Compound, method for producing compound, resin composition, film, organic semiconductor material, photovoltaic device, heat ray-absorbing material, phototransistor material, optical filter, solid-state imaging element, infrared camera, image forming material, toner for electrostatic charge image development, and printing ink

Abstract

Provided are a compound having a novel skeleton, a method for producing the same, and various articles comprising the compound. The compound is represented by a formula. R1 to R22 are each a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted vinyl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, an optionally substituted alkoxyl group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulphamoyl; A1 to A4 are each an electron-withdrawing group; X1 to X2 are each a single bond, (=CH)n1−(CH=CH)n2−, or an optionally substituted nitrogen atom; n1 is 0 or 1; and n2 is an integer of 0 to 12.

Description

Compound, method for producing compound, resin composition, film, organic semiconductor material, photovoltaic device, heat ray absorbing material, phototransistor material, optical filter, solid-state imaging element, infrared camera, image forming material, toner for developing electrostatic charge image, and printing ink

[0001] The present disclosure relates to a compound, a method for producing the compound, a resin composition, a film, an organic semiconductor material, a photovoltaic device, a heat ray absorbing material, a phototransistor material, an optical filter, a solid-state imaging element, an infrared camera, an image forming material, a toner for developing electrostatic images, and a printing ink.

[0002] Known dyes that absorb light in the visible to near-infrared region include specific squarylium compounds (e.g., Patent Document 1), specific pyrrolopyrrole compounds (e.g., Patent Document 2), and specific phthalocyanine compounds (e.g., Patent Document 3). Furthermore, compounds with high planarity are being investigated as organic semiconductor materials (e.g., Patent Documents 4 and 5).

[0003] Japanese Patent Application Laid-Open No. 2021-001342 International Publication No. 2020 / 175456 Japanese Patent Application Laid-Open No. 2016-108431 Japanese Patent Application Laid-Open No. 2023-131962 Japanese Patent Application Laid-Open No. 2018-150248

[0004] An object of the present disclosure is to provide a compound having a novel skeleton, a method for producing the same, and a resin composition, a film, an organic semiconductor material, a photovoltaic device, a heat ray absorbing material, a phototransistor material, an optical filter, a solid-state imaging element, an infrared camera, an image forming material, a toner for developing electrostatic images, and a printing ink, each of which contains the compound.

[0005] The compound according to this embodiment is a compound represented by any one of the following formulas (I) to (III). In the formula, R １ ~R ８ , R １１ ~R １４ , and R ２１ ~R ２２each independently represents a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted vinyl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, an optionally substituted alkoxyl group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group; A １ ~A ４ are each independently an electron-withdrawing group, １ ~X ２ are each independently a single bond, (=CH) ｎ１ -(CH=CH) ｎ２ n1 is 0 or 1, n2 is an integer of 0 to 12, n1+n2 is an integer of 1 or more, and n represents the number of repeating units and is an integer of 1 or more.

[0006] In one embodiment of the compound, １ ~A ４ are each independently a group represented by any one of the following formulas (a1) to (a6): In the formula, R ３１ ~R ４９ each independently represents a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted vinyl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, an optionally substituted alkoxyl group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group; * represents X １ or X ２ where A represents the bonding position. ３ ~A ４ In this case, R ３１ ~R ４９ Any one of R２１ or R ２２ or represents the bonding position to the adjacent repeating unit.

[0007] In one embodiment of the compound, １ ~A ２ are each independently a group represented by any one of the following formulas (c1) to (c7): In the formula, R ５０ ~R ６７ each independently represents a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted vinyl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, an optionally substituted alkoxyl group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group; * represents X １ or X ２ represents the bonding position with

[0008] In the method for producing the compound represented by formula (I) according to this embodiment, a compound represented by the following formula (X) is used as a raw material. In the formula, R １ ~R ８ each independently represent a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a vinyl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent.

[0009] In the method for producing the compound represented by any one of formulas (II) to (III) according to this embodiment, the compound represented by formula (I) is used as a raw material.

[0010] The present disclosure further provides a compound represented by formula (X). The present disclosure also provides a resin composition, a film, an organic semiconductor material, a photovoltaic device, a heat ray absorbing material, a phototransistor material, an optical filter, a solid-state imaging device, an infrared camera, an image forming material, a toner for developing electrostatic images, and a printing ink, each of which contains a compound represented by any one of formulas (I) to (III).

[0011] The present disclosure provides a compound having a novel skeleton, a method for producing the compound, and a resin composition, a film, an organic semiconductor material, a photovoltaic device, a heat ray absorbing material, a phototransistor material, an optical filter, a solid-state imaging element, an infrared camera, an image forming material, a toner for developing electrostatic images, and a printing ink, each of which contains the compound.

[0012] 1 is an absorption spectrum of Compound 9. 2 is an absorption spectrum of Compound 13. 3 is an absorption spectrum of Compound 14.

[0013] In this specification, unless otherwise specified, the numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. １ ~R ４ " is written as R １ , R ２ , R ３ and R ４ For example, the notation "Formulas (I) to (III)" includes each of Formulas (I), (II), and (III). The same applies to other symbols. In this specification, a compound represented by Formula (I) may be referred to as "Compound (I)" or the like. The same applies to other compounds, etc. In the examples, each compound may be referred to as Raw Material N, Target Product N, etc. depending on the situation (N indicates the compound number). In addition, when there are multiple identical symbols in a chemical formula, the identical symbols may have the same structure or may have different structures within the specified range.

[0014] [Compound] The compound of the present disclosure is a compound represented by any one of formulas (I) to (III) described below. These compounds have in common a skeleton represented by formula (A) below. The skeleton (A) has the characteristic of selectively absorbing light of a specific wavelength. In particular, by introducing various substituents, the absorption band of light in the visible to near-infrared region can be adjusted. Therefore, compounds (I) to (III) can be used, for example, as dyes (pigments) or infrared absorbing materials. Furthermore, the skeleton (A) has high planarity. Therefore, it can be used as an organic semiconductor material that requires crystallinity.

[0015] <Compound (I)> In the formula, R １ ~R ８ each independently represent a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a vinyl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent.

[0016] The alkyl group in the alkyl group which may have the above-mentioned substituent may be a linear alkyl group or a branched alkyl group. In addition, in this specification, the alkyl group includes not only saturated hydrocarbon groups but also groups in which a portion is an unsaturated bond (a double bond (alkenyl group) or a triple bond (alkynyl group)). The number of carbon atoms in the alkyl group is, for example, 1 to 30, preferably 1 to 24, more preferably 1 to 12, and even more preferably 1 to 8. Specific examples of the alkyl group include linear alkyl groups such as methyl, ethyl, hexyl, dodecyl, and eicosyl groups; branched alkyl groups such as 2-ethylhexyl groups; alkenyl groups such as ethenyl and dodecene groups; and alkynyl groups such as prop-2-yn-1- and propargyl groups.

[0017] Examples of the substituent that the alkyl group may have include a halogen atom, an alkoxy group, a cyano group, a nitro group, a hydroxyl group, a carbamoyl group, an N-substituted carbamoyl group, a sulfamoyl group, an N-substituted sulfamoyl group, a carboxyl group, a sulfo group, an amino group, a phenyl group, and a sulfanyl group. Examples of the alkyl group that the alkoxy group has as a substituent include the same as the alkyl group that may have the substituent described above. Examples of the substituent in the N-substituted carbamoyl group and the N-substituted sulfamoyl group include the same as the alkyl group that may have the substituent described above.

[0018] Examples of the aryl group in the aryl group which may have a substituent include a phenyl group, a naphthyl group, an anthracenyl group, etc. Examples of the substituent which the aryl group may have include the substituent which the alkyl group may have and an alkyl group which may have a substituent. Examples of the alkyl group which may have a substituent include the same as the alkyl group which may have a substituent.

[0019] Examples of the substituent in the optionally substituted vinyl group include the substituents that the aryl group may have, as well as the same substituents as the heterocyclic group that may have a substituent, which will be described later.

[0020] Examples of the cycloalkyl group in the cycloalkyl group which may have a substituent include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc. Examples of the substituent which the cycloalkyl group may have include the same substituents as those which the aryl group may have.

[0021] Examples of the heterocyclic group in the heterocyclic group which may have a substituent include a cyclopentyl group and a cyclohexyl group. Examples include furan, thiophene, pyrrole, oxazole, thiazole, imidazole, pyrazole, pyran, pyrone, pyridine, pyrone, pyridazine, pyrimidine, pyrazine, benzofuran, thionaphthene, indole, carbazole, coumarin, quinoline, phthalazine, and quinoxaline. Examples of the substituent which the heterocyclic group may have include the same as the substituent which the aryl group may have.

[0022] The alkyl group moiety of the alkoxyl group which may have a substituent may be the same as the alkyl group which may have a substituent described above. The aryl group moiety of the aryloxy group which may have a substituent may be the same as the aryl group which may have a substituent described above.

[0023] The alkyl group moiety of the optionally substituted alkylthio group may be the same as the alkyl group described above, which may have a substituent. The aryl group moiety of the optionally substituted arylthio group may be the same as the aryl group described above, which may have a substituent.

[0024] Examples of the substituent in the optionally substituted phthalimidomethyl group include the same substituents as those which the above-mentioned aryl group may have, and examples of the substituent in the optionally substituted sulfamoyl group include the same substituents as those which the above-mentioned aryl group may have.

[0025] R １ ~R ４ are each independently preferably a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a vinyl group which may have a substituent, a cycloalkyl group which may have a substituent, or a heterocyclic group which may have a substituent, and among these, a hydrogen atom, an alkyl group which may have a halogen atom or an aryl group as a substituent, an aryl group which may have a halogen atom or an alkyl group as a substituent, a vinyl group which may have an alkyl group, aryl group, or heterocyclic group as a substituent, a cycloalkyl group which may have a halogen atom or an alkyl group as a substituent, or a heterocyclic group which may have a halogen atom or an alkyl group as a substituent is preferred. １ ~R ４ Specific examples of the above include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, a hexadecyl group, a 2-ethylhexyl group, a cyclopropyl group, a 4-methoxyphenyl group, a 4-chlorophenyl group, a 5-methyl-2-furyl group, a 2-thienyl group, PhCH═CH—, Ph-C≡C—, thienyl-C≡C—, and a 4-hexyl-phenyl group (wherein Ph is a phenyl group).

[0026] R ５ ~R ６ R each independently includes a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, etc. Among these, a hydrogen atom, an alkyl group which may have a halogen atom or an aryl group as a substituent, an aryl group which may have a halogen atom or an alkyl group as a substituent, or a heterocyclic group which may have a substituent is preferred. ５ ~R ６ Specific examples of include a hydrogen atom, a halogen atom, a methyl group, a substituted ethenyl group, and a formyl group, and examples of the substituted ethenyl group include a group represented by the following formula (b1) (2-ethylidenemalononitrile), a group represented by the following formula (b2) (3-ethyl-5-methylene-2-thioxothiazolidin-4-one), and a group represented by the following formula (b3) (3-ethyl-5-methylene-2-thioxothiazolidin-4-one), etc. Here, Et is an ethyl group.

[0027] R ７ ~R ８ R are each independently preferably a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, or a cycloalkyl group which may have a substituent, and among these, a hydrogen atom, an alkyl group which may have a halogen atom or an aryl group as a substituent, or an aryl group which may have a halogen atom or an alkyl group as a substituent is preferred. ７ ~R ８ Specific examples of the group include a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 2 to 20 carbon atoms (such as a 2-ethylhexyl group), and a tert-butoxycarbonyl group.

[0028] The compound (I) can be suitably used as an organic semiconductor material or a dye, and can also be suitably used as a raw material for the compounds (II) to (III) described below.

[0029] Specific examples of compound (I) include compounds represented by the following formulae (I-1) to (I-3). The symbols in the formula are as described above.

[0030] <Compound (II)> In the formula, R １ ~R ８ each independently represents a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted vinyl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, an optionally substituted alkoxyl group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group; A １ ~A ２ are each independently an electron-withdrawing group, １ ~X ２ are each independently a single bond, (=CH) ｎ１ -(CH=CH) ｎ２ - or a nitrogen atom which may have a substituent.

[0031] R in formula (II) １ ~R ８ is R in the formula (I). １ ~R ８ The same applies to the preferred embodiments.

[0032] The electron-withdrawing group in the present disclosure refers to a substituent that more easily attracts electrons from the atom to which it is bonded compared to a hydrogen atom. Examples of electron-withdrawing groups include those having a Hammett substituent constant (σp-) that is positive, preferably 0.01 or greater. Examples of electron-withdrawing groups include a cyano group, a nitro group, a halogeno group, a nitrogen-containing heterocycle that may have a substituent, and groups containing these. The nitrogen-containing heterocycle as the electron-withdrawing group is sufficient as long as it has at least one nitrogen atom in the ring structure, and may further have other heteroatoms such as O, S, or Si, or may have other substituents. Furthermore, the nitrogen-containing heterocycle may or may not have aromaticity.

[0033] A １ ~A ２ is preferably a group selected from the following formulae (a1) to (a6) and (c1) to (c7). In the formula, R ３１ ~R ４９ each independently represents a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted vinyl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, an optionally substituted alkoxyl group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group; * represents X １ or X ２ represents the bonding position with

[0034] In the formula, R ５０ ~R ６７each independently represents a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted vinyl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, an optionally substituted alkoxyl group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group; * represents X １ or X ２ represents the bonding position with

[0035] R ３１ ~R ４９ and R ５０ ~R ６７ Each substituent in the formula (I) １ ~R ８ Examples include the same as above. ３１ ~R ４９ and R ５０ ~R ６７ Specific examples of include a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 12 carbon atoms, and a phenyl group which may have a substituent.

[0036] A １ and A ２ may be the same or different. From the viewpoint of ease of synthesis, A １ and A ２ It is preferable that A are the same, but by combining two or more raw materials in the manufacturing method described below, １ and A ２ It is also possible to synthesize different compounds.

[0037] X １ ~X ２ are each independently a single bond, (=CH) ｎ１ -(CH=CH) ｎ２ n1 is 0 or 1, n2 is an integer of 0 to 12, and n1+n2 is an integer of 1 or more.

[0038] X １ ~X２ When X is a single bond, the skeleton (A) and the electron-withdrawing group are directly bonded. １ ~X ２ (=CH) ｎ１ -(CH=CH) ｎ２ - When n1 is 0, X １ ~X ２ When n1 is 1, the end on the skeleton (A) side is a single bond, and the end on the electron-withdrawing group side is a double bond. １ ~X ２ When X is bonded to a carbon atom having a π bond (for example, when it is bonded to the electron-withdrawing groups of the formulae (a1) to (a4) and (c4)), the end is preferably a single bond (i.e., n1=0). １ ~X ２ When X is bonded to a carbon atom not having a π bond (for example, when it is bonded to the electron-withdrawing groups of the formulae (a5) to (a6), (c1) to (c3), and (c5) to (c7)), the terminal may be a single bond or a double bond, but a double bond (i.e., n1=1) is preferred. １ ~X ２ When the nitrogen atom has a substituent, X １ ~X ２ In addition, when the nitrogen atom does not have a substituent, the end on the skeleton (A) side is a single bond, and the end on the electron-withdrawing group side is a double bond. Examples of the substituent that the nitrogen atom may have include R ７ ~R ８ The same applies to preferred embodiments. When n1 is 0, n2 may be 1 to 12, preferably 1 to 6, and more preferably 1 to 4. When n1 is 1, n2 may be 0 to 12, preferably 0 to 6, and more preferably 0 to 4.

[0039] Specific examples of the compound (II) include compounds represented by the following formulas (II-1) to (II-6). The symbols in the formula are as described above.

[0040] <Compound (III)> In the formula, R １ ~R ４ , R １１ ~R １４ , and R ２１ ~R ２２ each independently represents a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted vinyl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, an optionally substituted alkoxyl group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group; A ３ ~A ４ are each independently an electron-withdrawing group, １ ~X ２ are each independently a single bond, (=CH) ｎ１ -(CH=CH) ｎ２ n1 is 0 or 1, n2 is an integer of 0 to 12, n1+n2 is an integer of 1 or more, and n represents the number of repeating units and is an integer of 1 or more.

[0041] R in formula (III) １ ~R ４ is R in the formula (I). １ ~R ４ The same applies to the preferred embodiments.

[0042] R １１ ~R １４ Each substituent in the formula (I) １ ~R ８ Examples include the same as above. １１ ~R １４ Specific examples of the alkyl group include a linear alkyl group having 1 to 12 carbon atoms and a phenyl group which may have a substituent.

[0043] R ２１ ~R ２２ Each substituent in the formula (I) １ ~R ８Examples include the same as above. ２１ ~R ２２ Specific examples of R include a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 12 carbon atoms, and a phenyl group which may have a substituent. ２１ ~R ２２ represents X in formula (II). １ -A １ The structure may be as follows. １ is preferably a group selected from the formulae (c1) to (c7).

[0044] A ３ ~A ４ As the electron-withdrawing group in １ ~A ２ The nitrogen-containing heterocycles represented by the formulae (a1) to (a6) are preferred, and the groups represented by the formulae (a1) to (a6) are preferred, provided that any of the nitrogen atoms in the nitrogen-containing heterocycle is bonded to the boron atom in formula (III).

[0045] X １ ~X ２ is X in the formula (II). １ ~X ２ The same applies to the preferred embodiments.

[0046] In formula (III), n represents the number of repeating units, and may be 1 or greater than 2. When n is greater than 2, n is preferably from 2 to 50, and more preferably from 2 to 30.

[0047] Specific examples of the compound (III) include compounds represented by the following formulae (III-1) to (III-5). The symbols in the formula are as described above.

[0048] [Method for Producing Compound (I)] The method for producing compound (I) is not particularly limited, but an example thereof may be a production method using the following compound (X) as a raw material. In the formula, R １ ~R ８each independently represent a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a vinyl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent.

[0049] For example, compound (I) can be obtained by adding a Bronsted acid such as p-toluenesulfonic acid to a solution in which compound (X) is dissolved or dispersed. For more specific reaction conditions, see the examples described below. Compound (X) is a novel compound. Next, an example of a method for producing compound (X) will be described.

[0050] [Method for Producing Compound (X)] Compound (X) can be produced, for example, according to Scheme 1 below using compound (XI) below as a starting material. However, R ａ is R of compound (X). ５ and R ６ is a substituent corresponding to ｂ is R of compound (X). ７ and R ８ or a protecting group corresponding to R ｃ is R of compound (X). １ ~R ４ is a substituent corresponding to

[0051] Compounds (XI) and (XII) are commercially available. Compound (XIV) can be prepared by the reaction of the desired R ｃ A commercially available product having X-R ｃ (X is a halogen atom) may be prepared and substituted with lithium when used. For more specific reaction conditions, see the examples described below.

[0052] [Method for producing compounds (II) and (III)] Next, the method for producing compounds (II) and (III) will be described. The method for producing compounds (II) and (III) is not particularly limited, but for example, compound (II) can be produced from compound (I) as a starting material according to the following scheme 2. However, R ｂ is R of compound (X). ７ and R ８ or a protecting group corresponding to R ｄ and R ｅ are substituents capable of reacting with each other, ａ is A of compound (II). １ and A ２ is a substituent corresponding to

[0053] The synthesis of compound (XV) can be carried out by adding a protecting group R ｂ , reactive group R ｄ The reactive group R ｄ , protecting group R ｂ may be introduced in this order, and R ５ and R ６ Just R ｂ It may also be written as: R ｄ and R ｅ An example of the combination is a combination where one is a halogen atom and the other is dioxaborolane. For more specific reaction conditions, see the examples described below.

[0054] Compound (III) can be produced from compound (II) according to the following scheme 3. However, R ｆ is R of compound (III). １１ ~R １４ A is a substituent corresponding to １ and A ２ is A of compound (III). ３ R ２１ and A ４ R ２２ It should be noted that specific reaction conditions can be seen from the examples described below.

[0055] [Uses of Compounds (I) to (III)] As described above, compounds (I) to (III) have the characteristic of selectively absorbing light of specific wavelengths, allowing for the adjustment of the light absorption band in the visible to near-infrared region. Furthermore, compounds (I) to (III) have high planarity. Due to these properties, compounds (I) to (III) can be suitably used, for example, as dyes (pigments), infrared absorbing materials, organic semiconductor materials, and the like. More specific examples include organic semiconductor materials, photovoltaic devices, heat ray absorbing materials, phototransistor materials, optical filters, solid-state imaging devices, infrared cameras, image forming materials, toners for developing electrostatic images, and printing inks. Compounds (I) to (III) may also be mixed with a resin to prepare a resin composition, which may then be used to form a coating film. In these articles, components other than compounds (I) to (III) can be appropriately selected from conventionally known components.

[0056] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. In the following examples, "Ar" represents an n-hexylphenyl group.

[0057] Synthesis Example 1: Synthesis of Compound 2 Compound 2 was synthesized as follows.

[0058] Dimethyl 2,5-Dibromoterephthalate (1) (3.21 g, 9.12 mmol), N-Boc-pyrrole-2-boronic acid (4.80 g, 22.7 mmol), Pd(PPh3)4 (1.05 g, 0.908 mmol), Na2CO3 (5.80 g, 54.7 mmol), and tetrahydrofuran (12 mL) were added to a 200 mL round-bottom flask. The reaction solution was purged with nitrogen and heated at reflux overnight. After cooling to room temperature, the THF was removed under reduced pressure using an evaporator. After extraction with chloroform three times, the organic layer was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The product was isolated by silica column chromatography (chloroform:hexane = 5:1 to 1:0). After concentration, the precipitated solid was washed with hexane and dried to obtain 4.04 g of target compound 2 as a white solid (85% yield). In the formula, Boc represents -COOC(CH ３ ) ３ is.

[0059] NMR of Compound 2 1 H NMR (400 MHz, CDCl3) δ 7.40 (q, J = 3.2, 2.0 Hz, 2H), 7.26 (s, 2H), 6.27 (t, J = 3.2 Hz, 2H), 6.18 (q, J = 3.2, 1.6 Hz, 2H), 3.74 (s, 6H), 1.35 (s, 18H).

[0060] Synthesis Example 2: Synthesis of Compound 3 Compound 3 was synthesized as follows. p-Bromohexylbenzene (20.8 g, 86.2 mmol) was added to a 500 mL three-neck flask and the atmosphere was purged with nitrogen. After adding anhydrous tetrahydrofuran (130 mL), the mixture was cooled to −78°C using a dry ice / acetone bath. n-BuLi (2.69 M, 30 mL, 81 mmol) was slowly added dropwise, followed by stirring at −78°C for 1 hour. A solution of starting material 2 (3.00 g, 5.72 mmol) in anhydrous tetrahydrofuran (120 mL) was slowly added dropwise to the reaction solution, followed by stirring at −78°C for 1 hour, then warming to room temperature and stirring for 2 hours. The reaction was quenched by adding 100 mL of aqueous ammonium chloride, and the tetrahydrofuran was removed under reduced pressure using an evaporator. Hexane was added, followed by ultrasonic irradiation, and the precipitated solid was collected by filtration using a Kiriyama funnel. The residue was washed with hexane and water and then dried to obtain 4.38 g of target product 3 (yield 84%).

[0061] NMR of Compound 3 1 H-NMR (400 MHz, CDCl3) δ 8.23 ​​(brs, 2H), 7.13 (d, J = 8.4 Hz, 8H), 7.09 (d, J = 8.8 Hz, 8H), 6.84 (s, 2H), 6.41-6.40 (m, 2H), 5.94-5.93 (m, 2H), 5.64-5.62 (m, 2H), 3.67 (s, 2H), 2.59 (t, J = 7.6 Hz, 8H), 1.60-1.57 (m, 8H), 1.31-1.27 (m, 24H), 0.88 (t, J = 7.2 Hz, 12H).

[0062] Synthesis Example 3-1: Synthesis of Compound 4 Compound 4 was synthesized as follows. Starting material 3 (457 mg, 0.503 mmol) was placed in a 50 mL two-neck flask and the atmosphere was purged with nitrogen. Anhydrous dichloromethane (10 mL) and anhydrous acetonitrile (10 mL) were added and dispersed ultrasonically. Then, p-toluenesulfonic acid monohydrate (205 mg, 1.08 mmol) was quickly added while stirring, and the mixture was stirred at room temperature for 15 minutes. The reaction solution was transferred to aqueous sodium bicarbonate (50 mL) and extracted three times with chloroform. The organic layer was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting solid was separated by silica column chromatography (developing solvent: chloroform:hexane = 1:1) to obtain 416 mg of target compound 4 as a white solid (yield: 95%).

[0063] Synthesis Example 3-2: Synthesis of Compound 4 Starting material 3 (457 mg, 0.503 mmol) was added to a 50 mL two-neck flask, and acetic acid (10 mL) and concentrated hydrochloric acid (2 mL) were added, followed by stirring for 15 minutes at 80° C. 20 mL of pure water was added to the reaction solution, and the precipitate was filtered and washed with methanol to obtain 416 mg of target compound 4 (yield 95%).

[0064] NMR of Compound 4 1 H-NMR (400 MHz, CDCl3) δ 8.15 (brs, 2H), 7.27 (s, 2H), 7.21 (d, J = 8.4 Hz, 8H), 7.01 (d, J = 8.2 Hz, 8H), 6.79 (t, J = 2.5 Hz, 2H), 6.21 (dd, J = 3.2, 2.0 Hz, 2H), 2.53 (t, J = 7.8 Hz, 8H), 1.59-1.55 (m, 8H), 1.31-1.28 (m, 24H), 0.86 (t, J = 6.9 Hz, 12H).

[0065] Synthesis Example 4: Synthesis of Compound 5 Compound 5 was synthesized as follows. In a 100 mL two-neck flask, starting material 4 (416 mg, 0.476 mmol) was added and dissolved in anhydrous dichloromethane (20 mL). The mixture was then cooled to 0 °C. A solution of di-tert-butyl dicarbonate (300 mg, 1.39 mmol) in anhydrous dichloromethane (5 mL) was slowly added. 4-dimethylaminopyridine (8 mg, 0.065 mmol) was then quickly added, and the mixture was stirred overnight at room temperature under a nitrogen atmosphere. The reaction solution was concentrated under reduced pressure using an evaporator and purified by silica column chromatography (eluent: chloroform:hexane = 1:2) to obtain 432 mg of target product 5 as a white solid (yield 85%).

[0066] NMR of Compound 5 1 H-NMR (400 MHz, CDCl3) δ 8.15 (s, 2H), 7.22-7.20 (m, 10H), 7.02 (d, J = 8.2 Hz, 8H), 6.22 (d, J = 3.2 Hz, 2H), 2.53 (t, J = 7.8 Hz, 8H), 1.60-157 (m, 24H), 1.31-1.27 (m, 24H), 0.86 (t, J = 6.4 Hz, 12H).

[0067] Synthesis Example 5: Synthesis of Compound 6 Compound 6 was synthesized as follows. Starting material 5 (0.253 mg, 0.236 mmol) was added to a 50 mL two-neck flask. After purging with nitrogen, anhydrous tetrahydrofuran (20 mL) was added to dissolve the material and cooled to −78°C. LDA (1.0 M, 2.3 mL, 2.3 mmol) was slowly added dropwise, followed by stirring at −78°C for 30 minutes. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.52 mL, 2.6 mmol) was then slowly added dropwise, followed by stirring at −78°C for 30 minutes. The mixture was then stirred in an ice bath for 30 minutes, returned to room temperature, and stirred for an additional 5 minutes. Water was added to quench the reaction, and the mixture was extracted three times with diethyl ether. The organic layer was dried over magnesium sulfate, filtered, and concentrated. The residue was purified by silica column chromatography (eluent: chloroform:hexane=2:1) ​​to obtain 277 mg (yield 84%) of target compound 6 as a pale yellow-green solid. Note that Bpin in the formula is 4,4,5,5-tetramethyl-3,2-dioxaborolanyl.

[0068] NMR of Compound 6 1 H-NMR (400 MHz, CDCl3) δ 7.94 (s, 2H), 7.16 (d, J = 8.2 Hz, 8H), 6.96 (d, J = 8.2 Hz, 8H), 6.67 (s, 2H), 2.50 (t, J = 7.6 Hz, 8H), 1.53-1.49 (m, 24H), 1.29-1.26 (m, 48H), 0.85 (t, J = 6.8 Hz, 12H)

[0069] Synthesis Example 6: Synthesis of Compound 7 Compound 7 was synthesized as follows. Starting material 6 (100 mg, 68.6 μmol), 7-bromo-2,1,3-benzothiadiazole-4-carboxaldehyde (67 mg, 0.28 mmol), [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride dichloromethane adduct (6 mg, 7 μmol), and potassium carbonate (30 mg, 0.22 mmol) were added to a screw tube. 1,4-Dioxane (3 mL) and water (1 mL) were added, and the reaction solution was bubbled with argon gas for 3 minutes. The reaction solution was heated and stirred at 100 °C overnight, then cooled to room temperature and water was added. The mixture was extracted three times with chloroform, and the organic layer was removed, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting solid was purified by silica column chromatography (eluent: chloroform:hexane = 3:1 to 5:1). The purple and blue bands were collected and concentrated under reduced pressure. The resulting mixture was heated under Kugelrohr at 185-190°C under reduced pressure (2 Torr) for 90 minutes. After further purification by silica column chromatography (chloroform:hexane = 3:1 to 5:1), the product was reprecipitated with diethyl ether / methanol. The precipitated solid was collected by filtration using a Kiriyama funnel, washed with methanol, and dried to obtain 34.2 mg (42% yield) of target compound 7 as a blue solid.

[0070] NMR of Compound 7 1 H-NMR (400 MHz, CDCl3) δ 11.30 (s, 2H), 10.58 (s, 2H), 8.14 (d, J = 7.8 Hz, 2H), 7.83 (d, J = 7.8 Hz, 2H), 7.59 (s, 2H), 7.31 (d, J = 8.2 Hz, 8H), 7.12-7.09 (m, 10H), 2.57 (t, J = 7.8 Hz, 8H), 1.63-1.56 (m, 8H), 1.35-1.26 (m, 24H), 0.86 (t, J = 6.8 Hz, 12H).

[0071] Synthesis Example 7: Synthesis of Compound 8 Compound 8 was synthesized as follows. Starting material 7 (20.5 mg, 17.1 μmol), 3-ethylrhodanine (30.1 mg, 0.187 mmol), and anhydrous chloroform (3 mL) were added to a screw tube. Two drops of piperidine were added using a Pasteur pipette, followed by nitrogen substitution and heating and stirring at 65 °C for 16 hours. After cooling to room temperature, the reaction solution was poured into methanol (50 mL), and the precipitated solid was collected by filtration using a Kiriyama funnel. The residue was then washed with methanol, dried, and purified by silica column chromatography (eluent: chloroform) to obtain the target compound 8 as a dark green solid in a yield of 23.8 mg (94%).

[0072] NMR of Compound 8 1 H-NMR (400 MHz, CDCl3) δ 11.21 (s, 2H), 8.47 (s, 2H), 7.81 (d, J = 8.0 Hz, 2H), 7.64 (d, J = 7.6 Hz, 2H), 7.56 (s, 2H), 7.31 (d, J = 8.4 Hz, 8H), 7.11 (d, J = 8.0 Hz, 8H), 7.04 (d, J = 1.2 Hz, 2H), 4.23 (q, J = 7.2 Hz, 4H), 2.57 (t, J = 8.0 Hz, 8H), 1.64-1.59(m, 8H), 1.35-1.26 (m, 30H), 0.86 (t, J = 7.2 Hz, 12H).

[0073] Synthesis Example 8: Synthesis of Compound 9 Compound 9 was synthesized as follows. In a nitrogen-purged glove box, starting material 8 (23.8 mg, 16.0 μmol), triphddenylborane (103 mg), and dehydrated toluene (3 mL) were added to a screw cap. The mixture was then heated and stirred at 160 °C for 2 days. After returning to room temperature, triphenylborane (203 mg) was added, and the mixture was again heated and stirred at 160 °C for 3 days. After returning to room temperature and removing the screw cap from the glove box, the fraction containing the target product was separated and isolated using silica column chromatography (chloroform:hexane = 1:1 to 2:1). After concentration, the product was isolated and purified using gel permeation column chromatography (developing solvent: chloroform) with a recycling function. Subsequently, reprecipitation was performed using chloroform / hexane, and the precipitate was collected by filtration using a Kiriyama funnel. The residue was washed with hexane and diethyl ether and dried to obtain 16.9 mg (58% yield) of the target product as a black solid.

[0074] NMR of Compound 9 1 H-NMR (400 MHz, CDCl3) δ 8.24 (s, 2H), 7.61 (d, J = 8.4 Hz, 2H), 7.49 (d, J = 8.4 Hz, 2H), 7.27-7.25 (m, 8H (predicted), overlapped with peaks originating from CHCl3), 7.05-7.03 (m, 14H), 6.93 (d, J = 8.4 Hz, 8H), 6.81 (d, J = 7.6 Hz, 8H), 6.62 (s, 2H), 4.20 (q, J = 7.0 Hz, 4H), 2.58 (t, J = 7.8 Hz, 8H), 1.69-1.61 (m, 8H), 1.42-1.27 (m, 30H), 0.91 (t, J = 7.2 Hz, 12H).

[0075] Synthesis Example 9: Synthesis of Compound 10 Compound 10 was synthesized as follows. Starting material 4 (88 mg, 0.10 mmol) was placed in a 50 mL two-neck flask, dissolved in anhydrous dichloromethane, and cooled to 0 °C. A separately prepared solution of phosphoryl chloride (0.20 mL) and N,N-dimethylformamide (0.30 mL) in anhydrous dichloromethane (10 mL) was slowly added dropwise. The mixture was stirred in an ice bath for 90 minutes and then stirred overnight at room temperature. The reaction solution was cooled in an ice bath, 10 mL of 5 M aqueous sodium acetate was added, and the mixture was stirred at room temperature for one day. After the reaction, the mixture was extracted five times with chloroform, and the organic layer was dried over magnesium sulfate and filtered. The target product was extracted from the residue with warmed tetrahydrofuran and mixed with the chloroform solution. These solutions were concentrated under reduced pressure, reprecipitated with chloroform / hexane, and the precipitated solid was collected by filtration. The residue was further washed with hexane and methanol and dried to obtain 84 mg of target product 10 (yield 90%).

[0076] NMR of Compound 10 1 H-NMR (400 MHz, CDCl3) δ 9.46 (brs, 2H), 9.40 (s, 2H), 7.51 (s, 2H), 7.16 (d, J = 8.0 Hz, 8H), 7.04 (d, J = 8.4 Hz, 8H), 6.88 (d, J = 1.6 Hz, 2H), 2.54 (t, J = 8.0 Hz, 8H), 1.62-1.52 (m, 8H (predicted), overlapped with peaks originating from water), 1.34-1.24 (m, 24H), 0.85 (t, J = 6.8 Hz, 12H).

[0077] Synthesis Example 10: Synthesis of Compound 11 Compound 11 was synthesized as follows. NaH (60 wt% in mineral oil, 52 mg, 1.3 mmol) was placed in a 20 mL two-neck flask and the atmosphere was replaced with nitrogen. In an ice bath, anhydrous N,N-dimethylformamide (3 mL) was added, followed by the rapid addition of starting material 10 (93 mg, 0.10 mmol). Subsequently, iodomethane (0.10 mL, 1.6 mmol) was added to the dispersion, followed by stirring in an ice bath for 1 hour. The mixture was then warmed to room temperature and stirred for 1 day. Water was then slowly added to quench the reaction. The precipitated solid was filtered, washed with water and then methanol, and dried to obtain 94 mg of target compound 11 as a yellow solid (yield: 98%).

[0078] NMR of Compound 11 1 H-NMR (400 MHz, CDCl3) δ 9.44 (s, 2H), 7.59 (s, 2H), 7.17 (d, J = 8.0 Hz, 8H), 7.06 (d, J = 8.4 Hz, 8H), 6.80 (s, 2H), 4.18 (s, 6H), 2.55 (t, J = 8.0 Hz, 8H), 1.60-1.53 ​​(m, 8H (predicted), overlapped with peaks originating from water), 1.34-1.26 (m, 24H), 0.87 (t, J = 6.8 Hz, 12H).

[0079] Synthesis Example 11: Synthesis of Compound 12 Compound 12 was synthesized as follows. NaH (60 wt% in mineral oil, 20 mg, 0.50 mmol) was placed in a 20 mL two-neck flask and the atmosphere was replaced with nitrogen. In an ice bath, anhydrous N,N-dimethylformamide (3 mL) was added, followed by the rapid addition of starting material 10 (40 mg, 43 mmol). Subsequently, 1-bromooctane (0.10 mL, 0.57 mmol) was added to the dispersion, and the mixture was allowed to warm to room temperature over 1 hour with stirring. After stirring at room temperature for another 1 hour, water was added to quench the reaction. After extraction with chloroform three times, the organic layer was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica column chromatography (developing solvent: chloroform:hexane = 2:1 to 3:1) to obtain 46 mg of target compound 12 as a yellow-brown solid (yield: 93%).

[0080] Synthesis Example 12: Synthesis of Compound 12 Compound 12 was synthesized as follows. A 200 mL flask was charged with starting material 10 (5.11 g, 5.5 mmol), N,N-dimethylformamide (100 mL), and potassium carbonate (4.56 g, 33 mmol), followed by stirring at room temperature for 5 minutes. Subsequently, 1-iodooctane (2.91 g, 12.1 mmol) was added, followed by stirring at 90°C for 4 hours. After cooling to room temperature, the reaction solution was quenched by adding ice water. The precipitate was collected by suction filtration and washed with methanol, yielding 6.06 g (95% yield) of target product 12 as a yellow-brown solid.

[0081] NMR of Compound 12 1H-NMR (400 MHz, CDCl3) δ 9.43 (s, 2H), 7.53 (s, 2H), 7.16 (d, J = 8.4 Hz, 8H), 7.05 (d, J = 8.8 Hz, 8H), 6.81 (s, 2H), 4.55 (t, J = 8.0 Hz, 4H), 2.55 (t, J = 8.0 Hz, 8H), 1.81-1.74 (m, 4H), 1.61-1.74 (m, 8H (predicted), overlapped with peaks originating from water), 1.34-1.19 (m, 44H), 0.88-0.82 (m, 18H).

[0082] Synthesis Example 13: Synthesis of Compound 13 Compound 13 was synthesized as follows. Starting material 12 (23.2 mg, 20.0 μmol), 3-ethylrhodanine (32.2 mg, 0.200 mmol), and anhydrous chloroform (3 mL) were added to a screw tube. Piperidine (0.10 mL, 1.0 mmol) was added dropwise, and the mixture was purged with nitrogen and heated and stirred at 65°C for 14 hours. The reaction solution was poured into methanol (50 mL), and the precipitated solid was collected by filtration using a Kiriyama funnel. The residue was washed with methanol, dried, and purified by silica column chromatography (chloroform:hexane = 1:1 to 3:2). After concentration, the product was purified by gel permeation column chromatography (eluent: chloroform) equipped with a recycling function to obtain 17.7 mg (62% yield) of target compound 13 as a blue solid.

[0083] NMR of Compound 13 1H-NMR (400 MHz, CDCl3) δ 7.56 (s, 2H), 7.45 (s, 2H), 7.15 (d, J = 8.4 Hz, 8H), 7.06 (d, J = 8.0 Hz, 8H), 6.55 (s, 2H), 4.25-4.16 (m, 8H), 2.55 (t, J = 7.8 Hz, 8H), 1.79-1.71 (m, 4H), 1.62-1.54 (m, 8H (predicted), overlapped with peaks originating from water), 1.37-1.20 (m, 50H), 0.89-0.82 (m, 18H).

[0084] Synthesis Example 14: Synthesis of Compound 14 Compound 14 was synthesized as follows. Starting material 12 (8.72 mg, 7.53 μmol), (5,6-Difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (20.1 mg, 87.3 μmol), and dehydrated chloroform (3 mL) were added to a screw tube. Piperidine (20 mL) was added dropwise to the solution, and after purging with nitrogen, the mixture was heated and stirred at 65°C for 12 hours. The reaction solution was poured into methanol (50 mL), and the precipitated solid was collected by filtration using a Kiriyama funnel. The residue was washed with methanol, dried, and purified by silica column chromatography (developing solvent: chloroform:hexane = 1:1 to 2:1) to obtain target compound 14 as a dark blue solid in a yield of 10.1 mg (85%).

[0085] NMR of Compound 14 1H-NMR (400 MHz, CDCl3) δ 8.72 (s, 2H), 8.50-8.47 (m, 4H), 7.65 (s, 2H), 7.56 (t, J = 7.8 Hz, 2H), 7.18 (d, J = 8.4 Hz, 8H), 7.10 (d, J = 8.4 Hz, 8H), 4.39 (t, J = 7.4 Hz, 4H), 2.56 (t, J = 7.8 Hz, 8H), 1.86-1.47 (m, 4H), 1.61-1.53 ​​(m, 8H (predicted), overlapped with peaks originating from water), 1.41-1.19 (m, 44H), 0.89-0.83 (m, 18H).

[0086] Synthesis Example 15: Synthesis of Compound 15 Compound 15 was synthesized as follows. Starting material 11 (44.9 mg, 46.9 μmol), malononitrile (70 mg, 1.1 mmol), ammonium acetate (35 mg, 0.45 mmol), and dehydrated chloroform (3 mL) were added to a screw tube and purged with nitrogen. After heating and stirring at 65 °C for 1 day, the reaction solution was concentrated. The target product was isolated by silica column chromatography (eluent: chloroform) and then purified by gel permeation column chromatography (eluent: chloroform) equipped with a recycling function. Further reprecipitation was performed with chloroform / methanol. The precipitated solid was filtered, washed with methanol, and dried to obtain 43.3 mg (88% yield) of target product 15 as a red solid.

[0087] NMR of Compound 15 1 H-NMR (400 MHz, CDCl3) δ 7.58 (s, 2H), 7.54 (s, 2H), 7.37 (s, 2H), 7.12 (d, J = 8.0 Hz, 8H), 7.08 (d, J = 8.4 Hz, 8H), 3.88 (s, 6H), 2.56 (t, J = 7.8 Hz, 8H), 1.62-1.58 (m, 8H), 1.37-1.29 (m, 24H), 0.88 (t, J = 6.6 Hz, 12H).

[0088] Synthesis Example 16: Synthesis of Compound 16 Compound 16 was synthesized as follows. Starting material 12 (1.15 g, 1.00 mmol) and starting material 15 (1.11 g, 3.00 mmol) were added to a 100 mL two-neck flask and purged with nitrogen. After adding anhydrous THF (1 mL) and dispersing with ultrasound, potassium tert-butoxide (0.79 g, 7 mmol) was quickly added while stirring in an ice bath. The mixture was stirred in an ice bath for 1 hour and then at room temperature for 15 hours. After cooling again in an ice bath, 2 N hydrochloric acid (10 mL) was added and the mixture was concentrated under reduced pressure. Methanol (50 mL) was added and the mixture was filtered with suction to obtain 1.13 g (93% yield) of target product 16 as an orange solid.

[0089] NMR of Compound 16 1 H-NMR (600 MHz, tetrachloroethane-d2) δ 9.50 (d, J = 7.6 Hz, 2H), 7.42 (s, 2H), 7.29 (d, J = 15.1 Hz, 2H), 7.16 (d, J = 8.2 Hz, 8H), 7.06 (d, J = 8.2 Hz, 8H), 6.79 (s, 2H), 6.43 (dd, J = 15.3 and 7.5 Hz, 2H), 4.20 (d, J = 7.9 Hz, 4H), 2.54 (t, J = 7.6 Hz, 8H), 1.76 (quint, J = 7.2 Hz, 4H), 1.55 (quint, J = 7.6 Hz, 8H), 1.32-1.14 (m, 44H), 0.87 (t, J = 6.9 Hz, 12H), 0.82 (t, J = 7.2 Hz, 6H).

[0090] Synthesis Example 17: Synthesis of Compound 18 Compound 18 was synthesized as follows. Raw material 16 (20.0 μmol), raw material 17 (0.200 mmol), and dehydrated chloroform (3 mL) were added to a screw tube. Piperidine (1.0 mmol) was added dropwise, and after purging with nitrogen, the mixture was heated and stirred at 65°C for 14 hours. The reaction solution was poured into methanol (50 mL), and the precipitated solid was collected by filtration using a Kiriyama funnel. The residue was washed with methanol, dried, and purified by silica column chromatography (chloroform:hexane = 1:1 to 3:2). After concentration, the product was purified by gel permeation column chromatography (developing solvent: chloroform) equipped with a recycling function to obtain the target product 18.

[0091] NMR of Compound 18 1 H-NMR (400 MHz, CDCl3) δ 8.49-8.54 (m, 4H), 8.25 (d, J = 12.4 Hz, 2H), 7.63-7.67 (m, 4H), 7.50 (s, 2H), 7.22 (s, 2H), 7.15-7.18 (m, 10H), 7.10 (d, J = 8 Hz, 8H), 4.23 (t, J = 8.0 Hz, 4H), 2.57 (t, J = 7.7 Hz, 8H), 1.78 (quint, J = 7.5 Hz, 4H), 1.61-1.56 (m, 8H), 1.35-1.17 (m, 44H), 0.88-0.84 (m, 18H).

[0092] Synthesis Example 18: Synthesis of Compound 20 Compound 20 was synthesized as follows. Raw material 16 (20.0 μmol), raw material 19 (0.200 mmol), and dehydrated chloroform (3 mL) were added to a screw tube. Piperidine (1.0 mmol) was added dropwise, and after purging with nitrogen, the mixture was heated and stirred at 65°C for 14 hours. The reaction solution was poured into methanol (50 mL), and the precipitated solid was collected by filtration using a Kiriyama funnel. The residue was washed with methanol, dried, and purified by silica column chromatography (chloroform:hexane = 1:1 to 3:2). After concentration, the product was purified by gel permeation column chromatography (developing solvent: chloroform) equipped with a recycling function to obtain the target product 20.

[0093] Synthesis Example 19: Synthesis of Compound 21 Compound 21 was synthesized as follows. Raw material 12 (20.0 μmol), raw material 19 (0.200 mmol), and dehydrated chloroform (3 mL) were added to a screw tube. Piperidine (1.0 mmol) was added dropwise, and after purging with nitrogen, the mixture was heated and stirred at 65°C for 14 hours. The reaction solution was poured into methanol (50 mL), and the precipitated solid was collected by filtration using a Kiriyama funnel. The residue was washed with methanol, dried, and purified by silica column chromatography (chloroform:hexane = 1:1 to 3:2). After concentration, the product was purified by gel permeation column chromatography (developing solvent: chloroform) equipped with a recycling function to obtain target product 21.

[0094] Synthesis Example 20: Synthesis of Compound 23 Compound 23 was synthesized as follows. Raw material 16 (20.0 μmol), raw material 22 (0.200 mmol), and dehydrated chloroform (3 mL) were added to a screw tube. Piperidine (1.0 mmol) was added dropwise, and after purging with nitrogen, the mixture was heated and stirred at 65°C for 14 hours. The reaction solution was poured into methanol (50 mL), and the precipitated solid was collected by filtration using a Kiriyama funnel. The residue was washed with methanol, dried, and purified by silica column chromatography (chloroform:hexane = 1:1 to 3:2). After concentration, the product was purified by gel permeation column chromatography (developing solvent: chloroform) equipped with a recycling function to obtain the target product 23.

[0095] NMR of Compound 23 1H-NMR (600 MHz, CDCl3) δ 8.56 (dd, J = 14.1, 12.4 Hz, 2H), 8.46 (dd, J = 10.0, 6.5 Hz, 2H), 8.38 (d, J = 12.4 Hz, 2H), 7.55 (t, J = 7.6 Hz, 2H), 7.51 (d, J = 2.4 Hz, 2H), 7.22 (d, J = 14.1 Hz, 2H), 7.15-7.16 (m, 10H), 7.10 (d, J = 7.2 Hz, 8H), 4.23 (t, J = 7.0 Hz, 4H), 2.57 (t, J = 7.7 Hz, 8H), 1.78 (quint, J = 7.5 Hz, 4H), 1.61-1.56 (m, 8H), 1.35-1.17 (m, 44H), 0.88-0.84 (m, 18H).

[0096] Synthesis Example 21: Synthesis of Compound 24 Compound 24 was synthesized according to the following procedure. Starting material 10 (93 mg, 0.10 mmol), 3-ethyl-2,4-dimethylpyrrole (30 mg, 0.24 mmol), and anhydrous dichloroethane (5 mL) were added to a 20 mL two-neck flask and purged with nitrogen. Phosphoryl chloride (20 mL) was added, and the mixture was heated and stirred at 80°C for 2 hours and 30 minutes. After cooling to room temperature, the mixture was concentrated under reduced pressure. Purification was performed using silica column chromatography (chloroform / hexane = 3 / 1 to 10 / 1), and the solvent was removed under reduced pressure. The resulting solid was transferred to a 50 mL two-neck flask and dissolved in anhydrous dichloromethane (15 mL). Triethylamine (0.3 mL) and boron trifluoride diethyl ether complex (0.4 mL) were added sequentially under a nitrogen atmosphere, and the mixture was refluxed overnight. After cooling to room temperature, the reaction solution was poured into methanol (80 mL), the resulting precipitate was filtered, the filter cake was washed with methanol and dried under reduced pressure to give 91 mg of target compound 24 as a black solid (yield 74%).

[0097] NMR of Compound 24 1H-NMR (400 MHz, CDCl3) δ 7.78 (s, 2H), 7.23 (d, J = 8.2 Hz, 8H), 7.04 (d, J = 8.2 Hz, 8H), 6.73 (s, 2H), 6.64 (s, 2H), 2.54 (t, J = 7.8 Hz, 8H), 2.38-2.35 (m, 10H), 2.11 (s, 6H), 1.56 (q, J = 7.8 Hz, 8H), 1.33-1.25 (m, 24H), 1.05 (t, J = 7.6 Hz, 6H), 0.85 (t, J = 6.9 Hz, 12H)

[0098] Synthesis Example 22: Synthesis of Compound 26 Compound 26 was synthesized as follows. In a 50 mL two-neck flask, starting material 25 (93 mg, 0.10 mmol) was dissolved in anhydrous tetrahydrofuran (15 mL). Under a nitrogen atmosphere, 3 mL of approximately 5 M sodium methoxide-methanol solution was added, and the mixture was stirred at room temperature for 4 hours. 1 M hydrochloric acid was added to neutralize the reaction solution, followed by extraction with hexane three times. The organic layer was washed with saturated brine, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting solid was purified by silica column chromatography (developing solvent: chloroform / hexane = 1 / 1), yielding 0.251 g (yield 98%) of target product 26 as a red oil.

[0099] NMR of Compound 26 1H-NMR (600 MHz, CDCl3) δ 8.00 (s, 1H), 7.23 (d, J = 7.2 Hz, 1H), 7.15 (td, J = 7.4 and 1.0 Hz, 1H), 7.09 (d, J = 6.9 Hz, 1H), 7.04 (td, J = 7.4 and 1.1 Hz, 1H), 6.70 (t, J = 2.4 Hz, 1H), 6.13 (dd, J = 2.4 and 1.8 Hz, 1H), 1.91 (td, J = 12.7, 4.5 Hz, 2H), 1.69 (td, J = 12.6, 4.2 Hz, 2H), 1.16-1.07 (m, 12H), 1.02-0.99 (m, 2H), 0.90-0.85 (m, 2H), 0.77 (q, J = 7.2 Hz, 6H)

[0100] Synthesis Example 23: Synthesis of Compound 27 Compound 27 was synthesized as follows. Starting material 10 (93 mg, 0.10 mmol), 3-ethyl-2,4-dimethylpyrrole (26) (78 mg, 0.24 mmol), and anhydrous dichloroethane (5 mL) were added to a 20 mL two-neck flask and purged with nitrogen. Phosphoryl chloride (20 mL) was added, and the mixture was heated and stirred at 80°C for 2 hours and 30 minutes. After cooling to room temperature, the mixture was concentrated under reduced pressure. Purification was performed using silica column chromatography (chloroform / hexane = 2 / 1 to 5 / 1), and the solvent was removed under reduced pressure. The resulting solid was transferred to a 50 mL two-neck flask and dissolved in anhydrous dichloromethane (20 mL). Triethylamine (0.3 mL) and boron trifluoride diethyl ether complex (0.4 mL) were added sequentially under a nitrogen atmosphere, and the mixture was refluxed overnight. After cooling to room temperature, the reaction solution was poured into methanol (80 mL), the resulting precipitate was filtered, the filter cake was washed with methanol and dried under reduced pressure to give 145 mg of target compound 27 as a black solid (yield 87%).

[0101] NMR of Compound 27 1H-NMR (400 MHz, CDCl3) δ 8.34 (s, 2H), 8.17 (d, J = 7.3 Hz, 2H), 7.46 (t, J = 7.6 Hz, 2H), 7.41 (t, J = 6.9 Hz, 2H), 7.33-7.29 (m, 10H), 7.10 (d, J = 8.2 Hz, 8H), 7.00 (s, 2H), 6.76 (s, 2H), 6.66 (s, 2H), 2.54 (t, J = 7.6 Hz, 8H), 1.95-1.89 (m, 4H), 1.77-1.70 (m, 4H), 1.30-0.99 (m, 64H), 0.85-0.77 (m, 24H)

[0102] <Spectroscopic Measurement> Compound 9, compound 13, and compound 14 were dissolved in chloroform, and the absorption spectra of the solutions were measured in the visible to near-infrared region. The results are shown in FIGS. 1 to 3. As shown in FIG. 1, compound 9 has a wide absorption band near 1100 nm in the near-infrared region, demonstrating its suitability as an infrared-absorbing material. As shown in FIG. 2, compound 13 has an absorption band near 600 nm, demonstrating its suitability as a blue dye. As shown in FIG. 3, compound 14 has an absorption band near 700 nm, demonstrating its suitability as a blue-green dye. As such, it was demonstrated that the compounds of this embodiment can adjust the absorption band of light in the visible to near-infrared region by the substituents, and can be suitably used as dyes or infrared-absorbing materials.

[0103] This application claims priority based on Japanese Patent Application No. 2024-30803, filed February 29, 2024, and Japanese Patent Application No. 2024-137666, filed August 19, 2024, the disclosures of which are incorporated herein in their entireties.

Claims

1. A compound represented by any one of the following formulas (I) to (III): In the formula, R １ ~R ８ , R １１ ~R １４ , and R ２１ ~R ２２ each independently represents a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted vinyl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, an optionally substituted alkoxyl group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group; A １ ~A ４ are each independently an electron-withdrawing group, １ ~X ２ are each independently a single bond, (=CH) ｎ１ -(CH=CH) ｎ２ n1 is 0 or 1, n2 is an integer of 0 to 12, n1+n2 is an integer of 1 or more, and n represents the number of repeating units and is an integer of 1 or more.

2. The above A １ ~A ４ are each independently a group represented by any one of the following formulas (a1) to (a6): In the formula, R ３１ ~R ４９ each independently represents a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted vinyl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, an optionally substituted alkoxyl group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group; * represents X １ or X ２ where A represents the bonding position. ３ ~A ４ In this case, R ３１ ~R ４９ Any one of R ２１ or R ２２ or represents the bonding position to the adjacent repeating unit.

3. The above A １ ~A ２ are each independently a group represented by any one of the following formulas (c1) to (c7): In the formula, R ５０ ~R ６７ each independently represents a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted vinyl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, an optionally substituted alkoxyl group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group; * represents X １ or X ２ represents the bonding position with 4. A method for producing a compound represented by formula (I) according to claim 1, which uses a compound represented by the following formula (X) as a starting material: In the formula, R １ ~R ８ each independently represent a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a vinyl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent.

5. A method for producing a compound represented by any one of formulas (II) to (III) according to claim 1, using the compound represented by formula (I) according to claim 1 as a starting material.

6. A compound represented by the following formula (X): In the formula, R １ ~R ８ each independently represent a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a vinyl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent.

7. A resin composition comprising the compound according to any one of claims 1 to 3 and a resin.

8. A film formed using the resin composition according to claim 7.

9. An organic semiconductor material comprising the compound according to any one of claims 1 to 3.

10. A photovoltaic device comprising a compound according to any one of claims 1 to 3.

11. A heat absorbing material comprising a compound according to any one of claims 1 to 3.

12. A phototransistor material comprising a compound according to any one of claims 1 to 3.

13. An optical filter comprising a compound according to any one of claims 1 to 3.

14. A solid-state imaging device comprising the compound according to any one of claims 1 to 3.

15. An infrared camera comprising a compound according to any one of claims 1 to 3.

16. An imaging material comprising the compound according to any one of claims 1 to 3.

17. A toner for developing electrostatic images, comprising the compound according to any one of claims 1 to 3.

18. A printing ink comprising a compound according to any one of claims 1 to 3.

Images