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

To provide an infrared-absorbing compound, a method for producing the compound, and various articles comprising the compound.SOLUTION: The compound is represented by one of the formulas (I) to (III), where: R1 to R22 are each a substituted / unsubstituted aryl group, or the like; A1 to A4 are each an electron-withdrawing group; X1 to X2 are each a single bond, or the like.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[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. [Background technology]

[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 (for example, Patent Documents 4 and 5). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-001342 [Patent Document 2] International Publication No. 2020 / 175456 [Patent Document 3] Japanese Patent Application Laid-Open No. 2016-108431 [Patent Document 4] Japanese Patent Publication No. 2023-131962 [Patent Document 5] Japanese Patent Application Publication No. 2018-150248 Summary of the Invention [Problem to be solved by the invention]

[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. [Means for solving the problem]

[0005] The compound according to this embodiment is a compound represented by any one of the following formulas (I) to (III). [ka] During the ceremony, R1 to R8, R 11 ~R 14 , and R 21 ~R 22 each independently represent 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, A1 to A4 each independently represent an electron-withdrawing group, X1 and X2 each independently represent a single bond, (=CH) n1 -(CH=CH) n2 - or an optionally substituted nitrogen atom, n1 is 0 or 1, n2 is an integer from 0 to 12, n1+n2 are integers equal to or greater than 1, n represents the number of repeating units and is an integer of 1 or more.

[0006] In one embodiment of the compound, A1 to A4 are each independently a group represented by any one of the following formulas (a1) to (a6). [ka] During the ceremony, R 31 ~R 49 each independently represent 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, * indicates the bonding position to X1 or X2. However, in A3 to A4, R 31 ~R 49 One of the following is R 21 or R 22 or represents the bonding position to the adjacent repeating unit.

[0007] In one embodiment of the compound, A1 and A2 are each independently a group represented by any one of the following formulae (c1) to (c7). [ka] During the ceremony, R 50 ~R 67each independently represent 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, * indicates the bonding position to X1 or X2.

[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. [ka] During the ceremony, R1 to R8 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] The method for producing a compound represented by any one of formulas (II) to (III) according to this embodiment uses the compound represented by formula (I) as a raw material.

[0010] Furthermore, the present disclosure 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). [Effects of the Invention]

[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. [Brief explanation of the drawings]

[0012] [Figure 1] 1 is an absorption spectrum of compound 9. [Figure 2] 1 is an absorption spectrum of compound 13. [Figure 3] 1 is an absorption spectrum of compound 14. DETAILED DESCRIPTION OF THE INVENTION

[0013] In this specification, unless otherwise specified, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In this specification, the compound represented by formula (I) may be referred to as "compound (I)" or the like. The same applies to other compounds. In the examples, each compound may be referred to as raw material N, target product N, or the like, depending on the situation (N represents the compound number). Furthermore, when there are a plurality of identical symbols in a chemical formula, the identical symbols may represent the same structure as each other, or may represent different structures as long as they are within a specified range.

[0014] [Compound] The compounds of the present disclosure are compounds represented by any of the formulas (I) to (III) described below. These compounds have in common a skeleton represented by the following formula (A). [ka] 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, the 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)> [ka] In the formula, R1 to R8 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. 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.

[0018] Examples of the aryl group in the aryl group which may have a substituent include a phenyl group, a naphthyl group, and an anthracenyl group. The substituent that the aryl group may have includes the substituent that the alkyl group may have and the alkyl group that may have a substituent. The alkyl group that may have a substituent includes the same as the alkyl group that 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, and a cyclohexyl group. The substituents which the cycloalkyl group may have include the same 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, as well as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, pyrazole, pyran, pyrone, pyridine, pyrone, pyridazine, pyrimidine, pyrazine, benzofuran, thionaphthene, indole, carbazole, coumarin, quinoline, phthalazine, and quinoxaline. The substituent that the heterocyclic group may have includes the same substituents as those that 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 portion of the aryloxy group which may have a substituent may be the same as the above-mentioned aryl group which may have a substituent.

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

[0024] The substituents on the optionally substituted phthalimidomethyl group include the same as the substituents that the above-mentioned aryl group may have. The substituents on the optionally substituted sulfamoyl group include the same as the substituents that the above-mentioned aryl group may have.

[0025] R1 to R4 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. Specific examples of R1 to R4 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] R5 and R6 each independently include 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. Specific examples of R5 and R6 include a hydrogen atom, a halogen atom, a methyl group, a substituted ethenyl group, and a formyl group. 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). Here, Et is an ethyl group. [ka]

[0027] R7 and R8 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. Specific examples of R7 and R8 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 the compound (I) include compounds represented by the following formulae (I-1) to (I-3). [ka] The symbols in the formula are as described above.

[0030] <Compound (II)> [ka] During the ceremony, R1 to R8 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; A1 and A2 each independently represent an electron-withdrawing group, X1 and X2 each independently represent a single bond, (=CH) n1 -(CH=CH) n2 - or a nitrogen atom which may have a substituent.

[0031] R1 to R8 in formula (II) are the same as R1 to R8 in formula (I), and preferred embodiments are also the same.

[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 than a hydrogen atom. Examples of the electron-withdrawing group include those having a Hammett substituent constant (σp-) that is a positive value, preferably 0.01 or more. Examples of the electron-withdrawing group include a cyano group, a nitro group, a halogeno group, a nitrogen-containing heterocycle which 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, Si, etc., and may also have other substituents. In addition, the nitrogen-containing heterocycle may or may not have aromaticity.

[0033] A1 and A2 are preferably groups selected from the following formulae (a1) to (a6) and (c1) to (c7). [ka] During the ceremony, R 31 ~R 49 each independently represent 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, * indicates the bonding position to X1 or X2.

[0034] [ka] During the ceremony, R 50 ~R 67 each independently represent 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, * indicates the bonding position to X1 or X2.

[0035] R 31 ~R 49 and R 50 ~R 67 Examples of the substituents in R include the same as those in R1 to R8 in formula (I). 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] A1 and A2 may be the same or different from each other. From the viewpoint of ease of synthesis, it is preferable that A1 and A2 are the same, but it is also possible to synthesize a compound in which A1 and A2 are different from each other by combining two or more raw materials in the production method described below.

[0037] X1 and X2 each independently represent a single bond, (=CH) n1 -(CH=CH) n2 - or an optionally substituted nitrogen atom, n1 is 0 or 1, n2 is an integer from 0 to 12, n1+n2 is an integer of 1 or greater.

[0038] When X1 and X2 are single bonds, the skeleton (A) and the electron-withdrawing group are directly bonded. X1~X2 is (=CH) n1 -(CH=CH) n2 In the case of -, when n1 is 0, both terminals of X1 to X2 are single bonds. When n1 is 1, the terminal on the skeleton (A) side is a single bond, and the terminal on the electron-withdrawing group side is a double bond. When X1 to X2 are bonded to a carbon atom having a π bond (for example, when bonded to the electron-withdrawing groups of the above formulae (a1) to (a4) and (c4)), the terminal is preferably a single bond (i.e., n1 = 0). When X1 to X2 are bonded to a carbon atom not having a π bond (for example, when bonded to the electron-withdrawing groups of the above formulae (a5) to (a6), formulae (c1) to (c3), and formulae (c5) to (c7)), the terminal may be a single bond or a double bond, but a double bond (i.e., n1 = 1) is preferred. When X1 and X2 are nitrogen atoms which may have a substituent, both ends of X1 and X2 are single bonds when the nitrogen atom has a substituent. 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 the same as those for R7 and R8 in formula (I), and preferred embodiments are also the same. 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 formulae (II-1) to (II-6). [ka] [ka] The symbols in the formula are as described above.

[0040] <Compound (III)> [ka] During the ceremony, R1~R4, R 11 ~R 14 , and R 21 ~R 22 each independently represent 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, A3 and A4 each independently represent an electron-withdrawing group, X1 and X2 each independently represent a single bond, (=CH) n1 -(CH=CH) n2 - or an optionally substituted nitrogen atom, n1 is 0 or 1, n2 is an integer from 0 to 12, n1+n2 are integers equal to or greater than 1, n represents the number of repeating units and is an integer of 1 or more.

[0041] R1 to R4 in formula (III) are the same as R1 to R4 in formula (I), and preferred embodiments are also the same.

[0042] R 11 ~R 14 Examples of the substituents in R include the same as those in R1 to R8 in formula (I). 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 Examples of the substituents in R include the same as those in R1 to R8 in formula (I). 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 may have a structure similar to X1-A1 in formula (II), where A1 is preferably a group selected from the groups represented by formulae (c1) to (c7).

[0044] The electron-withdrawing groups in A3 and A4 are preferably the nitrogen-containing heterocycles in A1 and A2 which may have a substituent, and are preferably the groups represented by the formulae (a1) to (a6), provided that any of the nitrogen atoms in the nitrogen-containing heterocycle is bonded to the boron in formula (III).

[0045] X1 and X2 are the same as X1 and X2 in the formula (II), and preferred embodiments are also the same.

[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 2-50, and more preferably 2-30.

[0047] Specific examples of the compound (III) include compounds represented by the following formulae (III-1) to (III-5). [ka] 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 is a production method using the following compound (X) as a raw material. [ka] During the ceremony, R1 to R8 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.

[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, a method for producing compound (X) will be described with an example.

[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. [ka] however, R a are substituents corresponding to R5 and R6 of compound (X), R b are substituents corresponding to R7 and R8 of compound (X) or are protecting groups, R c are substituents corresponding to R1 to R4 of the compound (X).

[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 XR 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 production methods of compounds (II) and (III) will be described. The production methods of compounds (II) and (III) are not particularly limited, but for example, compound (II) can be produced from compound (I) above as a starting material according to the following scheme 2. [ka] however, R b are substituents corresponding to R7 and R8 of compound (X) or are protecting groups, R d and R e are substituents capable of reacting with each other, A a are substituents corresponding to A1 and A2 in compound (II).

[0053] The synthesis of compound (XV) is carried out by adding a protecting group R b , reactive group R d The reactive group R d , protecting group R b R5 and R6 may be introduced in the order b It is also possible to use 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. [ka] however, R f is R of compound (III) 11 ~R 14 is a substituent corresponding to A1 and A2 are A3R of compound (III). 21 and A4R 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, the compounds (I) to (III) have the characteristic of selectively absorbing light of a specific wavelength, and can adjust the absorption band of light in the visible to near-infrared region. Furthermore, the compounds (I) to (III) have high planarity. Due to these properties, the compounds (I) to (III) can be suitably used, for example, as dyes (pigments), infrared absorbing materials, organic semiconductor materials, and the like. More specifically, examples of the compounds 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. Alternatively, compounds (I) to (III) may be mixed with a resin to prepare a resin composition, and a coating film may be formed using the resin composition. In these articles, components other than compounds (I) to (III) may be appropriately selected from conventionally known components. [Example]

[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. [ka]

[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 mixture 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 three extractions with chloroform, 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 addition, Boc in the formula is -COOC(CH3)3.

[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. [ka] p-Bromohexylbenzene (20.8 g, 86.2 mmol) was added to a 500 mL three-neck flask and the atmosphere was purged with nitrogen. Anhydrous tetrahydrofuran (130 mL) was added and 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 and the mixture was stirred 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 mixture and the mixture was stirred at -78 °C for 1 hour. The mixture was then warmed to room temperature and stirred for 2 hours. The reaction was quenched by adding 100 mL of aqueous ammonium chloride solution, and the tetrahydrofuran was removed under reduced pressure using an evaporator. Hexane was added, and the precipitated solid was collected by ultrasonic irradiation using a Kiriyama funnel. The residue was washed with hexane and water and then dried to obtain 4.38 g of the target product 3 (yield 84%).

[0061] NMR of compound 3 1H-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. [ka] Starting material 3 (457 mg, 0.503 mmol) was placed in a 50 mL two-neck flask and the atmosphere was replaced 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 (95% yield) of the target compound as a white solid.

[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 and stirred for 15 minutes at 80 °C. 20 mL of purified water was added to the reaction solution, and the precipitate was filtered and washed with methanol to obtain 416 mg of the target product (95% yield).

[0064] NMR of compound 4 1H-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. [ka] In a 100 mL two-neck flask, starting material 4 (416 mg, 0.476 mmol) was added and dissolved in anhydrous dichloromethane (20 mL) and 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 the desired 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. [ka] 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 (developing solvent: chloroform:hexane=2:1) ​​to obtain 277 mg (yield 84%) of target product 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. [ka] 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 reduced pressure (2 Torr) at 185-190°C for 90 minutes under Kugelrohr. 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. [ka] 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, and the mixture was then purged with nitrogen and heated and stirred 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 washed with methanol, dried, and purified by silica column chromatography (eluent: chloroform) to give 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. [ka] 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 tube. 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 tube from the glove box, the fraction containing the target compound was separated and isolated by silica column chromatography (chloroform:hexane = 1:1 to 2:1). After concentration, the product was isolated and purified by gel permeation column chromatography (eluent: chloroform) with a recycling function. The product was then reprecipitated with 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 compound 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. [ka] A 50 mL two-neck flask was charged with starting material 4 (88 mg, 0.10 mmol), 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 1 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 warm 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 (90% yield).

[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. [ka] NaH (60 wt% in mineral oil, 52 mg, 1.3 mmol) was added to 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, and the mixture was stirred 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 the desired product 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 11-1: Synthesis of Compound 12] Compound 12 was synthesized as follows. [ka] NaH (60 wt% in mineral oil, 20 mg, 0.50 mmol) was added to 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 h with stirring. After stirring at room temperature for another 1 h, 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 (eluent: chloroform:hexane = 2:1 to 3:1) to obtain 46 mg of the desired product 12 as a tan solid (93% yield).

[0080] [Synthesis Example 11-2: Synthesis of Compound 12] Compound 12 was synthesized as follows. [ka] 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 to obtain 6.06 g (95% yield) of target product 12 as a tan 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 12: Synthesis of Compound 13] Compound 13 was synthesized as follows. [ka] 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 cap 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 filter cake 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 the target product 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 13: Synthesis of Compound 14] Compound 14 was synthesized as follows. [ka] 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 (eluent: chloroform:hexane = 1:1 to 2:1) to obtain the desired product 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. [ka] 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 1H-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. [ka] 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 the atmosphere was replaced 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 the desired product 16 as an orange solid.

[0089] NMR of compound 16 1H-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. [ka] Starting material 16 (20.0 μmol), starting material 17 (0.200 mmol), and dehydrated chloroform (3 mL) were added to a screw tube. Piperidine (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 (developing solvent: chloroform) equipped with a recycling function to obtain the target product 18.

[0091] NMR of compound 18 1H-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. [ka] 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. [ka] Starting material 12 (20.0 μmol), starting 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 21.

[0094] [Synthesis Example 20: Synthesis of Compound 23] Compound 23 was synthesized as follows. [ka] Starting material 16 (20.0 μmol), starting material 22 (0.200 mmol), and dehydrated chloroform (3 mL) were added to a screw tube. Piperidine (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 (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 as follows. [ka] 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 by 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), and 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 1 H-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. [ka] 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 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) to obtain 0.251 g (98% yield) 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. [ka] 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 by 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), and 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 1 H-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> The above compounds 9, 13 and 14 were dissolved in chloroform, and the absorption spectra of the solutions in the visible to near-infrared region were measured. The results are shown in FIGS. As shown in FIG. 1, Compound 9 has a wide absorption band in the near-infrared region around 1100 nm, demonstrating that it is suitable as an infrared absorbing material. As shown in FIG. 2, compound 13 has an absorption band around 600 nm, indicating that it is suitable as a blue dye. As shown in FIG. 3, compound 14 has an absorption band around 700 nm, indicating that it is suitable as a blue-green dye. As described above, it has been shown that the compound of this embodiment can adjust the absorption band of light in the visible to near-infrared region by changing the substituent, and can be suitably used as a dye or an infrared absorbing material.

Claims

1. A compound represented by any one of the following formulas (I) to (III): 【Chemical 1】 During the ceremony, R １ ~R ８ , R １１ ~R １４ , and R ２１ ~R ２２ each independently represent 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, X １ ~X ２ are each independently a single bond, (=CH) ｎ１ -(CH=CH) ｎ２ - or an optionally substituted nitrogen atom, n1 is 0 or 1; n2 is an integer from 0 to 12, n1+n2 is an integer of 1 or more, 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): 【Chemistry 2】 During the ceremony, R ３１ ~R ４９ each independently represent 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, * is X １ or X ２ represents the bonding position with However, A 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): 【Chemistry 3】 During the ceremony, R ５０ ~R ６７ each independently represent 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, * is 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 raw material: 【Chemistry 4】 During the ceremony, 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): 【Chemistry 5】 During the ceremony, 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 the compound according to any one of claims 1 to 3.

12. A phototransistor material comprising the 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.

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