As the alkyl group in R, an alkyl group having 1 to 4 carbon atoms is preferred. 22a , R 22b , R 23a and R 23b As the alkyl group in, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group or an ethyl group is even more preferred. In one embodiment, R 22a , R 22b , R 23a and R 23b Preferably, the same or different elements represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom, a methyl group, or an ethyl group, even more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0036] In the group represented by general formula (5), R 51 This indicates an alkylene group. Examples of alkylene groups include those with 1 to 10 carbon atoms. 51Examples of alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, and desilene groups. The number of carbon atoms in the alkylene group is preferably 1 to 8, more preferably 2 to 8, even more preferably 4 to 8, and particularly preferably 6 to 8.

[0037] In the group represented by general formula (5), R 55 R indicates a cyano group. 52a , R 52b , R 53a and R 53b As the alkyl group in, an alkyl group having 1 to 4 carbon atoms is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group or an ethyl group is even more preferred. In one embodiment, R 52a , R 52b , R 53a and R 53b Preferably, the same or different elements represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom, a methyl group, or an ethyl group, even more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0038] In the group represented by general formula (5), R 56a , R 56b , R 56c , R 56d and R 56e , and R 57a , R 57b , R 57c , R 57d and R 57e As the alkyl group in this compound, an alkyl group having 1 to 6 carbon atoms is preferred, an alkyl group having 1 to 4 carbon atoms is more preferred, a linear or branched alkyl group having 1 to 4 carbon atoms is even more preferred, and a methyl group, an ethyl group, or a tert-butyl group is even more preferred. In one embodiment, R 56a , R 56b , R 56c , R 56d and R 56e It is preferable that the same or different elements represent a hydrogen atom or a methyl group, and more preferably a hydrogen atom. In one embodiment, R 57a , R 57b , R 57c , R 57d and R 57e It is preferable that R represents the same or different hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In one embodiment, R 57a , R 57c and R 57e It is more preferably the same or different hydrogen atom or a C1-C6 alkyl group, even more preferably a C1-C4 alkyl group, particularly preferably a methyl group, an ethyl group, or a tert-butyl group, and most preferably a methyl group or a tert-butyl group. In one embodiment, R 57a and R 57e R represents a tert-butyl group, 57c It is particularly preferable that R exhibits a methyl group. 57b and R 57d It is particularly preferable that this represents a hydrogen atom.

[0039] In general formula (3), R 31 , R 32a , R 32b , R 33a , R 33b and R 34 As the alkyl group in, an alkyl group having 1 to 4 carbon atoms is preferred, and a linear or branched alkyl group having 1 to 4 carbon atoms is more preferred. In one embodiment, R 31 It is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group, an ethyl group, or an n-propyl group, even more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. 32a , R 32b , R 33a and R 33b It is preferable that the same or different elements represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom, a methyl group, or an ethyl group, even more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom. In one embodiment, R 34It is preferable that the alkyl group has 1 to 3 carbon atoms, more preferably a methyl group, an ethyl group, or an n-propyl group, even more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

[0040] In the above general formula (1), A represents the group shown in the above general formula (4). In general formula (4), R 45 R indicates a cyano group. 46a , R 46b , R 46c , R 46d and R 46e , and R 47a , R 47b , R 47c , R 47d and R 47e As the alkyl group in this compound, alkyl groups having 1 to 6 carbon atoms are preferred, alkyl groups having 1 to 4 carbon atoms are more preferred, linear or branched alkyl groups having 1 to 4 carbon atoms are even more preferred, and methyl groups, ethyl groups, and tert-butyl groups are particularly preferred. In one embodiment, R 46a , R 46b , R 46c , R 46d and R 46e It is preferable that the same or different elements represent a hydrogen atom or a methyl group, and more preferably a hydrogen atom. In one embodiment, R 47a , R 47b , R 47c , R 47d and R 47e It is preferable that R represents the same or different hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In one embodiment, R 47a , R 47c and R 47e It is more preferably the same or different hydrogen atom or a C1-C6 alkyl group, even more preferably a C1-C4 alkyl group, particularly preferably a methyl group, an ethyl group, or a tert-butyl group, and most preferably a methyl group or a tert-butyl group. In one embodiment, R 47a and R47e R represents a tert-butyl group, 47c It is particularly preferable that R exhibits a methyl group. 47b and R 47d It is particularly preferable that this represents a hydrogen atom.

[0041] As an example of a preferred embodiment of compound (1) of the present invention, in general formula (1), D represents general formula (2), and in general formula (2), R 21 R represents an alkyl group having 1 to 6 carbon atoms, which may have substituents, or a group represented by general formula (5). 22a , R 22b , R 23a and R 23b The compounds are preferably the same or different compounds that exhibit a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In another embodiment, it is also preferable that in general formula (1), D represents general formula (3). In general formula (4), R 46a , R 46b , R 46c , R 46d and R 46e R represents a hydrogen atom. 47a , R 47c and R 47e R represents the same or different hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 47b and R 47d Preferably, it represents a hydrogen atom. Examples of such compounds include compounds I to IV prepared in the examples.

[0042] The method for producing compound (1) of the present invention will be described below with an example of a synthesis method, but the method for producing the compound of the present invention is not limited to the method described below. Furthermore, when carrying out the reaction described later, functional groups other than the site in question may be protected in advance with an appropriate protecting group as needed, and then deprotected at an appropriate stage.

[0043] If compound (1) is the compound represented by the following general formula (1A), it can be synthesized, for example, by the following reaction. Compound (1A) is an example of a compound in which D is the group represented by general formula (2) in general formula (1). Compound (1A) can be synthesized by reacting the compound represented by the following general formula (IM1) (compound (IM1)) and the compound represented by general formula (IM2) (compound (IM2)).

[0044] [ka]

[0045] In the above general formula (IM1), R 101 and R 102 R represents, either the same or different, a hydrogen atom, an alkyl group, an aryl group, or an acyl group. In the above formula, R 45 R indicates a cyano group. 101 and R 102 Preferably, these are the same or different hydrogen atoms, phenyl groups, or acetyl groups. In the above formula, R 21 And preferred embodiments thereof are as described above R 21 and the same as the preferred embodiment thereof. 46a , R 46b , R 46c , R 46d , R 46e , R 47a , R 47b , R 47c , R 47d and R 47e Furthermore, these preferred embodiments are as described above R 46a , R 46b , R 46c , R 46d , R 46e , R 47a , R 47b , R 47c , R 47d and R 47e The same applies to each of these preferred embodiments.

[0046] The reaction between compound (IM1) and compound (IM2) is usually carried out in a solvent in the presence of a base. The base is not particularly limited and includes, for example, triethylamine, piperidine, diazabicycloundecene (DBU®), potassium carbonate, sodium hydroxide, sodium methylate, and sodium bicarbonate. The solvent is not particularly limited and can be any solvent that is inert to the reaction. Examples include alcoholic solvents such as methanol, ethanol, propanol, and butanol; aromatic hydrocarbon solvents such as toluene and xylene; and various organic solvents such as acetonitrile, dimethylformamide, tetrahydrofuran, dioxane, dimethyl sulfoxide, acetic acid, acetic anhydride, and methyl ethyl ketone. The reaction temperature can be 0°C to 120°C, with 5°C to 80°C being preferred. The reaction time can be, for example, 0.1 hours to 50 hours, with 0.5 hours to 24 hours being preferred. Compound (IM1) can be synthesized, for example, by the method described in Helvetica Chimica Acta 1987, 70(6), 1583. Compound (IM2) can be synthesized, for example, by the method described in Japanese Patent Application Publication No. 2014-088467.

[0047] If compound (1) is the compound represented by general formula (1A), compound (1A) can also be synthesized by the following reaction. Compound (1A) can be synthesized by reacting the compound represented by the following general formula (IM3) (compound (IM3)) and the compound represented by general formula (IM4) (compound (IM4)).

[0048] [ka]

[0049] In the above general formula (IM4), R 103 and R 104 R represents, either the same or different, a hydrogen atom, an alkyl group, an aryl group, or an acyl group. In the above formula, R 45 R indicates a cyano group. 103 and R 104Preferably, these are the same or different hydrogen atoms, phenyl groups, or acetyl groups. In the above formula, R 21 And preferred embodiments thereof are as described above R 21 and the same as the preferred embodiment thereof. 46a , R 46b , R 46c , R 46d , R 46e , R 47a , R 47b , R 47c , R 47d and R 47e Furthermore, these preferred embodiments are as described above R 46a , R 46b , R 46c , R 46d , R 46e , R 47a , R 47b , R 47c , R 47d and R 47e The same applies to each of these preferred embodiments.

[0050] The reaction between compound (IM3) and compound (IM4) is usually carried out in a solvent in the presence of a base. The base is not particularly limited and includes, for example, triethylamine, piperidine, diazabicycloundecene (DBU), potassium carbonate, sodium hydroxide, sodium methylate, and sodium bicarbonate. The solvent is not particularly limited and can be any solvent that is inert to the reaction. Examples include alcoholic solvents such as methanol, ethanol, propanol, and butanol; aromatic hydrocarbon solvents such as toluene and xylene; and various organic solvents such as acetonitrile, dimethylformamide, tetrahydrofuran, dioxane, dimethyl sulfoxide, acetic acid, acetic anhydride, and methyl ethyl ketone. The reaction temperature can be 0°C to 120°C, with 5°C to 80°C being preferred. The reaction time can be, for example, 0.1 hours to 50 hours, with 0.5 hours to 24 hours being preferred. Compound (IM3) can be synthesized, for example, by the method described in European Journal of Organic Chemistry 2009, (25), 4357. Compound (IM4) can be synthesized, for example, by the method described in Tetrahedron Letters 2008, 49(16), 2631. In the case of a compound in which D in general formula (1) is the group shown in general formula (3), it can also be obtained by either of the above reactions.

[0051] The isolation and purification of each product in the above manufacturing method can be carried out by appropriately combining methods commonly used in organic synthesis, such as filtration, extraction, washing, drying, concentration, crystallization, and various types of chromatography. Furthermore, intermediates can be subjected to the next reaction without any special purification.

[0052] Compound (1) of the present invention typically has an absorption maximum wavelength of 360 to 430 nm. Having an absorption maximum wavelength of 360 to 430 nm allows for selective absorption of ultraviolet and blue light. Compound (1) of the present invention preferably has an absorption maximum wavelength of 370 to 420 nm, and more preferably has an absorption maximum wavelength of 380 to 410 nm. The absorption maximum wavelength can be measured by the method described in the examples.

[0053] Compound (1) of the present invention is preferably a compound that dissolves in the following organic solvents. Examples of organic solvents include aromatic hydrocarbons (e.g., toluene, xylene, etc.), ketones (methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, 3-heptanone, etc.), ethers (e.g., propylene glycol monomethyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, etc.), esters (e.g., methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, ethyl acetate, butyl acetate, methyl 3-methoxypropionate, etc.), and mixtures of two or more of these. Compound (1) is preferably soluble in at least one of the above organic solvents at a concentration of 0.1% by mass or more, for example, preferably soluble at a concentration of 0.1% by mass or more and 50% by mass or less, more preferably soluble at a concentration of 1% by mass or more and 40% by mass or less, and even more preferably soluble at a concentration of 3% by mass or more and 30% by mass or less. More preferably, the solubility in organic solvents at 20°C is within this range. Having solubility in organic solvents within this range is preferable because it results in good manufacturability when using compound (1) of the present invention for, for example, in the manufacture of blue light shielding lenses.

[0054] Compound (1) of the present invention typically has an absorption maximum wavelength of 360-430 nm and can effectively absorb light of this wavelength. Compound (1) of the present invention can effectively absorb light around 400 nm. Compound (1) of the present invention has good light resistance and is less susceptible to changes in the waveform of its absorption spectrum due to ultraviolet light. Compound (1) of the present invention is suitably used, for example, as a blue light shielding material such as blue light shielding lenses; an ultraviolet absorber; and a recording material for recording media. Furthermore, Compound (1) of the present invention is also suitably used as a dye for optical filters such as color filters and color conversion filters.

[0055] Compound (1) of the present invention can be mixed with, for example, a resin to form a dye composition. The dye composition is suitably used as a coloring composition. The above resins are not particularly limited, and thermoplastic resins, photocurable resins, thermosetting resins, etc., can be appropriately selected depending on the application of the colored composition. Examples include acrylic resins, polycarbonate resins, polystyrene resins, low-density polyethylene resins, polypropylene resins, polyurethane resins, polyamide resins, polyacetal resins, polyphenylene sulfide resins, polyethylene terephthalate resins, polybutylene terephthalate resins, polycycloolefin resins, polysulfone resins, polyethersulfone resins, fluororesins, silicone resins, polyester resins, epoxy resins, phenolic resins, and melamine resins. These may be used individually or in combination of two or more.

[0056] The amount of compound (1) in the dye composition is preferably 0.001 to 50% by mass, and more preferably 0.01 to 40% by mass, relative to the total solid content of the dye composition.

[0057] The dye composition may contain optional components other than compound (1) and resin of the present invention, depending on its intended use. Examples of optional components include antioxidants, defoamers, other dyes (dyes, pigments, etc.), infrared absorbers, polymerizable monomers, polymerization initiators, sensitizers, and the like. It may also contain ultraviolet absorbers other than compound (1). The method for producing the pigment composition is not particularly limited; for example, the compound (1) of the present invention and the resin, along with any optional components that may be added, may be mixed.

[0058] Compound (1) of the present invention, and dye compositions containing Compound (1) of the present invention, are suitably used, for example, in the manufacture of blue light shielding materials, ultraviolet absorbers, recording materials, and cosmetics. Blue light shielding materials, ultraviolet absorbers, recording materials, and cosmetics containing compound (1) of the present invention are also included in the present invention. The blue light shielding materials, ultraviolet absorbers, recording materials, and cosmetics only need to contain compound (1), and their composition is not particularly limited. The blue light shielding material is not particularly limited and examples include blue light cut films; blue light blocking lenses such as lenses for blue light blocking eyeglasses or contact lenses. These blue light shielding materials may be blue light shielding molded articles formed by molding a material containing compound (1) of the present invention. As an example of a lens, which is a blue light shielding material, various methods can be employed to manufacture it, such as kneading compound (1) of the present invention into a transparent resin and molding it by injection molding, compression molding, extrusion molding, etc., or forming an optical functional layer containing compound (1) of the present invention on a support described later. UV absorbers can be used in a variety of materials such as glass, plastics, fibers, paper, paints, inks, and cosmetics. UV absorbers can be mixed with various materials, and may be dispersed or dissolved within the materials. Furthermore, UV absorbers may be chemically or physically supported on various materials. Examples of recording materials containing compound (1) of the present invention include optical discs and the like.

[0059] Compound (1) of the present invention, and dyes and dye compositions for optical filters containing Compound (1) of the present invention, are suitably used, for example, in the manufacture of optical filters.

[0060] The optical filter may contain compound (1) of the present invention and may, for example, have a support, similar to conventional filters, and optionally have an optical functional layer. In the optical filter, it is preferable that compound (1) of the present invention is contained in the support or the optical functional layer.

[0061] The composition of the support and the optical functional layer is not particularly limited. For example, the support is usually formed using a transparent resin. Examples of transparent resins include cyclic olefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, polyamide (aramid) resins, polyarylate resins, polysulfone resins, polyethersulfone resins, poly-paraphenylene resins, polyamide-imide resins, polyethylene naphthalate (PEN) resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, and the like.

[0062] The method for manufacturing an optical filter is not particularly limited. For example, as a method for forming an optical functional layer containing compound (1) of the present invention on a support, one method is to dissolve or disperse compound (1) of the present invention and a binder resin, etc., in a solvent, and then form a coating film on the support by a coating method such as dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, spin coating, or extrusion coating. The solvent is not particularly limited, but examples include the organic solvents mentioned above.

[0063] Furthermore, as a method for producing an optical functional layer or support containing compound (1) of the present invention, compound (1) of the present invention may be mixed with a photocurable resin and / or a thermosetting resin and a photopolymerization initiator and / or a thermal polymerization initiator, and then a cured film may be formed by light irradiation and / or heat treatment, which may be used as an optical functional layer or support.

[0064] Optical filters, such as color filters and color conversion filters, can be suitably used in imaging devices, lighting equipment, window glass, and other materials for insect repellent purposes (suppressing the arrival of phototactic flying insects). [Examples]

[0065] The following are examples illustrating the present invention in more detail, but the present invention is not limited to these examples.

[0066] The instruments and measurement conditions used to measure the physical properties of the obtained compounds are as follows: (LC / MS) Shimadzu Corporation High Performance Liquid Chromatograph Mass Spectrometer LCMS-2010EV (ESI method) (NMR) Nuclear magnetic resonance device JNM-ECZ400S manufactured by JEOL Ltd.

[0067] <Example 1> (1) Preparation of compound I-1 The compound represented by the following formula (I-1) (compound I-1) was synthesized by the method described below. In the formula, Ph represents the phenyl group.

[0068] [ka]

[0069] In a reactor equipped with a thermometer and condenser, 5.1 g of 2-methylthiazoline, 7.1 g of methyl iodide, and 20 mL of acetonitrile were charged and reacted at 40°C for 3 hours. 9.8 g of N,N'-diphenylformamidine and 30 mL of isopropyl alcohol were added to the reaction mixture and reacted at 70°C for 3 hours. After cooling to room temperature, 10 mL of isopropyl alcohol was added, the precipitate was filtered off and washed with isopropyl alcohol. The mixture was dried at 80°C to obtain 9.1 g of compound I-1. 1 H NMR(400MHz,DMSO-d6,298K) δ(ppm)=11.29(brs,1H),8.16(d,1H),7.40-7.30(m,4H),7.19-7.12(m,1H),5.85(d,1H),4.18(t,2H),3.47(t,2H),3.25-3.21(m,3H)

[0070] (2) Preparation of Compound I Compound I, represented by the following formula (I), was synthesized from compound I-1. In the formula, t-Bu represents a tert-butyl group.

[0071] [ka]

[0072] In a reactor equipped with a thermometer, 3.5 g of compound I-1, 15 mL of dimethylformamide, and 3.2 g of 2,6-di-tert-butyl-4-methylcyclohexyl 2-cyanoacetate were charged. At 5°C, 1.1 g of acetic anhydride and 1.1 g of triethylamine were added, and the mixture was stirred at room temperature for 2 hours. Water was added, and the precipitated solid was collected by filtration and washed with methanol. After drying at 60°C, 2.0 g of compound I was obtained. 1 H NMR(400MHz,DMSO-d6,298K) δ(ppm)=7.70(d,1H),5.57(s,1H),5.46(d,1H),3.99(t,2H),3.34(t,2H),3 .08(s,3H),1.56-1.41(m,3H),1.25-1.12(m,4H),0.95(d,3H),0.79(s,18H) LC-MS: m / z = 419[M+H] +

[0073] <Example 2> (1) Preparation of compound II-1 The compound represented by the following formula (II-1) (compound II-1) was synthesized by the following method.

[0074] [ka]

[0075] Compound II-1 was prepared using the same procedure as in the preparation of Compound I-1 in Example 1, except that methyl iodide was replaced with ethyl-2-iodoacetate. 1 H NMR(400MHz,DMSO-d6,298K) δ(ppm)=11.52(brs,1H),8.35-8.25(m,1H),7.45-7.38(m,4H),7.24-7.20(m ,1H),5.81(d,1H),4.73(s,2H),4.26-4.18(m,4H),3.55(t,2H),1.25(t,3H)

[0076] (2) Preparation of Compound II

[0077] [ka]

[0078] Compound I (compound II) represented by the above formula (II) was produced by the same procedure as in the production of compound I in Example 1, except that compound I-1 was replaced with compound II-1. 1H NMR(400MHz,DMSO-d6,298K) δppm=7.72(d,1H),5.58(s,1H),5.43(d,1H),4.51(s,2H),4.14(q,2H),4.00(t,2) H),3.36(t,2H),1.42-1.60(m,3H),1.13-1.25(m,7H),0.95(d,3H),0.79(s,18H) MS:m / z=491[M+H] +

[0079] <Example 3> (1) Preparation of compound III-1 The compound represented by the following formula (III-1) (compound III-1) was synthesized by the method described below. In the formula, Ac represents an acetyl group.

[0080] [ka]

[0081] In a reactor equipped with a thermometer and condenser, 14.7 g of 2,6-di-tert-butyl-4-methylcyclohexyl 2-cyanoacetate, 9.8 g of N,N'-diphenylformamidine, and 50 mL of isopropyl alcohol were charged. 1.5 g of diazabicycloundecene (DBU) was added, and the mixture was heated and stirred at 75°C for 6 hours. After cooling to room temperature, the precipitated crystals were filtered off. 15.9 g of the solid obtained by washing with isopropyl alcohol and drying at 70°C was charged into a reactor equipped with a thermometer. 0.5 g of 4-dimethylaminopyridine, 40 mL of toluene, and 4.9 g of acetic anhydride were added, and 4.9 g of triethylamine was added dropwise. After stirring at room temperature for 2 hours, the reaction mixture was washed with water and the organic layer was concentrated. The resulting crude product was crystallized with methanol water, filtered, and dried at 70°C to obtain 13.3 g of compound III-1. 1H NMR(400MHz, CDCl3, 298K) δ(ppm)=9.12(s,1H),7.62-7.56(m,3H),7.32-7.29(m,2H),5.79(s,1H),2.06(s, 3H),1.55-1.36(m,3H),1.27(q,2H),1.20-1.12(m,2H),0.94(d,3H),0.87(s,18H)

[0082] (2) Preparation of compound III-2 The compound represented by the following formula (III-2) (compound III-2) was synthesized by the following method.

[0083] [ka]

[0084] In a reactor equipped with a thermometer, 4.2 g of 2-methylimidazoline, 6.9 g of potassium carbonate, and 25 mL of acetonitrile were charged, and 15.6 g of methyl iodide was added dropwise under a water bath. The mixture was then heated and stirred at 45°C for 18 hours, and the insoluble matter of the reaction mixture was filtered off. The filtrate was concentrated, and the resulting crude product was washed with ethyl acetate and dried at 60°C to obtain 11.6 g of compound III-2.

[0085] (3) Preparation of Compound III Compound III, represented by the following formula (III), was synthesized from compounds III-1 and III-2.

[0086] [ka]

[0087] In a reactor equipped with a thermometer, 3.5 g of compound III-1, 2.9 g of compound III-2, and 12 mL of acetonitrile were charged. 1.5 g of diazabicycloundecene was added dropwise, and the mixture was stirred at room temperature for 18 hours. After the reaction was complete, the precipitated crystals were collected by filtration, washed with acetonitrile, purified by silica gel column chromatography, concentrated, and dried at 80°C to obtain 0.88 g of compound III. 1 H NMR(400MHz, CDCl3, 298K) δ(ppm)=8.09(d,1H),5.71(s,1H),5.01(d,1H),3.56(s,4H),3.09(s,6H),1 .56(brd,2H),1.48-1.33(m,3H),1.12(brd,2H),1.02(d,3H),0.89(s,18H) MS:m / z=416[M+H] +

[0088] <Example 4> (1) Preparation of compound IV-1 The compound represented by the following formula (IV-1) (compound IV-1) was synthesized by the following method.

[0089] [ka]

[0090] Compound IV-1 was obtained by performing the same procedure as in the preparation of compound I-1 in Example 1, except that methyl iodide was replaced with 1,6-diiodohexane and the number of moles was doubled. 1 H NMR(400MHz,DMSO-d6,298K) δ(ppm)=11.26(brs,2H),8.27-8.13(m,2H),7.42-7.31(m,8H),7.15(t,2H),6.04-5.9 2(m,2H),4.22(brt,4H),3.66-3.58(m,4H),3.48(t,4H),1.66(brs,4H),1.34(brs,4H)

[0091] (2) Preparation of Compound IV

[0092] [ka]

[0093] In the preparation of compound I in Example 1, compound I-1 was replaced with compound IV-1, and the number of moles of 2,6-di-tert-butyl-4-methylcyclohexyl 2-cyanoacetate was doubled. The same procedure was followed to obtain the compound represented by formula (IV) above (compound IV). 1 H NMR(400MHz, CDCl3, 298K) δ(ppm)=7.93(d,2H),5.74(s,2H),5.63(d,2H),3.93(t,4H),3.45(t,4H),3.23(t,4H),1.70-1.66 (m,3H),1.59-1.54(m,3H),1.48-1.32(m,10H),1.18-1.13(m,4H),1.04-1.00(m,8H),0.88(s,36H) MS:m / z=892[M+H] +

[0094] <Comparative Example 1> The compound represented by the following formula (V) (compound V) was synthesized by the following method.

[0095] [ka]

[0096] Compound V was obtained by the same procedure as in the preparation of Compound I in Example 1, except that 2,6-di-tert-butyl-4-methylcyclohexyl 2-cyanoacetate was replaced with ethyl cyanoacetate. 1 H NMR(400MHz,CDCl3,298K) δppm=7.90(d,1H),5.63(d,1H),4.22(q,2H),3.90(t,2H),3.24(t,2H),3.09(s,3H),1.30(t,3H) LC-MS: m / z = 239 [M + H] +

[0097] <Comparative Example 2> The compound represented by the following formula (VI) (compound VI) was synthesized by the following method.

[0098] [ka]

[0099] Compound VI was obtained in the same manner as described in Japanese Patent Publication No. 2018-188565.

[0100] The compounds obtained in the examples and comparative examples were evaluated as follows. <Absorption wavelength measurement test> The absorption spectra of the compounds obtained in the examples and comparative examples were measured in chloroform, and the absorption maximum wavelength (λmax) in the 300-800 nm range was determined. Measuring equipment: JASCO Corporation, UV-visible spectrophotometer V-560 The results are shown in Table 1.

[0101] <Measurement of absorption spectra before and after UV irradiation> The compounds obtained in the examples and comparative examples were dissolved in chloroform and placed in a lidded cell, and their absorption spectra at wavelengths of 300-800 nm were measured using the above-mentioned UV-Vis spectrophotometer. At this time, the solution concentration was adjusted so that the absorbance of the absorption maximum was approximately 1.0. The data acquisition interval for the absorption spectrum measurement was set to 1 nm. After measuring the absorption spectrum of the solution before light irradiation, the chloroform solution of the compound was irradiated with light at a wavelength of 365 nm and an irradiation intensity of 460 mW for 10 minutes. For the solution after light irradiation, the absorption spectrum at wavelengths of 300-800 nm was measured using a UV-Vis spectrophotometer with a data acquisition interval of 1 nm.

[0102] Furthermore, the change in absorbance of the compound at wavelengths of 300-500 nm before and after light irradiation was determined from the absorption spectrum. Here, the change in absorbance at 300-500 nm is the sum of the absolute values ​​of the difference in absorbance before and after irradiation at each wavelength (1 nm increment) in the range of 300-500 nm, and was calculated according to the following formula (I). Formula 1

[0103] JPEG2026114053000024.jpg34156

[0104] [However, N is an integer between 300 and 500.] The results are shown in Table 1. A smaller change in absorbance indicates that the waveform of the absorption spectrum is less likely to change due to ultraviolet light.

[0105] <Lightfastness Test> The compounds obtained in the examples and comparative examples were subjected to lightfastness tests. Ten mg of each compound was dissolved in 5 mL of an 8 wt% polymethacrylate toluene solution, and the solution was applied to a glass substrate by spin coating and dried to produce a thin film. The fabricated thin film was continuously irradiated with light from a xenon lamp (142 klux) for 12 hours. The transmittance of the thin film before irradiation (0 hours) and after irradiation was measured using a spectrophotometer, and the remaining percentage of the compound was measured according to the following formula (II). Compound retention rate (%) = {(1-T1) / (1-T0)} × 100 (II) [However, T0 is the transmittance before xenon lamp irradiation, and T1 is the transmittance after xenon lamp irradiation; both T0 and T1 are between 0 and 1.] Note that "transmittance" refers to the transmittance at the absorption maximum wavelength of each compound. The higher the retention rate, the less the compound is decomposed by light, indicating higher light resistance. Lightfastness was evaluated according to the following criteria. A: Compound retention rate of 70% or more B: Compound retention rate is 50% or more, but less than 70%. C: Compound retention rate is less than 50% The results are shown in Table 1.

[0106] [Table 1]

[0107] Compounds I to IV obtained in Examples 1 to 4 exhibited high absorbance around 400 nm and good light resistance. Furthermore, compounds I to IV showed little change in the waveform of their absorption spectra due to ultraviolet light.

Claims

1. A compound represented by the following general formula (1). 【Chemistry 1】 (In general formula (1), D represents the group shown in general formula (2) or general formula (3), and A represents the group shown in general formula (4). 【Chemistry 2】 (In general formula (2), R ２１ R represents an alkyl group which may have substituents or a group represented by general formula (5), ２２ａ , R ２２ｂ , R ２３ａ and R ２３ｂ (The symbols * represent a hydrogen atom or an alkyl group, either identical or different, and * represents a bonding site with a carbon atom in general formula (1).) 【Transformation 3】 (In General Formula (3), R ３１ represents an alkyl group, and R ３２ａ , R ３２ｂ , R ３３ａ and R ３３ｂ are the same or different and each represents a hydrogen atom or an alkyl group, and R ３４ represents an alkyl group, and * indicates the bonding site with the carbon atom in General Formula (1). ) 【Chemistry 4】 (In general formula (4), R ４５ R indicates a cyano group. ４６ａ , R ４６ｂ , R ４６ｃ , R ４６ｄ and R ４６ｅ R represents a hydrogen atom or an alkyl group, either identical or different. ４７ａ , R ４７ｂ , R ４７ｃ , R ４７ｄ and R ４７ｅ (The symbols * represent a hydrogen atom or an alkyl group, either identical or different, and * represents a bonding site with a carbon atom in general formula (1).) 【Transformation 5】 (In general formula (5), R ５１ R indicates an alkylene group. ５２ａ , R ５２ｂ , R ５３ａ and R ５３ｂ R represents a hydrogen atom or an alkyl group, either identical or different. ５５ R indicates a cyano group. ５６ａ , R ５６ｂ , R ５６ｃ , R ５６ｄ and R ５６ｅ R represents a hydrogen atom or an alkyl group, either identical or different. ５７ａ , R ５７ｂ , R ５７ｃ , R ５７ｄ and R ５７ｅ The symbols * represent a hydrogen atom or an alkyl group, either identical or different, and * indicates the bonding site with the nitrogen atom in general formula (2).

2. The compound according to claim 1, wherein D represents the group shown in general formula (2) in general formula (1).

3. In general formula (2), R ２１ R represents an alkyl group having 1 to 6 carbon atoms, which may have substituents. ２２ａ , R ２２ｂ , R ２３ａ and R ２３ｂ The compound according to claim 1 or 2, wherein is the same or different, representing a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

4. In general formula (4), R ４６ａ , R ４６ｂ , R ４６ｃ , R ４６ｄ and R ４６ｅ R represents a hydrogen atom. ４７ａ , R ４７ｃ and R ４７ｅ R represents the same or different hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ４７ｂ and R ４７ｄ The compound according to claim 1 or 2, wherein is a hydrogen atom.

5. In general formula (5), R ５１ This represents an alkylene group having 1 to 8 carbon atoms, R ５２ａ , R ５２ｂ , R ５３ａ and R ５３ｂ R represents a hydrogen atom. ５６ａ , R ５６ｂ , R ５６ｃ , R ５６ｄ and R ５６ｅ R represents a hydrogen atom. ５７ａ , R ５７ｃ and R ５７ｅ R represents the same or different hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ５７ｂ and R ５７ｄ The compound according to claim 1 or 2, wherein is a hydrogen atom.

6. In general formula (3), R ３１ R represents an alkyl group having 1 to 3 carbon atoms. ３２ａ , R ３２ｂ , R ３３ａ and R ３３ｂ R represents the same or different hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ３４ The compound according to claim 1, wherein is an alkyl group having 1 to 3 carbon atoms.

7. A dye composition characterized by comprising the compound described in claim 1 or 2.

8. A blue light shielding molded article characterized by containing the compound described in claim 1 or 2.

9. An ultraviolet absorber characterized by containing the compound described in claim 1 or 2.

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