Heterocyclic compounds and luminescent materials

Abstract

Provided are a novel heterocyclic compound, a method for producing the same, and a luminescent material containing the same. 【Solution means】The heterocyclic compound is represented by formula (1). TIFF2026096729000040.tif3168 [In formula (1), ring A represents an aromatic ring having 5 to 24 nuclear atoms which may have a substituent. R 1 each independently represents an oxygen atom or a sulfur atom. R 2 each independently represents a hydrogen atom, a linear, branched or cyclic hydrocarbon group having 1 to 4 carbon atoms or a linear, branched or cyclic fluorine-containing hydrocarbon group having 1 to 4 carbon atoms. Also, R 2 can combine with ring A to form a ring. X 1 each independently represents a nitrogen atom or a carbon atom which may be substituted. Y 1 each independently represents a divalent organic group having 5 to 14 nuclear atoms which may have a substituent. n each independently represents 0 or 1. Ar 1 each independently represents a heteroaromatic group having 5 to 14 nuclear atoms containing a nitrogen atom which may have a substituent. m represents an integer of 2 to 6.]

Description

【Technical Field】 【0001】 The present invention relates to a heterocyclic compound and a luminescent material. 【Background Art】 【0002】 Compounds that emit light in solution or in the solid state have attracted attention because they can be applied to fluorescent dyes, light-emitting layers of organic ELs, etc. due to their diverse optical properties. 【0003】 In Patent Documents 1, 2, and Non-Patent Document 1, it is disclosed that compounds having a terpyridine skeleton exhibit luminescent properties and are useful as a light-emitting layer of organic ELs. 【Prior Art Documents】 【Patent Documents】 【0004】 【Patent Document 1】 Japanese Patent Application Laid-Open No. 2019-026619 【Patent Document 2】 Japanese Patent Application Laid-Open No. 2017-019761 【Non-Patent Document 1】 Kido et al., Advanced Materirals, 2019, 31, 1808300. 【Summary of the Invention】 【Problems to be Solved by the Invention】 【0005】 The present invention has been made in view of the above background art, and an object thereof is to provide a novel heterocyclic compound, a method for producing the same, and a luminescent material containing the same. 【Means for Solving the Problems】 【0006】 The present inventors have found a compound of the present embodiment (hereinafter sometimes referred to as "heterocyclic compound (1)"), and have also established a method for producing the same. Further, they have found that a material containing the heterocyclic compound (1) exhibits luminescent properties, and have completed the present invention. 【0007】 In other words, the present invention encompasses the following aspects. 【0008】 A first aspect of this disclosure is a heterocyclic compound represented by formula (1). [ka] [In formula (1), Ring A represents an aromatic ring with 5 to 24 nuclear atoms, which may have substituents. R 1 Each of these independently represents either an oxygen atom or a sulfur atom. R 2 Each of these independently represents a hydrogen atom, a linear, branched, or cyclic hydrocarbon group having 1 to 4 carbon atoms, or a linear, branched, or cyclic fluorine-containing hydrocarbon group having 1 to 4 carbon atoms. Also, R 2 It combines with ring A to form the following equation (2) [ka] (In formula (2), R 1 This is synonymous with the above. 3 Each of these independently represents either an oxygen atom or a sulfur atom. * indicates a bond position. A ring containing the substructure shown by ) can be formed. X 1 Each of these independently represents a nitrogen atom or an optionally substituted carbon atom. Y 1 Each of these independently represents a divalent organic group having 5 to 14 nuclear atoms, which may have substituents. Each n independently represents either 0 or 1. Ar 1 Each of these independently represents a heteroaromatic group containing a nitrogen atom and having 5 to 14 nuclear atoms, which may have substituents. m represents an integer between 2 and 6. 【0009】 A second aspect of this disclosure is formula (3a) [ka] (In formula (3a), X1 Each independently represents a nitrogen atom or a carbon atom which may be substituted. Y 1 Each represents a divalent organic group having 5 to 14 nuclear atoms which may have a substituent. n each independently represents 0 or 1. Ar 1 Each independently represents a heteroaromatic group having 5 to 14 nuclear atoms containing a nitrogen atom which may have a substituent. R 4 Each independently represents a hydrogen atom, a linear, branched or cyclic hydrocarbon group having 1 to 4 carbon atoms or a linear, branched or cyclic fluorinated hydrocarbon group having 1 to 4 carbon atoms. The amine compound represented by ) and the compound represented by formula (4a) 【Chemical formula】 (In formula (4a), Ring A represents an aromatic ring having 5 to 24 nuclear atoms which may have a substituent. R 1 Each represents an oxygen atom or a sulfur atom. Z each independently represents a halogen atom or a hydroxyl group.) are reacted in the presence of at least one additive selected from the group consisting of a base and a condensing agent, and formula (1a) 【Chemical formula】 (In formula (1a), Ar 1 、X 1 、R 1 、R 4 、Y 1 、m, n and ring A have the same meanings as described above.) is a method for producing a heterocyclic compound represented by. 【0010】 The third aspect of the present disclosure is formula (3b) 【Chemical formula】 (In formula (3b), X 1Each of these independently represents a nitrogen atom or an optionally substituted carbon atom. Y 1 This represents a divalent organic group with 5 to 14 nuclear atoms, which may have substituents. Each n independently represents either 0 or 1. Ar 1 Each of these independently represents a heteroaromatic group having 5 to 14 nuclei containing a nitrogen atom, which may have substituents. ) and formula (4b) [ka] (In formula (4b), Ring A represents an aromatic ring with 5 to 24 nuclear atoms, which may have substituents. R 1 and R 3 Each of these independently represents either an oxygen atom or a sulfur atom. m represents an integer from 2 to 6. The compound represented by formula (1b) is reacted with the compound represented by formula (1b) in the presence of at least one additive selected from the group consisting of acids, bases, and condensing agents. [ka] (In formula (1b), Ar 1 , X 1 , R 1 , R 3 , Y 1 The following is a method for producing a heterocyclic compound represented by ). 【0011】 A fourth aspect of this disclosure is a luminescent material comprising a heterocyclic compound represented by formula (1). [ka] [Effects of the Invention] 【0012】 According to the present invention, a complex compound, a method for producing the same, and a luminescent material containing the same are provided. [Brief explanation of the drawing] 【0013】 [Figure 1] This figure shows the results of fluorescence spectrophotometric measurements of the DMF solution (C-2) at room temperature. [Modes for carrying out the invention] 【0014】 Preferred embodiments of the present invention will be described in detail below. 【0015】 <Heterocyclic compounds> The heterocyclic compound of this embodiment (hereinafter also referred to as heterocyclic compound (1)) is the compound represented by the following formula (1). [ka] In the formula, Ar 1 , X 1 , R 1 , R 2 , Y 1 , m, n and ring A are as defined above, except for the compounds represented by the following formulas (A-100) and (B-100). [ka] 【0016】 Examples of aromatic rings with 5 to 24 nuclear atoms represented by ring A include benzene rings, pyridine rings, pyrazine rings, naphthalene rings, coumarin rings, quinoxaline rings, anthracene rings, tetracene rings, triphenylene rings, perylene rings, and coronene rings. There are no restrictions on the bond position between ring A and formula (2). Ring A is preferably an aromatic ring with 6 to 10 nuclear atoms, and more preferably a benzene ring, naphthalene ring, or perylene ring, due to the ease of obtaining raw materials and the ease of synthesis. Ring A may also be substituted with one or more groups selected from the group consisting of halogen atoms, hydrocarbon groups with 1 to 6 carbon atoms, aromatic hydrocarbon groups with 6 to 12 nuclear atoms, and heteroaromatic groups with 3 to 6 nuclear atoms. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms. Chlorine atoms or bromine atoms are preferred due to the ease of obtaining raw materials. The hydrocarbon group may be linear, branched, or cyclic, and examples include methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, 2-methylpropyl group, 2-methylcyclopropyl group, 3-methylpropyl group, cyclobutyl group, pentyl group, 2-methylbutyl group, 3-methylbutyl group, 4-methylbutyl group, cyclopentyl group, hexyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 2,3-dimethylbutyl group, 3-ethylpentyl group, cyclohexyl group, etc. Methyl group, ethyl group, or propyl group are preferred because the raw materials are readily available. The aromatic hydrocarbon group is a monovalent group. The number of nuclear atoms in the aromatic hydrocarbon group is preferably 6 to 10. Furthermore, the aromatic hydrocarbon group may be a monocyclic aromatic hydrocarbon group, an aromatic hydrocarbon group in which two or more aromatic rings are linked, or a fused aromatic hydrocarbon group. More specifically, examples of the aromatic hydrocarbon group include a phenyl group, a biphenylyl group, or a naphthyl group. The heteroaromatic group may be a monocyclic heteroaromatic group, a heteroaromatic group in which two or more aromatic rings are linked, or a fused heteroaromatic group, and if the heteroaromatic group has multiple aromatic rings, it is sufficient that at least one of the aromatic rings contains a heteroatom (e.g., an oxygen atom, a nitrogen atom, a sulfur atom, etc.).Examples of such heteroaromatic groups include pyrrolyl, thienyl, furyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, thiadiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, pyridyl, pyrimidyl, pyrazyl, and 1,3,5-triazinyl groups. Furyl, thienyl, or pyrazyl groups are preferred because their raw materials are readily available. 【0017】 R 1 Each of these independently represents either an oxygen atom or a sulfur atom, and oxygen atoms are preferred because they are easy to synthesize. 【0018】 R 2 Each of these independently represents a hydrogen atom, a linear, branched, or cyclic hydrocarbon group having 1 to 4 carbon atoms, or a linear, branched, or cyclic fluorine-containing hydrocarbon group having 1 to 4 carbon atoms. Examples of such 1 to 4 carbon atom hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, 2-methylpropyl, 2-methylcyclopropyl, and 3-methylpropyl groups. The linear, branched, or cyclic fluorine-containing hydrocarbon groups having 1 to 4 carbon atoms include trifluoromethyl, difluoromethyl, perfluoroethyl, 2,2,2-trifluoroethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, perfluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 1,1-difluoropropyl, perfluoroisopropyl, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl, and perfluoropropyl groups. Examples include fluorocyclopropyl group, 2,2,3,3-tetrafluorocyclopropyl group, perfluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 4,4,4-trifluorobutyl group, 1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl group, 1-(trifluoromethyl)propyl group, 1-methyl-3,3,3-trifluoropropyl group, perfluorocyclobutyl group, 2,2,3,3,4,4-hexafluorocyclobutyl group, etc. 2More specifically, examples include hydrogen atoms, methyl groups, or trifluoromethyl groups. Hydrogen atoms are preferred because they are easy to synthesize. Also, R 2 It combines with ring A to form the following equation (2) [ka] (In the formula, R 1 , R 3 And * are synonymous with the above. Forming a ring containing the substructure shown in ) is preferable in that it can provide high thermal stability and high chemical stability. 【0019】 R 3 R represents an oxygen atom or a sulfur atom, and is easy to synthesize. 3 An oxygen atom is preferred. 【0020】 X 1 Each of these independently represents a nitrogen atom or an optionally substituted carbon atom. 1 When is a carbon atom, examples of substituents include hydrocarbon groups having 1 to 6 carbon atoms, aromatic hydrocarbon groups having 6 to 12 nuclear atoms, or heteroaromatic groups having 3 to 6 nuclear atoms. More specifically, examples include methyl groups, ethyl groups, phenyl groups, thienyl groups, etc. 1 It is preferable that the material consists entirely of carbon atoms, as this makes synthesis easier. 【0021】 Y 1 Each of these independently represents a divalent organic group having 5 to 14 nuclear atoms, which may have substituents. Examples of such organic groups include substituted phenylene groups, naphthylene groups, anthracenyl groups, etc., and there are no restrictions on the bond position. 1Phenylene groups are preferred because they are easy to synthesize. Examples of substituents include halogen atoms, hydrocarbon groups having 1 to 6 carbon atoms, aromatic hydrocarbon groups having 6 to 12 nuclear atoms, or heteroaromatic groups having 3 to 6 nuclear atoms. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms, with chlorine atoms being preferred because they are easy to synthesize. More specifically, examples of hydrocarbon groups include methyl groups, ethyl groups, propyl groups, or butyl groups. Examples of aromatic hydrocarbon groups include phenyl groups, naphthyl groups, or anthryl groups, with phenyl groups being preferred because they are easy to synthesize. Examples of such heteroaromatic groups include pyrrolyl, thienyl, furyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, thiadiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, pyridyl, pyrimidyl, pyrazyl, and 1,3,5-triazinyl groups. Furyl or thienyl groups are preferred for their ease of synthesis. Y 1 If there are multiple groups, it is preferable that they are all the same group for ease of synthesis. 【0022】 n independently represents either 0 or 1, and n is preferably 1 because the raw materials are readily available and the synthesis is easy. 【0023】 Ar 1 Each of these independently represents a heteroaromatic group having 5 to 14 nuclear atoms including a nitrogen atom, which may have substituents. Examples of such heteroaromatic groups include pyrazolyl, imidazolyl, thienyl, furyl, benzofuranyl, benzothienyl, dibenzofuranyl, dibenzothienyl, pyrimidyl, pyrazinyl, pyridyl, quinolinyl, isoquinolinyl, and the like. Furthermore, the pyridyl group is preferred because the raw materials are readily available and easy to synthesize, and the 2-pyridyl group is more preferred because it is easy to synthesize. As for the substituent, see Y above. 1Examples of halogen atoms include the halogen atoms exemplified above, hydrocarbon groups with 1 to 6 carbon atoms, aromatic hydrocarbon groups with 6 to 12 nuclear atoms, or heteroaromatic groups with 3 to 6 nuclear atoms. More specifically, a chlorine atom can be exemplified as a halogen atom. More specifically, a methyl group, ethyl group, propyl group, or butyl group can be exemplified as a hydrocarbon group. More specifically, a furyl group or thienyl group can be exemplified as a heteroaromatic group. Ar 1 It is preferable that all the components are the same group, as this facilitates synthesis. 【0024】 m represents an integer between 2 and 6. An integer between 2 and 4 is preferred because the raw materials are readily available, and m is more preferably 2 or 3 because it is easy to synthesize. 【0025】 The heterocyclic compound (1) in this embodiment is not limited to this embodiment, and examples include compounds represented by the following formulas (A-1) to (A-20), (B-1) to (B-20), (C-1) to (C-24), and (D-1) to (D-24). Compounds represented by (A-1) to (A-12), (B-1) to (B-16), (C-1) to (C-6), and (D-1) to (D-6) are preferred in terms of ease of synthesis, and compounds represented by (A-1), (B-1), (B-11), (B-16), and (C-2) are more preferred in terms of high reaction yield. 【0026】 [ka] TIFF2026096729000014.tif12390TIFF2026096729000015.tif130109TIFF2026096729000016.tif132119TIFF20260967290 00017.tif199125TIFF2026096729000018.tif194128TIFF2026096729000019.tif183120TIFF2026096729000020.tif232147 【0027】 <Method for producing heterocyclic compounds> The compound represented by the following formula (1a) (hereinafter sometimes referred to as "heterocyclic compound (1a)"), which is included in heterocyclic compound (1) of this embodiment, can be produced by reacting an amine compound represented by formula (3a) and a compound represented by formula (4a) (hereinafter sometimes referred to as "amine compound (3a)" and "compound (4a)," respectively) in the presence of at least one additive selected from the group consisting of a base and a coupling agent, as shown in step 1 below. [ka] In the formula, X 1 , Y 1 Ar 1 , R 1 Z, m, n, and ring A are as defined above. 4 Each of these independently represents a hydrogen atom, a linear, branched, or cyclic hydrocarbon group having 1 to 4 carbon atoms, or a linear, branched, or cyclic fluorine-containing hydrocarbon group having 1 to 4 carbon atoms. The hydrocarbon group having 1 to 4 carbon atoms is as described above. 2 Examples of hydrocarbon groups similar to those exemplified above can be given. Examples of fluorine-containing hydrocarbon groups having 1 to 4 carbon atoms include the aforementioned R 2 Examples similar to the fluorine-containing hydrocarbon groups exemplified above can be given. In terms of the high reaction yield of heterocyclic compound (1a), R 4 R is a hydrogen atom, 1 Z is preferably an oxygen atom and Z is preferably a chlorine atom or a hydroxyl group, and more preferably Z is a chlorine atom. 【0028】 The compound represented by amine compound (3a) can be synthesized, for example, based on the methods disclosed in the literature (International Publication No. 2012 / 148090A1; International Publication No. 2019 / 072143A1; Chemistry-A European Journal, 2006, 12, 4241; Journal of the Chemical Society, Perkin Transactions 1, 2001, 7, 1045; Journal of the American Chemical Society, 2002, 124, 1364; Journal of the American Chemical Society, 2005, 127, 13567; Journal of the American Chemical Society, 2000, 122, 9993; Tetrahedron, 2020, 76, 131283), or commercially available products may be used. 【0029】 The compound represented by formula (4a) can be synthesized, for example, based on the methods disclosed in the literature (Chemistry-A European Journal, 2016, 22, 3115; New Journal of Chemistry 2019, 43, 19355; Journal of the American Chemical Society, 2011, 133, 8961; Angewandte Chemie, International Edition, 2011, 50, 6552; Chemical Communications, 2011, 47, 10112; International Publication No. 2015 / 068858), or commercially available products may be used. 【0030】 In step 1, the equivalent amount of amine compound (3a) relative to compound (4a) is preferably in the range of 1.5 to 3.0 equivalents, and more preferably in the range of 2.0 to 2.5 equivalents, when m is 2, in order to obtain a good reaction yield of the heterocyclic compound (1a) in this embodiment. When m is 3, the equivalent amount of amine compound (3a) relative to compound (4a) is preferably in the range of 2.0 to 4.0 equivalents, and more preferably in the range of 2.5 to 3.8 equivalents. When m is 4, the equivalent amount of amine compound (3a) relative to compound (4a) is preferably in the range of 4.0 to 5.0 equivalents. When m is 5, the equivalent amount of amine compound (3a) relative to compound (4a) is preferably in the range of 5.0 to 6.0 equivalents. When m is 6, the equivalent amount of amine compound (3a) relative to compound (4a) is preferably in the range of 6.0 to 7.0 equivalents. 【0031】 Step 1 can be carried out in the presence of a base. Examples of such bases include organic bases such as triethylamine, pyridine, 4-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undeca-7-ene, tetramethylethylenediamine, and 1,4-diazabicyclo[2.2.2]octane; metal hydroxides such as sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, and barium hydroxide; metal carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate; metal acetates such as potassium acetate and sodium acetate; metal phosphates such as potassium phosphate and sodium phosphate; metal fluoride salts such as sodium fluoride, potassium fluoride, and cesium fluoride; and metal alkoxides such as sodium methoxide, potassium methoxide, sodium ethoxide, potassium isopropyl oxide, potassium tert-butoxide, and sodium tert-butoxide. Triethylamine is preferred over 4-(dimethylamino)pyridine due to the readily available raw materials, and is more preferred because it yields a high reaction yield. 【0032】 Step 1 can be carried out in the presence of a condensing agent. The condensing agent may be 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, N,N'-carbonyldiimidazole, 1,1'-carbonyldi(1,2,4-triazole), 4-(4,6-dimethoxy-1,3,5-triazine-2-yl)-4-methylmorpholinium chloride n hydrate, or 1H-benzotriazole-1-yl Bromotris(dimethylamino)phosphonium hexafluorophosphate, 1H-benzotriazole-1-yloxytripyrrolidinophosphonium hexafluorophosphate, (7-azabenzotriazole-1-yloxy)tripyrrolidinophosphonium hexafluorophosphate, chlorotripyrrolidinophosphonium hexafluorophosphate, bromotris(dimethylamino)phosphonium hexafluorophosphate, 3-(diethoxyphosphoryloxy)-1,2,3-benzotriazine-4(3H)-one, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, O-(N-succinimidyl)-N,N,N',N'-tetramethyluronium tetrafluoroborate, O-(N-succinimidyl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, O-(3,4-dihydro-4-oxo-1,2,3-ben Zotriazin-3-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate, S-(1-oxide-2-pyridyl)-N,N,N',N'-tetramethylthiuronium tetrafluoroborate, O-[2-oxo-1(2H)-pyridyl]-N,N,N',N'-tetramethyluronium tetrafluoroborate, {{[(1-cyano-2-ethoxy-2-oxoethylidene)amino]oxy}-4-morpholinomethylene}dimethylammonium hexafluorophosphate, 2-chloro-1,Examples of condensing agents include 3-dimethylimidazolinium hexafluorophosphate, 1-(chloro-1-pyrrolidinylmethylene)pyrrolidinium hexafluorophosphate, 2-fluoro-1,3-dimethylimidazolinium hexafluorophosphate, fluoro-N,N,N',N'-tetramethylformamidinium hexafluorophosphate, 1-hydroxybenzotriazole, 1-hydroxy-7-azabenzotriazole, N-hydroxysuccinimide, and N,N'-disuccinimidyl carbonate; however, 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and N,N'-dicyclohexylcarbodiimide are preferred due to their high reaction yield. 【0033】 The base or condensing agent may be used individually or in any ratio. Using a base is preferable, and using triethylamine is more preferable, in terms of high reaction yield. The equivalent amounts of these additives relative to the amine compound (3a) are preferably in the range of 1.5 to 3.0 equivalents and more preferably in the range of 2.0 to 2.5 equivalents when m is 2, in terms of good reaction yield of the heterocyclic compound (1a) in this embodiment. When m is 3, it is preferably in the range of 2.0 to 4.0 equivalents and more preferably in the range of 2.5 to 3.5 equivalents. When m is 4, it is preferably in the range of 4.0 to 6.0 equivalents. When m is 5, it is preferably in the range of 6.0 to 7.0 equivalents. When m is 6, it is preferably in the range of 7.0 to 8.0 equivalents. 【0034】 Step 1 can be carried out in a solvent. Examples of the solvent include inorganic acid solvents such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; organic acid solvents such as formic acid, acetic acid, trifluoroacetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, methanesulfonic acid, and trifluoromethanesulfonic acid; ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, tetrahydrofuran, and 1,4-dioxane; halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, and chlorobenzene; and aprotic polar solvents such as dimethylformamide, dimethyl sulfoxide, dimethylimidazolidinone, and hexamethyl phosphate triamide. These may be used individually or mixed in any ratio. There are no particular restrictions on the amount of solvent used. Of these, dichloromethane, tetrahydrofuran, 1,4-dioxane, and chloroform are preferred in terms of high reaction yield, and dichloromethane is more preferred in terms of economy and ease of post-treatment. 【0035】 Step 1 can be carried out at a temperature appropriately selected from -80°C to 100°C, but it is preferable to carry it out at a temperature appropriately selected from -20°C to 60°C in order to obtain a high reaction yield of the heterocyclic compound (1a). 【0036】 The reaction conditions in step 1 are not particularly limited. For example, the heterocyclic compound (1a) of this embodiment can be obtained in good yield by applying the reaction conditions disclosed in Examples 2 and 4 or the reaction conditions for amidation reactions that are well known to those skilled in the art. 【0037】 The heterocyclic compound (1b) included in the heterocyclic compound (1) of this embodiment (hereinafter sometimes referred to as "heterocyclic compound (1b)") can be produced by reacting an amine compound represented by formula (3b) and a compound represented by formula (4b) (hereinafter sometimes referred to as "amine compound (3b)" and "compound (4b)", respectively) in the presence of at least one additive selected from the group consisting of acids, bases, and condensing agents, as shown in step 2 below. [ka] In the formula, X 1 Ar 1 , R 1 , R 3 m, n, and ring A are the same as above. 【0038】 The compounds represented by amine compound (3b) can be synthesized, for example, based on methods disclosed in the literature (International Publication No. 2012 / 148090A1; International Publication No. 2019 / 072143A1; Chemistry-A European Journal, 2006, 12, 4241; Journal of the Chemical Society, Perkin Transactions 1, 2001, 7, 1045; Journal of the American Chemical Society, 2002, 124, 1364; Journal of the American Chemical Society, 2005, 127, 13567; Journal of the American Chemical Society, 2000, 122, 9993; Tetrahedron, 2020, 76, 131283), or commercially available products may be used. 【0039】 The compound represented by formula (4b) can be synthesized, for example, by methods disclosed in the literature (International Publication No. 2012 / 141293A2; International Publication No. WO2008 / 041636A2), or commercially available products may be used. 【0040】 In step 2, the equivalent amount of amine compound (3b) relative to compound (4b) is preferably in the range of 1.5 to 3.0 equivalents, and more preferably in the range of 2.0 to 2.5 equivalents, when m is 2, in order to obtain a good reaction yield of the heterocyclic compound (1b) in this embodiment. When m is 3, the equivalent amount of amine compound (3b) relative to compound (4b) is preferably in the range of 2.0 to 4.0 equivalents, and more preferably in the range of 2.5 to 3.8 equivalents. When m is 4, the equivalent amount of amine compound (3b) relative to compound (4b) is preferably in the range of 4.0 to 5.0 equivalents. When m is 5, the equivalent amount of amine compound (3b) relative to compound (4b) is preferably in the range of 5.0 to 6.0 equivalents. When m is 6, the equivalent amount of amine compound (3b) relative to compound (4b) is preferably in the range of 6.0 to 7.0 equivalents. 【0041】 Step 2 can be carried out in the presence of an acid. Examples of the acid include inorganic acid solvents such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; and organic acids such as formic acid, acetic acid, trifluoroacetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, oxalic acid, methanesulfonic acid, and trifluoromethanesulfonic acid. Acetic acid or propionic acid are preferred because they offer a high reaction yield. These may be used individually or mixed in any ratio, and there are no particular restrictions on the amount used. 【0042】 Step 2 can be carried out in the presence of a base. Examples of such bases include organic bases such as triethylamine, pyridine, 4-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undeca-7-ene, tetramethylethylenediamine, and 1,4-diazabicyclo[2.2.2]octane; metal hydroxides such as sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, and barium hydroxide; metal carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate; metal acetates such as potassium acetate and sodium acetate; metal phosphates such as potassium phosphate and sodium phosphate; metal fluoride salts such as sodium fluoride, potassium fluoride, and cesium fluoride; and metal alkoxides such as sodium methoxide, potassium methoxide, sodium ethoxide, potassium isopropyl oxide, potassium tert-butoxide, and sodium tert-butoxide. Triethylamine, pyridine, or 4-dimethylaminopyridine are preferred in terms of high reaction yield. 【0043】 Step 2 can be carried out in the presence of a condensing agent. The condensing agent may be 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, N,N'-carbonyldiimidazole, 1,1'-carbonyldi(1,2,4-triazole), 4-(4,6-dimethoxy-1,3,5-triazine-2-yl)-4-methylmorpholinium chloride n hydrate, or 1H-benzotriazole-1-yl Bromotris(dimethylamino)phosphonium hexafluorophosphate, 1H-benzotriazole-1-yloxytripyrrolidinophosphonium hexafluorophosphate, (7-azabenzotriazole-1-yloxy)tripyrrolidinophosphonium hexafluorophosphate, chlorotripyrrolidinophosphonium hexafluorophosphate, bromotris(dimethylamino)phosphonium hexafluorophosphate, 3-(diethoxyphosphoryloxy)-1,2,3-benzotriazine-4(3H)-one, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, O-(N-succinimidyl)-N,N,N',N'-tetramethyluronium tetrafluoroborate, O-(N-succinimidyl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, O-(3,4-dihydro-4-oxo-1,2,3-ben Zotriazin-3-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate, S-(1-oxide-2-pyridyl)-N,N,N',N'-tetramethylthiuronium tetrafluoroborate, O-[2-oxo-1(2H)-pyridyl]-N,N,N',N'-tetramethyluronium tetrafluoroborate, {{[(1-cyano-2-ethoxy-2-oxoethylidene)amino]oxy}-4-morpholinomethylene}dimethylammonium hexafluorophosphate, 2-chloro-1,Condensing agents such as 3-dimethylimidazolinium hexafluorophosphate, 1-(chloro-1-pyrrolidinylmethylene)pyrrolidinium hexafluorophosphate, 2-fluoro-1,3-dimethylimidazolinium hexafluorophosphate, fluoro-N,N,N',N'-tetramethylformamidinium hexafluorophosphate, 1-hydroxybenzotriazole, 1-hydroxy-7-azabenzotriazole, N-hydroxysuccinimide, and N,N'-disuccinimidyl carbonate can be exemplified, and 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and N,N'-dicyclohexylcarbodiimide are preferred in terms of high reaction yield. 【0044】 The acid, base, or condensing agent may be used individually or in any ratio. Using a base is preferable in that it provides a high reaction yield. The equivalent amounts of these additives relative to the amine compound (3b) are preferably in the range of 1.5 to 3.0 equivalents when m is 2, when m is 3, when m is 3, when m is 4, when m is 4, when m is 4, when m is 5, when m is 6, when m is 6, when m is 7.0 to 8.0 equivalents. 【0045】 Step 2 can be carried out in a solvent. Examples of the solvent include ethers such as diethyl ether, diisopropyl ether, methyl-tert-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, tetrahydrofuran, and 1,4-dioxane; halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, and chlorobenzene; and aprotic polar solvents such as dimethylformamide, dimethyl sulfoxide, dimethylimidazolidinone, and hexamethyl phosphate triamide. These may be used individually or mixed in any ratio. There are no particular restrictions on the amount of solvent used. Of these, acetic acid or propionic acid are more preferred in terms of high reaction yield. 【0046】 Step 2 can be carried out at a temperature appropriately selected from -80°C to 200°C, but it is preferable to carry it out at a temperature appropriately selected from -20°C to 150°C in order to obtain a high reaction yield of the heterocyclic compound (1a). 【0047】 The reaction conditions in step 2 are not particularly limited. For example, the heterocyclic compound (1a) of this embodiment can be obtained in good yield by applying the reaction conditions disclosed in Examples 1, 3, and 5 or known imidation reaction conditions. <Luminescent materials> The luminescent material of this embodiment includes a heterocyclic compound represented by formula (1) above. The luminescent material of this embodiment exhibits the effect of emitting light in both a solution state dissolved in a solvent and a solid state. 【0048】 The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In addition, 1 A Bruker ASCENDHD (400 MHz; manufactured by Bruker) was used to measure the H-NMR spectrum. 1The 1H-NMR spectrum was measured using trifluoroacetic acid-d1 (TFA-d1) or deuterated chloroform (CDCl3) as the measurement solvent, with tetramethylsilane (TMS) as the internal standard. 【0049】 Example 1: Heterocyclic compound (A-1) [ka] Under an argon atmosphere, 4'-amino-2,2':6',2''-terpyridine (0.42 g, 1.7 mmol) and pyromellitic anhydride (0.17 g, 0.80 mmol) were added to propionic acid (20 mL), and the mixture was stirred at 140°C for 20 hours. The precipitated solid was then filtered, washed with methanol, and vacuum-dried to obtain the target compound (A-1) (yield 0.45 g, yield 83%). 1 H-NMR(TFA-d1)δ(ppm)9.10-9.04(m,8H),8.83-8.72(m,8H),8.87(s,2H),8.15(t,J=6.3Hz,4H). 【0050】 Example 2: Heterocyclic compound (B-1) [ka] Under an argon atmosphere, 4''-amino-2,2':6',2''-terpyridine (0.042 g, 0.17 mmol) and triethylamine (0.017 g, 0.17 mmol) were dissolved in dichloromethane (2 mL), and then terephthaloyl chloride (0.16 g, 0.080 mmol) was added and the mixture was stirred at room temperature for 12 hours. The precipitated solid was then filtered, washed with methanol, and vacuum-dried to obtain the target compound (B-1) (yield 0.010 g, yield 20%). 1 H-NMR(TFA-d1)δ(ppm)9.12-9.00(m,8H),8.82-8.67(m,8H),8.18-8.08(m,8H). 【0051】 Example 3: Heterocyclic compound (B-11) [ka] Under an argon atmosphere, 4'-amino-2,2':6',2''-terpyridine (0.49 g, 1.5 mmol) and 1,4,5,8-naphthalenetetracarboxylic dianhydride (0.15 g, 0.56 mmol) were added to propionic acid (10 mL), and the mixture was stirred at 150 °C for 24 hours. The precipitated solid was then filtered, washed with methanol, and vacuum-dried to obtain the target compound (B-11) (yield 0.50 g, yield 88%). 1 H-NMR(TFA-d1)δ(ppm)9.12(d,J=6.6Hz,4H),9.03(s,4H),8.92(d,J=7.9Hz,4H),8. 85-8.76(m,8H),8.20(t,J=6.6Hz,4H),8.10(d,J=7.9Hz,4H),7.70(d,J=7.9Hz,4H). 【0052】 Example 4: Heterocyclic compound (C-2) [ka] Under an argon atmosphere, 4-([2,2':6',2''-terpyridine]-4'-yl)aniline (1.5 g, 4.6 mmol) and trimethylamine (0.47 g, 4.6 mmol) were dissolved in dichloromethane (60 mL), and then trimesic acid chloride (0.32 g, 1.5 mmol) was added and the mixture was stirred at room temperature for 12 hours. The precipitated solid was then filtered, washed with methanol, and vacuum-dried to obtain the target compound (D-2) (yield 1.11 g, yield 65%). 1 H-NMR(TFA-d1)δ(ppm)10.2-10.0(m,9H),9.93(d,J=8.8H,6H),9.89-9.80(m,12H),9.23(t,J=6.5Hz,6H),9.15-8.95(m,12H). 【0053】 Example 5: Heterocyclic compound (B-16) [ka] Under an argon atmosphere, 4'-amino-2,2':6',2''-terpyridine (0.097 g, 0.30 mmol) and 3,4,9,10-perylenetetracarboxylic dianhydride (0.059 g, 0.15 mmol) were added to imidazole (2.0 g), and the mixture was stirred at 110°C for 24 hours. The precipitated solid was then filtered, washed with methanol and acetone, and vacuum-dried to obtain the target compound (B-16) (yield 0.060 g, yield 40%). 1 H-NMR(TFA-d1)δ(ppm)9.11(d,J=5.5Hz,4H),9.03-8.75(m,20H),8.19(d,J=6.5Hz,4H),8.10(d,J=8.6Hz,4H),7.70(d,J=8.6Hz,4H). 【0054】 Synthesis Reference Example 1: Heterocyclic Compound (A-100) [ka] Under an argon atmosphere, 4-([2,2':6',2''-terpyridine]-4'-yl)aniline (0.49 g, 1.5 mmol) and pyromellitic anhydride (0.16 g, 0.73 mmol) were added to acetic acid (25 mL), and the mixture was stirred at 110°C for 12 hours. After cooling to room temperature, water was added, and the precipitated solid was filtered off. The mixture was then washed with methanol and vacuum-dried to obtain the target compound (A-100) (yield 0.38 g, yield 62%). 1 H-NMR(CDCl3)δ(ppm)8.80(s,4H),8.75(d,J=6.0Hz,4H),8.69(d,J=6.0Hz,4H),8.56(s,2H) ,8.10(d,J=8.0Hz,4H),7.90(t,J=6.0Hz,4H),7.69(d,J=8.0Hz,4H),7.38(d,J=6.0Hz,4H). 【0055】 Synthesis Reference Example 2: Heterocyclic Compound (B-100) [ka] Under an argon atmosphere, 4-([2,2':6',2''-terpyridine]-4'-yl)aniline (1.0 g, 3.3 mmol) and triethylamine (0.66 g, 6.6 mmol) were dissolved in dichloromethane (100 mL), and then terephthaloyl chloride (0.33 g, 1.6 mmol) was added and the mixture was stirred at room temperature for 12 hours. The precipitated solid was then filtered, washed with methanol, and vacuum-dried to obtain the target compound (B-100) (yield 1.06 g, yield 85%). 1 H-NMR(TFA-d1)δ(ppm):9.99(d,J=5.8H,4H),9.68(d,J=8.2H,4H),9.62-9.53(m,8H),8.98(t,J=6.9Hz,4H),8.91(s,4H),8.78-8.67(m,8H). 【0056】 <Evaluation of the luminescence of heterocyclic compounds> The emission spectrum of (C-2) was measured using a fluorescence spectrophotometer (JASCOFP-8500, manufactured by JASCO Corporation; excitation bandwidth: 5 nm, fluorescence bandwidth: 5 nm, response: 10 msec, sensitivity: Manual, scanning mode: continuous scan, scanning speed: 100 nm / min). A DMF solution of (C-2) was used for the measurement. The emission spectrum when excited at an excitation wavelength of 400 nm is shown in Figure 1 and will be described later. 【0057】 The DMF solution of (C-2) was found to have a peak at 523 nm and exhibit yellow emission. In other words, it was confirmed that the present invention (C-2) can achieve the expression of various emission colors.

Claims

[Claim 1] A heterocyclic compound represented by formula (1). 【Chemistry 1】 [In formula (1), Ring A represents an aromatic ring with 5 to 24 nuclear atoms, which may have substituents. R １ Each of these independently represents either an oxygen atom or a sulfur atom. R ２ Each of these independently represents a hydrogen atom, a linear, branched, or cyclic hydrocarbon group having 1 to 4 carbon atoms, or a linear, branched, or cyclic fluorine-containing hydrocarbon group having 1 to 4 carbon atoms. Also, R ２ It combines with ring A to form the following equation (2) 【Chemistry 2】 (In the formula, R １ This is synonymous with the above. R ３ Each of these independently represents either an oxygen atom or a sulfur atom. * indicates a bond position. A ring containing the substructure shown by ) can be formed. X １ Each of these independently represents a nitrogen atom or an optionally substituted carbon atom. Y １ Each of these independently represents a divalent organic group having 5 to 14 nuclear atoms, which may have substituents. Each n independently represents either 0 or 1. Ar １ Each of these independently represents a heteroaromatic group having 5 to 14 nuclear atoms, including a nitrogen atom, which may have substituents. m represents an integer between 2 and 6. However, the compounds shown in the following formulas (A-100) and (B-100) are not included. 【Transformation 3】 [Claim 2] Ar １ The heterocyclic compound according to claim 1, wherein Ar is each independently a pyridyl group, an imidazolyl group, a pyrimidinyl group, a coumarinyl group or a triazinyl group, which may each independently have a substituent. [Claim 3] R ２ R combines with ring A to form a ring containing the substructure shown in formula (2), and in the ring structure R １ and R ３ The heterocyclic compound according to claim 1, wherein both atoms are oxygen atoms. [Claim 4] R １ is an oxygen atom, R ２ The heterocyclic compound according to claim 1, wherein is a hydrogen atom. [Claim 5] The heterocyclic compound according to claim 1, wherein in formula (1), ring A is a substituted benzene ring, pyridine ring, pyrazine ring, naphthalene ring, coumarin ring, quinoxaline ring, anthracene ring, tetracene ring, triphenylene ring, perylene ring, or coronene ring. [Claim 6] The heterocyclic compound according to claim 1, wherein n is 0. [Claim 7] The heterocyclic compound according to claim 1, wherein the heterocyclic compound represented by formula (1) is at least one selected from the group consisting of compounds represented by formulas (A-1), (B-1), (B-11), (B-16), and (C-2). 【Chemistry 4】 [Claim 8] Formula (3a) 【Transformation 5】 (In formula (3a), X １ Each of these independently represents a nitrogen atom or an optionally substituted carbon atom. Y １ This represents a divalent organic group having 5 to 14 nuclear atoms, which may have substituents. Each n independently represents either 0 or 1. Ar １ Each of these independently represents a heteroaromatic group having 5 to 14 nuclear atoms, including a nitrogen atom, which may have substituents. R ４ Each of these independently represents a hydrogen atom, a linear, branched, or cyclic hydrocarbon group having 1 to 4 carbon atoms, or a linear, branched, or cyclic fluorine-containing hydrocarbon group having 1 to 4 carbon atoms.) and the amine compound represented by formula (4a) 【Transformation 6】 (In formula (4a), Ring A represents an aromatic ring with 5 to 24 nuclear atoms, which may have substituents. R １ Each of these independently represents either an oxygen atom or a sulfur atom. Each Z independently represents either a halogen atom or a hydroxyl group. m represents an integer from 2 to 6. The compound represented by formula (1a) is reacted with the compound represented by formula (1a) in the presence of at least one additive selected from the group consisting of a base and a coupling agent. 【Transformation 7】 (In formula (1a), Ar １ , X １ , R １ , R ４ , Y １ A method for producing a heterocyclic compound represented by (where m, n, and ring A are as defined above). [Claim 9] Formula (3b) 【Transformation 8】 (In formula (3b), X １ Each of these independently represents a nitrogen atom or an optionally substituted carbon atom. Y １ This represents a divalent organic group having 5 to 14 nuclear atoms, which may have substituents. Each n independently represents either 0 or 1. Ar １ Each of these independently represents a heteroaromatic group having 5 to 14 nuclei containing a nitrogen atom, which may have substituents.) and formula (4b) 【Chemistry 9】 (In formula (4b), Ring A represents an aromatic ring with 5 to 24 nuclear atoms, which may have substituents. R １ and R ３ Each of these independently represents either an oxygen atom or a sulfur atom. m represents an integer from 2 to 6. The compound represented by formula (1b) is reacted with the compound represented by formula (1b) in the presence of at least one additive selected from the group consisting of acids, bases, and condensing agents. 【Chemistry 10】 (In formula (1b), Ar １ , X １ , R １ , R ３ , Y １ A method for producing a heterocyclic compound represented by (where m, n, and ring A are as defined above). [Claim 10] A luminescent material containing the heterocyclic compound described in claim 1.

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