Method for producing ligand and method for producing triaryl amine compound

Abstract

To provide a method for producing a ligand in high yield while reducing production costs.SOLUTION: A method for producing a ligand includes: a reaction step for subjecting, for example, an isoquinoline compound and a naphthalene compound to the following reaction, in the presence of a condensing agent, to synthesize a ligand; and a purification step for purifying the ligand derived from the reaction step by a chromatographic technique employing a developing solution including a halogen-based solvent.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing a ligand. The present invention also relates to a method for producing a triarylamine compound. [Background technology]

[0002] Triarylamine compounds are chemical substances that are widely used as essential substances in optical and electronic devices such as organic light-emitting diodes, organic solar cells, and organic field-effect transistors, as well as essential substances in pharmaceutical scaffolds.

[0003] Triarylamine compounds have traditionally been produced by the "carbon-nitrogen cross-coupling reaction" using a Pd-based catalyst, but there has been a demand for alternative catalysts due to their scarcity, high prices, toxicity, etc.

[0004] In order to meet the above demands, attention has been focused on Cu-based catalysts and Fe-based catalysts, and a method for producing a triarylamine compound using such a catalyst and a catalytic ligand has been reported. Non-Patent Document 1 reports that, as an alternative to a Pd-based catalyst, a Cu-based catalyst can be combined with a specific catalytic ligand to couple a diarylamine compound with an aryl bromide to synthesize a triarylamine compound. Furthermore, Non-Patent Document 1 describes a method for producing the ligand, and states that the yield is 70%. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] Sasa Li, Xia Huang et al., Organic Letter, 2022, 24, pp.5817-5824 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the method for producing the ligand described in Non-Patent Document 1 leaves room for improvement in terms of the yield of the ligand.

[0007] Therefore, an object of the present invention is to provide a method for producing a ligand which is excellent in yield and capable of reducing production costs. [Means for solving the problem]

[0008] As a result of intensive research, the present inventors have now found that the yield of the ligand can be improved by devising a reaction step and / or a purification step in which an isoquinoline compound represented by formula (1) and a naphthalene compound represented by formula (2) are reacted in the presence of a condensing agent to obtain a ligand.

[0009] That is, according to the present invention, the following inventions are provided. [1] The following formula (1): [ka] (In formula (1), R 1 may be bonded to any carbon atom on the ring and represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a halogenoalkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, a hydroxy group, a mercapto group, a nitro group, an amino group, an aminoalkylthio group, or a heteroaryl group. and an isoquinoline compound represented by the formula: The following formula (2): [ka] (In formula (2), R 2 may be bonded to any carbon atom on the ring and represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a halogenoalkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, a hydroxy group, a mercapto group, a nitro group, an amino group, an aminoalkylthio group, or a heteroaryl group. and a naphthalene compound represented by the formula: The following formula (3): [ka] (In formula (3), R 1 is the same as in formula (1), and R 2 is the same as formula (2). A reaction step of synthesizing a ligand represented by the formula: A purification step of purifying the ligand represented by formula (3) obtained in the reaction step by a chromatography method using a developing solution containing a halogen-based solvent. A method for producing a ligand, comprising: [2] The method according to [1], wherein the reaction temperature in the reaction step is 45 to 85°C and the reaction time is 1 to 6 hours. [3] Formula (4): [ka] (In formula (4), Z is -C(R 5 )(R 6 )- or an oxygen atom, or Z is absent, where Z is -C(R 5 )(R 6 )- or an oxygen atom, the dashed lines α and β each represent a single bond, and when Z is absent, the dashed lines α and β each do not exist. R 3 , R 4 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. R 5 , R 6 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. and a diarylamine compound represented by the formula: The following formulas (5-1) to (5-3): [ka] [ka] In formula (5-2), Y represents a carbonyl group, a sulfonyl group, or a phenylphosphine oxide group. m represents 0 or 1. The dashed line γ is absent or represents a single bond. [ka] and an aryl bromide compound represented by a formula selected from the group consisting of Reacting in the presence of a Cu-based catalyst and a ligand obtained by the production method according to [1] or [2], The following formulas (6-1) to (6-3): [ka] [ka] [ka] (Z, R in formulas (6-1), (6-2) and (6-3) 3 , R 4 , dashed lines α and β are the same as in formula (4), and Y, m, and dashed line γ are the same as in formula (5-2). A method for producing a triarylamine compound, comprising a reaction step of synthesizing a triarylamine compound represented by a formula selected from the group consisting of: [4] R 1 and R 2 The method according to any one of [1] to [3], wherein [5] In the diarylamine compound represented by formula (4), Z is -C(R 5 )(R 6 )-indicated, R 3 and R 4 respectively represent hydrogen atoms, R 5 and R 6 each represents an alkyl group having 1 to 6 carbon atoms, The aryl bromide compound is a compound represented by formula (5-1), The triarylamine compound is a compound represented by formula (6-1): The manufacturing method described in [3] or [4]. Effect of the Invention

[0010] In the reaction step and / or purification step in which an isoquinoline compound represented by formula (1) and a naphthalene compound represented by formula (2) are reacted in the presence of a condensing agent to obtain a ligand represented by formula (3), the yield of the ligand can be improved by setting specific conditions. This is advantageous in that a triarylamine compound can be produced using the ligand obtained by the present invention. [Brief description of the drawings]

[0011] [Figure 1] 1 shows the 13C-NMR spectrum of the ligand obtained in Example 1. [Diagram 2] 13C-NMR spectrum of the triarylamine compound obtained in Example 2 is shown. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] [Method for producing catalyst ligand] The method for producing a catalytic ligand of the present invention includes a reaction step of synthesizing a ligand represented by formula (3) by reacting an isoquinoline compound represented by formula (1) with a naphthalene compound represented by formula (2) in the presence of a condensing agent, and a purification step.

[0013] (Isoquinoline compounds) The isoquinoline compound used in the present invention is represented by the following formula (1): [ka] (In formula (1), R 1 may be bonded to any carbon atom on the ring and represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a halogenoalkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, a hydroxy group, a mercapto group, a nitro group, an amino group, an aminoalkylthio group, or a heteroaryl group. It is expressed as:

[0014] R 1 The "halogen atom" in the above formula includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and is preferably a chlorine atom or a bromine atom.

[0015] R 1 The "alkyl group having 1 to 6 carbon atoms" in the above formula (I) is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms (C 1-6 An alkyl group having 1 to 4 carbon atoms is preferable, and an alkyl group having 1 to 2 carbon atoms is more preferable. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, an isohexyl group, a cyclopropyl group, etc. Among these, those having 1 to 3 carbon atoms are preferred, and a methyl group or an ethyl group is more preferred.

[0016] R 1 The "halogenoalkyl group" in the above formula is a halogeno C 1-8 Alkyl groups are preferred, and halogeno groups are preferred. 1-6 An alkyl group is more preferable. Specific examples thereof include a chloromethyl group, a fluoromethyl group, a chloroethyl group, a fluoroethyl group, and a trifluoromethyl group.

[0017] R 1 The "alkenyl group" in the formula (I) is a linear or branched alkenyl group having 2 to 8 carbon atoms (C 2-8 Alkenyl groups having 2 to 6 carbon atoms are preferred. Specific examples include vinyl, allyl, isopropenyl, 2-methallyl, 2-butenyl, and 3-butenyl groups. Of these, those having 2 to 4 carbon atoms are preferred.

[0018] R 1 The "alkynyl group" in the formula (I) is a straight-chain or branched-chain alkynyl group having 2 to 8 carbon atoms (C 2-8Alkynyl groups having 2 to 6 carbon atoms are preferred. Specific examples include an ethynyl group, a propynyl group, and a butynyl group. Of these, those having 2 to 4 carbon atoms are preferred.

[0019] R 1 The "alkoxy group" in the above formula is a linear or branched alkoxy group having 1 to 8 carbon atoms (C 1-8 Alkoxy groups) are preferred, with alkoxy groups having 1 to 6 carbon atoms being preferred, and alkoxy groups having 1 to 3 carbon atoms being more preferred. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, and tert-butoxy groups. Of these, those having 1 to 3 carbon atoms are preferred, and methoxy or ethoxy groups are more preferred.

[0020] R 1 The "alkylthio group" in the above formula is a linear or branched alkylthio group having 1 to 8 carbon atoms (C 1-8 An alkylthio group having 1 to 6 carbon atoms is preferable. Specific examples include a methylthio group, an ethylthio group, an isopropylthio group, and an n-propylthio group.

[0021] R 1 The "aminoalkylthio group" in 1-8 Alkylthio groups are included, and amino C 1-6 An alkylthio group is preferred, and specific examples thereof include an aminomethylthio group, an aminoethylthio group, and an aminopropylthio group.

[0022] R 1 The "heteroaryl group" in the above formula (1) includes a 5- or 6-membered heteroaryl group having 1 to 3 atoms selected from a nitrogen atom, an oxygen atom, and a sulfur atom. Specific examples include a pyrrolyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a pyridyl group, a pyrimidinyl group, and a pyrazyl group. Of these, a furyl group, a thienyl group, and a pyridyl group are preferred.

[0023] R in formula (1) 1 is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a halogenoalkyl group, an alkenyl group, an alkynyl group or an alkoxy group, and more preferably a hydrogen atom.

[0024] R 1 may be substituted at any of the 1-, 3-, 4-, 5-, 6-, 7- and 8-positions of the isoquinoline ring, and is preferably substituted at the 5- or 6-position.

[0025] (Naphthalene compounds) The naphthalene compound used in the present invention is represented by the following formula (2): [ka] (In formula (2), R 2 may be bonded to any carbon atom on the ring and represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a halogenoalkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, a hydroxy group, a mercapto group, a nitro group, an amino group, an aminoalkylthio group, or a heteroaryl group. It is expressed as:

[0026] R in Equation (2) 2 The halogen atom, the alkyl group having 1 to 6 carbon atoms, the halogenoalkyl group, the alkenyl group, the alkynyl group, the alkoxy group, the alkylthio group, the aminoalkylthio group and the heteroaryl group in the above formula (1) are 1 In the above formula, the halogen atom, the alkyl group having 1 to 6 carbon atoms, the halogenoalkyl group, the alkenyl group, the alkynyl group, the alkoxy group, the alkylthio group, the aminoalkylthio group and the heteroaryl group are the same as those mentioned above.

[0027] R in formula (1) 2is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a halogenoalkyl group, an alkenyl group, an alkynyl group or an alkoxy group, and more preferably a hydrogen atom.

[0028] R 2 may be substituted at any of the 3-, 4-, 5-, 6-, 7- and 8-positions of the naphthalene ring, and is preferably substituted at the 6- or 7-position.

[0029] The amount of the naphthalene compound represented by formula (2) used is not particularly limited as long as it does not impede the effects of the present invention, but may be, for example, 0.3 to 2.0 times the molar amount, and preferably 0.5 to 1.5 times the molar amount, of the isoquinoline compound represented by formula (1).

[0030] (Condensing Agent) The condensing agent used in the reaction step of the isoquinoline compound represented by formula (1) and the naphthalene compound represented by formula (2) is not particularly limited as long as it is one that is used in normal amidation, and examples of the condensing agent include alkyl chloroformate (e.g., isobutyl chloroformate, ethyl chloroformate), N-alkylmorpholine (e.g., 4-methylmorpholine, 4-ethylmorpholine), carbodiimide (e.g., N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride), uronium, phosphonium, 2-alkyl-1-alkyl Examples of the chloroformate include 2-isobutoxy-1-isobutoxycarbonyl-1,2-dihydroquinoline, 2-alkoxy-1-alkoxycarbonyl-1,2-dihydroquinoline (e.g., 2-ethoxy-1-ethoxycarbonyl-1,2-dihydroquinoline), and combinations thereof. Preferred are alkyl chloroformate, 4-ethylmorpholine, and combinations thereof, and more preferred are isobutyl chloroformate, 4-ethylmorpholine, and combinations thereof.

[0031] The amount of the condensing agent used is not particularly limited as long as it does not impede the effects of the present invention, but may be, for example, 1.0 to 6.0 times by mole, and preferably 2.0 to 4.0 times by mole, relative to the isoquinoline compound represented by formula (1). When a combination of multiple compounds is used as the condensing agent, the amount of the condensing agent used means the total amount of the multiple compounds.

[0032] (ligand) The reaction product (ligand) synthesized in the above reaction step is represented by the following formula (3): [ka] It is a ligand represented by the formula:

[0033] In formula (3), R 1 is the same as in formula (1), and R 2 is synonymous with equation (2).

[0034] A preferred embodiment of the ligand represented by the above formula (3) is a compound represented by the following formula (3-1). [ka]

[0035] In the method for producing a ligand of the present invention, R 1 and R of the naphthalene compound represented by formula (2) 2 According to a preferred embodiment of the combination with R 1 and R 2 each represents a hydrogen atom.

[0036] (Reaction conditions for the reaction step of an isoquinoline compound and a naphthalene compound) The temperature when reacting the isoquinoline compound represented by formula (1) with the naphthalene compound represented by formula (2) in the presence of a condensing agent is not particularly limited, but from the viewpoint of economical reaction costs, it is preferably 45 to 85°C, more preferably 55 to 75°C.

[0037] The time for reacting the isoquinoline compound represented by formula (1) and the naphthalene compound represented by formula (2) in the presence of a condensing agent is not particularly limited, but from the viewpoint of economical reaction costs, it is, for example, 1 to 6 hours, and preferably 2 to 5 hours.

[0038] The reaction step of the isoquinoline compound and the naphthalene compound may be carried out in the presence of a solvent. The solvent is not particularly limited, and a conventional organic solvent can be used. As the organic solvent, for example, ether solvents such as tetrahydrofuran (THF), dioxane, diethyl ether, glyme, diglyme, etc.; aromatic hydrocarbon solvents such as benzene, toluene, o-, m-, p-xylene, mesitylene, etc.; aliphatic hydrocarbon solvents such as hexane and cyclohexane; halogen-based solvents such as dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, o-dichlorobenzene, etc.; fluorine-containing organic solvents such as hexafluorobenzene, m-bis(trifluoromethyl)benzene, p-bis(trifluoromethyl)benzene, α,α,α-trifluoromethylbenzene, dichloropentafluoropropane, etc. can be used. Among these, tetrahydrofuran, dioxane, etc., and mixtures thereof are preferred.

[0039] (Ligand purification process) The method for producing the ligand of the present invention may further include a step of purifying the ligand synthesized above. The purification method is not particularly limited, and a conventionally known purification method can be applied. Examples of the purification method include a chromatographic method (also called chromatography), recrystallization, liquid separation, reduced pressure filtration, solvent distillation, washing with a solvent, ultrasonic washing, and combinations thereof. It is preferable to purify (preferably separate) by a chromatographic method using a developing solution containing a halogen-based solvent.

[0040] According to one embodiment of the present invention, from the viewpoint of improving the isolation yield, the purification step is preferably carried out by purifying (preferably, isolating) the ligand by a chromatography method (preferably, preparative chromatography or silica gel packed filtration method) among the above. In particular, a chromatography method (preferably, preparative chromatography or silica gel packed filtration method) using a developing solution containing a halogenated solvent is more preferable because it can improve the isolation yield by utilizing the solubility of the ligand in the halogenated solvent. Examples of halogen-based solvents include aliphatic halogenated solvents such as dichloromethane, chloroform, and 1,2-dichloroethane, and preferably dichloromethane. As a developing solution containing a halogen-based solvent, a mixture of a halogen-based solvent and hexane is more preferable. Conditions for preparative chromatography include, for example, the following conditions. Developing solvent: CH2Cl2 / hexane = 8 / 2 mixed solvent Column: normal phase silica gel (preferably Universal Column (Yamazen Co., Ltd.)) Equipment: Smart Flash AKROS (manufactured by Yamazen Co., Ltd.) Temperature: room temperature Detection wavelength: 254 nm

[0041] According to another embodiment of the present invention, when a chromatography method is adopted as the purification step, it is preferable to purify the ligand by recrystallization after the chromatography method. As a solvent used for recrystallization, for example, the same solvent as the developing solution of the above-mentioned chromatography method can be used. As a temperature for carrying out recrystallization, for example, -20 to 50°C can be mentioned, and preferably room temperature.

[0042] (Application) The ligand obtained by the method for producing a ligand of the present invention can be suitably used, for example, as a ligand for a metal catalyst, particularly as a catalytic ligand for a carbon-nitrogen cross-coupling reaction in a synthesis reaction of a triarylamine compound, preferably as a ligand for a Cu-based catalyst.

[0043] [Method of producing triarylamine compound] The method for producing a triarylamine compound according to the present invention comprises a reaction step of reacting a diarylamine compound represented by formula (4) with an aryl bromide compound represented by a formula selected from the group consisting of formulas (5-1) to (5-3) in the presence of a Cu-based catalyst and the above-mentioned ligand to synthesize a triarylamine compound represented by a formula selected from the group consisting of formulas (6-1) to (6-3).

[0044] (Diarylamine compounds) The diarylamine compound used in the present invention is represented by the following formula (4): [ka] (In formula (4), Z is -C(R 5 )(R 6 )- or an oxygen atom, or Z is absent, where Z is -C(R 5 )(R 6 )- or an oxygen atom, the dashed lines α and β each represent a single bond, and when Z is absent, the dashed lines α and β each do not exist. R 3 , R 4 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. R 5 , R 6 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. It is expressed as:

[0045] R 3 , R 4 , R 5 , R 6 The "alkyl group having 1 to 6 carbon atoms" in the above formula (I) is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms (C 1-6 An alkyl group having 1 to 4 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, an isohexyl group, a cyclopropyl group, etc. Among these, those having 1 to 3 carbon atoms are preferred, and a methyl group or an ethyl group is more preferred.

[0046] R 3 , R 4 The "alkoxy group having 1 to 6 carbon atoms" in the above formula (I) is a linear or branched alkoxy group having 1 to 6 carbon atoms (C 1-6 Alkoxy groups) are preferred, with alkoxy groups having 1 to 4 carbon atoms being preferred, and alkoxy groups having 1 to 3 carbon atoms being more preferred. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, and tert-butoxy groups. Of these, those having 1 to 3 carbon atoms are preferred, and methoxy or ethoxy groups are more preferred.

[0047] Z in formula (4) is preferably -C(R 5 )(R 6 )- or an oxygen atom, more preferably -C(R 5 )(R 6 )-.

[0048] R in Equation (4) 3 , R 4 is preferably R 3 , R 4 Both are hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, or alkoxy groups having 1 to 6 carbon atoms. More preferably, R 3 , R 4 Both are hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, or alkoxy groups having 1 to 4 carbon atoms, and more preferably, R 3 , R 4 Both are hydrogen atoms.

[0049] R in Equation (4) 5 , R 6 is preferably R 5 , R 6Both are an alkyl group having 1 to 6 carbon atoms or a hydrogen atom, and more preferably, R 5 , R 6 Both are alkyl groups having 1 to 4 carbon atoms, and more preferably, R 5 , R 6 Both are methyl groups.

[0050] In formula (4), Z, R 3 , R 4 , R 5 and R 6 According to a preferred embodiment of the combination of 5 )(R 6 )- or an oxygen atom, R 3 , R 4 Both are hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, or alkoxy groups having 1 to 4 carbon atoms, and R 5 , R 6 In formula (4), Z and R are each an alkyl group having 1 to 6 carbon atoms or a hydrogen atom. 3 , R 4 , R 5 and R 6 According to a more preferred embodiment of the combination of 5 )(R 6 )-wherein R 5 , R 6 Both are alkyl groups having 1 to 4 carbon atoms. 3 , R 4 Both are hydrogen atoms.

[0051] Preferred embodiments of the diarylamine compound represented by the above formula (4) include the compounds represented by the following formulas (4-1) to (4-3). [ka] [ka] [ka]

[0052] (Aryl bromide compounds) The aryl bromide compound used in the present invention is an aryl bromide compound represented by a formula selected from the group consisting of the following formulas (5-1) to (5-3). [ka] [ka] In formula (5-2), Y represents a carbonyl group, a sulfonyl group, or a phenylphosphine oxide group. m represents 0 or 1. The dashed line γ is absent or represents a single bond. [ka]

[0053] In formula (5-2), Y is preferably a carbonyl group.

[0054] In formula (5-2), when m is 1 and the dashed line γ is a single bond (i.e., when it is a fluorene ring), one bromo group may be substituted at any of the 1-, 2-, 3-, or 4-positions of the fluorene ring, and the other bromo group may be substituted at any of the 5-, 6-, 7-, or 8-positions of the fluorene ring. Preferably, one bromo group is substituted at the 3-position of the fluorene ring and the other bromo group is substituted at the 6-position of the fluorene ring, or one bromo group is substituted at the 2-position of the fluorene ring and the other bromo group is substituted at the 7-position of the fluorene ring. More preferably, one bromo group is substituted at the 3-position of the fluorene ring and the other bromo group is substituted at the 6-position of the fluorene ring. In formula (5-2), when m is 0 or 1 and the dashed line γ is not present, the two bromo groups may independently be substituted at any one of the 2-position (ortho-position), 3-position (meta-position), and 4-position (para-position) of each benzene ring, and preferably, both bromo groups are substituted at the 2-position of each benzene ring, both bromo groups are substituted at the 4-position of each benzene ring, or one bromo group is substituted at the 2-position of one benzene ring and the other bromo group is substituted at the 4-position of the other benzene ring.

[0055] According to a preferred embodiment of the combination of Y, m, dashed line γ, and the position of the bromo group in formula (5-2), Y is a carbonyl group, a sulfonyl group, or a phenylphosphine oxide group, m is 1, dashed line γ is absent, and both bromo groups are substituted at the 4-position of the respective benzene rings. According to another preferred embodiment of the combination of Y, m, dashed line γ, and the position of the bromo group in formula (5-2), Y is a carbonyl group, a sulfonyl group, or a phenylphosphine oxide group, m is 1, dashed line γ is a single bond, one bromo group is substituted at the 3-position of the fluorene ring, and the other bromo group is substituted at the 6-position of the fluorene ring. According to another preferred embodiment relating to the combination of Y, m, dashed line γ, and the position of the bromo group in formula (5-2), m is 0 (i.e., a single bond between the two benzene rings), the dashed line γ does not exist, and both bromo groups substitute at the 2-position of each benzene ring or substitute at the 4-position of each benzene ring.

[0056] A preferred embodiment of the aryl bromide compound represented by the above formula (5-2) is a compound represented by the following formula (5-2-1). [ka]

[0057] According to a preferred embodiment of the present invention, the aryl bromide compound is preferably an aryl bromide compound of formula (5-1) or formula (5-2), more preferably an aryl bromide compound of formula (5-1).

[0058] The amount of the aryl bromide compound represented by the formula selected from the group consisting of formulas (5-1) to (5-3) used is not particularly limited as long as it does not impair the effects of the present invention, and may be, for example, 0.3 to 1.5 times by mol, and preferably 0.5 to 1.2 times by mol, based on the diarylamine compound represented by formula (4).

[0059] (Cu-based catalyst) The Cu catalyst (copper catalyst) used in the reaction step of the diarylamine compound represented by formula (4) and the aryl bromide compound represented by any one of formulas (5-1) to (5-3) is not particularly limited as long as it is a catalyst capable of causing a carbon-nitrogen cross-coupling reaction between the aryl bromide compound and the diarylamine compound, and a conventionally known catalyst can be used. Examples of such Cu catalyst include copper iodide (preferably copper iodide (I) (CuI)), copper acetate (preferably copper acetate (II) (Cu(CH3COO)2)), copper chloride (preferably copper chloride (II) (CuCl2)), and copper bromide (preferably copper bromide (II) (CuBr2)), and preferably copper iodide.

[0060] The amount of the Cu-based catalyst used is not particularly limited as long as it does not impede the effects of the present invention, but may be, for example, 0.01 to 0.4 times by mol, and preferably 0.03 to 0.2 times by mol, based on the diarylamine compound represented by formula (4).

[0061] (ligand) The ligand used together with the Cu-based catalyst in the reaction step of the diarylamine compound represented by formula (4) and the aryl bromide compound represented by any one of formulas (5-1) to (5-3) is not particularly limited as long as it does not impair the effects of the present invention. From the viewpoint of improving the yield of the target product, however, the ligand represented by formula (3) is preferred.

[0062] The amount of the ligand used is not particularly limited as long as it does not impede the effects of the present invention, but may be, for example, 0.01 to 0.4 times by mol, and preferably 0.03 to 0.2 times by mol, based on the diarylamine compound represented by formula (4).

[0063] (base) According to one embodiment of the present invention, in the reaction step of the diarylamine compound represented by formula (4) with the aryl bromide compound represented by any one of formulas (5-1) to (5-3), it is preferable to further make a base exist from the viewpoint of improving the yield of the target product. Examples of such bases include inorganic bases, and preferably potassium phosphate (K3PO4), potassium carbonate (K2CO3), and cesium carbonate (Cs2CO3), and more preferably potassium phosphate (K3PO4).

[0064] The amount of the base used is not particularly limited as long as it does not impede the effects of the present invention, and may be, for example, 0.01 to 4.0 times by mol, and preferably 0.5 to 2.0 times by mol, based on the diarylamine compound represented by formula (4).

[0065] (Triarylamine compounds) The reaction product (triarylamine compound) synthesized in the above reaction step is represented by the following formulas (6-1) to (6-3): [ka] [ka] [ka] (Z, R in formulas (6-1), (6-2) and (6-3) 3 , R 4 , dashed lines α and β are defined as in formula (4), and Y, m, and dashed line γ are defined as in formula (5-2). The triarylamine compound is represented by a formula selected from the group consisting of:

[0066] Preferred embodiments of the triarylamine compounds represented by the above formulas (6-1) to (6-3) include the compounds represented by the following formulas (6-1-1) to (6-3-1). [ka] [ka] [ka]

[0067] In the method for producing a triarylamine compound of the present invention, preferred embodiments relating to the combination of a diarylamine compound represented by any one of formulas (4-1) to (4-3), an aryl bromide compound represented by any one of formulas (5-1), (5-2-1) and (5-3), and a triarylamine compound represented by any one of formulas (6-1-1) to (6-3-1) include a combination of a compound of formula (4-1), a compound of formula (5-1) and a compound of formula (6-1-1), a combination of a compound of formula (4-1) to (4-3), a compound of formula (5-2-1) and a compound of formula (6-2-1), and a combination of a compound of formula (4-3), a compound of formula (5-3) and a compound of formula (6-3-1).

[0068] (Reaction conditions for the reaction step of an aryl bromide compound and a diarylamine compound) The atmosphere in which the diarylamine compound represented by formula (4) and the aryl bromide compound represented by any one of formulas (5-1) to (5-3) are reacted in the presence of a Cu-based catalyst and a ligand is not particularly limited, but from the viewpoint of suppressing a decrease in activity of the catalyst due to moisture inclusion, an inert gas atmosphere is preferable, and a nitrogen or argon atmosphere is more preferable.

[0069] The temperature at which the diarylamine compound represented by formula (4) and the aryl bromide compound represented by any one of formulas (5-1) to (5-3) are reacted in the presence of a Cu-based catalyst and a ligand is not particularly limited, but from the viewpoint of improving the yield of the target product, it is preferably 50 to 200°C, more preferably 80 to 150°C.

[0070] The time for reacting the diarylamine compound represented by formula (4) with the aryl bromide compound represented by any one of formulas (5-1) to (5-3) in the presence of a Cu catalyst and a ligand is not particularly limited, but is, for example, 3 to 15 hours, preferably 6 to 12 hours. The completion of the reaction can be confirmed by TLC analysis.

[0071] The humidity when reacting the diarylamine compound represented by formula (4) with the aryl bromide compound represented by any one of formulas (5-1) to (5-3) in the presence of a Cu-based catalyst and a ligand is not particularly limited, but the humidity in the reaction system may be, for example, 100 ppm or less, preferably 50 ppm or less, more preferably 10 ppm or less, and may be 1 ppm or more. The oxygen concentration in the reaction system is not particularly limited, but for example, 100 ppm or less, preferably 50 ppm or less, more preferably 10 ppm or less, and may be 1 ppm or more. The method for controlling the water content and oxygen concentration in the reaction system is not particularly limited, and it is preferable to control them in a closed container such as a glove box.

[0072] When the diarylamine compound represented by formula (4) is reacted with the aryl bromide compound represented by any one of formulas (5-1) to (5-3) in the presence of a Cu catalyst and a ligand, the reaction may be carried out in the presence of a solvent. The solvent is not particularly limited and may be a conventional organic solvent, but is preferably an aprotic polar solvent, specifically sulfolane, dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), dimethylacetamide (DMA), etc., and is preferably sulfolane or N,N-dimethylformamide (DMF).

[0073] (Purification process of triarylamine compound) The method for producing the triarylamine compound of the present invention may further include a step of purifying the triarylamine compound synthesized above.The purification method is not particularly limited, and conventionally known purification methods can be applied.The purification method includes, for example, chromatography, recrystallization, liquid separation, reduced pressure filtration, solvent distillation, washing with a solvent, and ultrasonic washing.

[0074] According to one embodiment of the present invention, in terms of improving the isolation yield, the purification step is preferably carried out by purifying (preferably, preparative) the triarylamine compound by a chromatography method (preferably, preparative chromatography) among the above. The developing solution used in the chromatography method is not particularly limited, but preferably includes hexane, pentane, toluene, methylene chloride, ethyl acetate, etc., and combinations thereof, and more preferably a mixture of hexane and ethyl acetate. Conditions for preparative chromatography include, for example, the following conditions. Developing solvent: Hexane / Ethyl acetate = 7 / 3 mixed solvent Column: normal phase silica gel (preferably Universal Column (Yamazen Co., Ltd.)) Equipment: Smart Flash AKROS (manufactured by Yamazen Co., Ltd.) Temperature: room temperature Detection wavelength: 254 nm

[0075] (Application) The triarylamine compounds obtained by the production method of the present invention can be suitably used as materials for optical and electronic devices such as organic light-emitting diodes, organic solar cells, and organic field-effect transistors, and as pharmaceutical frameworks. EXAMPLES

[0076] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0077] [Example 1] <Production of Ligand (N-(2-Methyl-1-naphthalenyl)-1-isoquinolinecarboxamide)> To a solution of isoquinoline-1-carboxylic acid (1.039 g, 6 mmol, 1.0 equiv.) in 24 ml dehydrated tetrahydrofuran (THF), NEM (4-ethylmorpholine, 1.92 mL, 15 mmol, 2.5 equiv.) and isobutyl chloroformate (780 μL, 6 mmol, 1.0 equiv.) were added slowly under ice-water bath. The resulting mixture was stirred under ice-water bath for 15 minutes, and then 2-methylnaphthalen-1-amine (1.131 g, 7.2 mmol, 1.2 equiv.) was added. The resulting mixture was stirred and reacted at 65° C. for 4 hours, and then concentrated under reduced pressure to remove the solvent and obtain a residue (crude product) (Reaction Scheme I). The resulting residue (crude product) was purified by preparative chromatography (using a mixed solvent of CH2Cl2 / hexane = 8 / 2 as the developing solvent, column: normal phase silica gel (Universal column L size (Yamazen Corporation)), equipment: Smart Flash AKROS (Yamazen Corporation), temperature: room temperature, detection wavelength: 254 nm), and then recrystallized at room temperature using a mixed solvent of CH2Cl2 / hexane = 8 / 2 to obtain the ligand (product) as white crystals (1.593 g, yield 85.0%). [ka]

[0078] <Ligand 13 C-NMR measurement> The purified product was analyzed under the following conditions: 13 C-NMR measurements were performed. [ 13 C-NMR measurement conditions] NMR measurement equipment: AVANCE NEO spectrometer, Ascend 600 magnet (manufactured by BRUKER JAPAN) · 13 C-NMR measurement conditions: Frequency 150.89 MHz, CDCl3 solvent

[0079] The resulting ligand 13The C-NMR spectrum is shown in Figure 1. 13 C-NMR spectrum data was obtained. Spectral analysis confirmed that the compound was N-(2-methyl-1-naphthalenyl)-1-isoquinolinecarboxamide.

[0080] 13 C NMR (150.89MHz, CDCl3) δ 164.7, 147.8, 140.3, 137.6, 133.2, 132.8, 130.7, 130.6, 130.1, 128.9, 128.8, 128.1, 128.0, 127.4 (2C), 126.9, 126.5, 125.2, 124.8, 122.6, 18.9

[0081] [Example 2] <Production of triarylamine compound (9,10-Dihydro-9,9-dimethyl-10-[4-(4-pyridinyl)phenyl]acridine)> In a 20 mL vial equipped with a Teflon septum stir bar, CuI (9.5 mg, 0.05 mmol, 0.05 equiv.), the ligand obtained in Example 1 (23.4 mg, 0.075 mmol, 0.075 equiv.), and 1 mL of sulfolane were added. The resulting mixture was stirred at 35° C. for 10 min, followed by the addition of potassium phosphate (318.4 mg, 1.5 mmol, 3.0 equiv.). The resulting mixture was stirred at 25° C. for 10 min, followed by the addition of 4-(4-bromophenyl)pyridine (234.0 mg, 1.0 mmol, 1.0 equiv.) and 9,9-dimethyl-9,10-dihydroacridine (251.2 mg, 1.20 mmol, 1.2 equiv.). The resulting mixture was degassed by purging with nitrogen for 20 minutes in a glove box controlled to a humidity of 10 ppm or less and an oxygen concentration of 10 ppm or less under a nitrogen atmosphere, and then stirred and reacted for 8 hours at 100° C. After cooling, the resulting mixture was poured into water (50 mL), and the resulting organic layer was collected, dehydrated with anhydrous sodium sulfate, and concentrated to obtain a crude product (Reaction Formula II). After confirming the completion of the reaction by TLC analysis (hexane / ethyl acetate = 7 / 3) of the crude product, the obtained crude product was purified by preparative chromatography (using a mixed solvent of hexane / ethyl acetate = 7 / 3 as the developing solvent, column: normal phase silica gel (Universal column M size (manufactured by Yamazen Corporation)), equipment: Smart Flash AKROS (manufactured by Yamazen Corporation), temperature: room temperature, detection wavelength: 254 nm) to obtain a white crystalline product (triarylamine compound) (257 mg, yield 71%). [ka]

[0082] <Triarylamine compounds 13 C-NMR measurement> The obtained triarylamine compound was subjected to the following reaction under the following conditions: 13 C-NMR measurements were performed. [ 13 C-NMR measurement conditions] NMR measurement equipment: AVANCE NEO spectrometer, Ascend 600 magnet (manufactured by BRUKER JAPAN) · 13 C-NMR measurement conditions: Frequency 150.89 MHz, CDCl3

[0083] The obtained triarylamine compound 13 The C-NMR spectrum is shown in Figure 2. As a result of spectrum analysis, it was confirmed that the compound was 9,10-dihydro-9,9-dimethyl-10-[4-(4-pyridinyl)phenyl]acridine.

[0084] [Spectral Data ( 13 C NMR (150.89 MHz, CDCl3) δ 150.4, 147.4, 142.2, 140.7, 138.0, 132.1, 130.1, 129.5, 126.4, 125.3, 121.6, 120.8, 114.0, 36.0, 31.3

Claims

1. The following formula (1): 【Chemistry 1】 (In formula (1), R １ may be bonded to any carbon atom on the ring and represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a halogenoalkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, a hydroxy group, a mercapto group, a nitro group, an amino group, an aminoalkylthio group, or a heteroaryl group. and an isoquinoline compound represented by the formula: The following formula (2): 【Chemistry 2】 (In formula (2), R ２ may be bonded to any carbon atom on the ring and represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a halogenoalkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, a hydroxy group, a mercapto group, a nitro group, an amino group, an aminoalkylthio group, or a heteroaryl group. and a naphthalene compound represented by the formula: The following formula (3): 【Chemistry 3】 (In formula (3), R １ is the same as in formula (1), and R ２ is the same as formula (2). A reaction step of synthesizing a ligand represented by the formula: A purification step of purifying the ligand represented by formula (3) obtained in the reaction step by a chromatography method using a developing solution containing a halogen-based solvent. A method for producing a ligand comprising the steps of:

2. The method according to claim 1, wherein the reaction temperature in the reaction step is 45 to 85° C. and the reaction time is 1 to 6 hours.

3. The following formula (4): 【Chemistry 4】 (In formula (4), Z is -C(R ５ ) (R ６ )- or an oxygen atom, or Z is absent, where Z is -C(R ５ ) (R ６ )--or an oxygen atom, the dashed lines α and β each represent a single bond, and when Z is absent, the dashed lines α and β each do not exist. R ３ , R ４ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. R ５ , R ６ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. and a diarylamine compound represented by the formula: The following formulas (5-1) to (5-3): 【Chemistry 5】 【Chemistry 6】 (In formula (5-2), Y represents a carbonyl group, a sulfonyl group, or a phenylphosphine oxide group. m represents 0 or 1. The dashed line γ is absent or indicates a single bond. 【Chemistry 7】 and an aryl bromide compound represented by a formula selected from the group consisting of Reacting in the presence of a Cu-based catalyst and a ligand obtained by the method of claim 1, The following formulas (6-1) to (6-3): 【Chemistry 8】 【Chemistry 9】 【Chemistry 10】 (Z, R in formulas (6-1), (6-2) and (6-3) ３ , R ４ , dashed lines α and β are defined as in formula (4), and Y, m, and dashed line γ are defined as in formula (5-2). A method for producing a triarylamine compound, comprising a reaction step of synthesizing a triarylamine compound represented by a formula selected from the group consisting of:

4. R １ and R ２ The method according to claim 1 or 2, wherein is a hydrogen atom.

5. In the diarylamine compound represented by formula (4), Z is -C(R ５ ) (R ６ ) - indicates R ３ and R ４ respectively represent hydrogen atoms, R ５ and R ６ each represents an alkyl group having 1 to 6 carbon atoms, The aryl bromide compound is a compound represented by formula (5-1), The triarylamine compound is a compound represented by formula (6-1): The method according to claim 3.

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