Method for producing compounds and catalyst compositions

Abstract

To provide a method for producing a compound that can expand a selection range of usable monomers in a direct arylation reaction without using any metal component other than palladium, and to provide a catalyst composition.SOLUTION: There is provided a method for producing a compound having a first partial structure in which a first carbon atom constituting a first aromatic ring structure and a second carbon atom constituting a second aromatic ring structure are directly connected through a single bond, the method comprising the step of reacting a first compound having a partial structure in which a hydrogen atom is bonded to the first carbon atom constituting the first aromatic ring structure and a second compound having a partial structure in which a chlorine atom or a trifluoromethanesulfonic acid group is bonded to the second carbon atom constituting the second aromatic ring structure in the presence of a palladium complex and two kinds of phosphine compounds.SELECTED DRAWING: None

Description

[Technical Field] 【0001】 This invention relates to a method for producing compounds and a catalyst composition. [Background technology] 【0002】 Polymers with aromatic ring structures in their main chain possess superior properties not found in existing materials, such as high heat resistance, high oxidation resistance, high dimensional stability, high acid-base resistance, low water absorption, and low hydrolysis resistance. They are attracting widespread attention as next-generation materials for fields such as high-speed communications and the aerospace industry. 【0003】 As a method for producing the above polymers, coupling reactions such as the Suzuki-Miyaura coupling and the Migita-Kosugi-Still coupling have been widely used. 【0004】 In the Suzuki-Miyaura coupling, organoboron compounds are used as raw material monomers, while in the Migita-Kosugi-Still coupling, organotin compounds are used as raw material monomers. The metallic components derived from these organometallic compounds remain in the material, which has been a factor in degrading material properties. 【0005】 As a method for producing polymers without using organometallic compounds, methods have been reported in which the bond (CH bond) between the carbon atom constituting the aromatic ring structure in the monomer structure and the hydrogen atom directly connected to this carbon atom is cleaved with a transition metal such as palladium, and then coupled with an aromatic halide (see Patent Document 1 and Non-Patent Document 1 below). [Prior art documents] [Patent Documents] 【0006】 [Patent Document 1] Japanese Patent Publication No. 2012-251121 [Non-patent literature] 【0007】 [Non-Patent Document 1] Polym.Chem.2019,10,2298-2304 Summary of the Invention Problems to be Solved by the Invention 【0008】 In the above Patent Document 1, X-Ar 2 -X (X is a halogen atom) is described as a raw material monomer that couples with H-Ar 2 -H. However, the reaction proceeds with a good yield under the reaction conditions described in the above Patent Document 1 only when X is a bromine atom. In addition, the monomer in which X is a bromine atom is more expensive than the monomer in which X is another halogen atom (for example, a chlorine atom). Therefore, it is desired to expand the range of selection of available raw material monomers and to develop a method that can use a cheaper raw material monomer. 【0009】 In the above Non-Patent Document 1, it is described that direct arylation polycondensation was realized by using a dichloroaryl monomer as a raw material monomer and a binary catalyst of palladium / copper as a catalyst, and a high molecular weight polymer could be produced in a good yield. However, there is a possibility that a copper component derived from the catalyst remains in the obtained polymer. If a material in which a copper component remains in the polymer is used as an electronic or communication material, etc., there is a risk of causing performance degradation. In addition, it is difficult to remove the copper component remaining in the polymer. Therefore, it is desired to develop a method with less residual metal components. 【0010】 The present invention has been made based on the above circumstances, and in the direct arylation reaction (DArP: Direct Arylation Polymerization), an object is to provide a method for producing a compound and a catalyst composition that can expand the selection options of available monomers without using a metal component other than palladium. Means for Solving the Problems 【0011】 The invention made to solve the above problems is a method for producing a compound having a first partial structure in which a first carbon atom constituting a first aromatic ring structure is directly connected to a second carbon atom constituting a second aromatic ring structure by a single bond (hereinafter, also referred to as "[A] compound"), comprising a first compound having a partial structure in which a hydrogen atom is bonded to the first carbon atom constituting the first aromatic ring structure (hereinafter, also referred to as "[B] compound") and a second compound having a partial structure in which a chlorine atom or a trifluoromethanesulfonic acid group is bonded to the second carbon atom constituting the second aromatic ring structure (hereinafter, also referred to as "[C] compound"), and reacting them in the presence of a palladium complex, a compound represented by the following formula (1), and a compound represented by the following formula (2) (hereinafter, the two compounds are collectively also referred to as "phosphine compound") (hereinafter, also simply referred to as "reaction step"). It is a method for producing a compound (hereinafter, simply referred to as "production method"). [Chemical formula] (In formula (1), Me is a methyl group.) (In formula (2), Cy is a cyclohexyl group and i-Pr is an isopropyl group.) 【0012】 Another invention made to solve the above problems is a catalyst composition used in a direct arylation reaction, which contains a palladium complex, a compound represented by the above formula (1), and a compound represented by the above formula (2). [Advantages of the Invention] 【0013】 According to the production method and catalyst composition of the present invention, in the direct arylation reaction, the options of available monomers can be expanded without using a metal component other than palladium. [Embodiments for Carrying out the Invention] 【0014】 Hereinafter, the production method and catalyst composition of the present invention will be described in detail. 【0015】 [Production Method] The manufacturing method is a method for producing compound [A] described later. The manufacturing method comprises a step (reaction step) in which compound [B] and compound [C] are reacted in the presence of a palladium complex, a compound represented by formula (1) described later, and a compound represented by formula (2) described later. 【0016】 The manufacturing method may further include other steps besides the reaction step described above. 【0017】 According to this manufacturing method, by using two specific phosphine compounds as ligands for the palladium catalyst in the reaction step, it becomes possible to use only palladium as the metal component and utilize monomers such as aromatic C-Cl and aromatic C-OR. Therefore, according to this manufacturing method, it is possible to broaden the range of usable monomers in the direct arylation reaction without using metal components other than palladium. 【0018】 Furthermore, this manufacturing method allows for the production of compound [A] in good yield. 【0019】 The following describes the processes involved in this manufacturing method. 【0020】 [Reaction Process] In this step, compound [B] and compound [C] are reacted in the presence of a palladium complex and two phosphine compounds. This step synthesizes compound [A], which will be described later. The reaction in this step is a direct arylation reaction in which the CH bond in compound [B] is directly functionalized by compound [C]. 【0021】 The reaction temperature in this process is, for example, around 50°C to 160°C, with 60°C to 120°C being preferred. The reaction time is, for example, around 0.1 hours to 200 hours, with 1 hour to 30 hours being preferred. 【0022】 While there are no particular restrictions on the atmosphere in which this process is carried out, an inert gas atmosphere such as a nitrogen atmosphere or a vacuum atmosphere that can suppress catalyst deactivation is preferred. 【0023】 This process is usually carried out in a solvent. Examples of solvents include hydrocarbon solvents, ether solvents, and amide solvents. 【0024】 Examples of hydrocarbon solvents include n-pentane, n-hexane, toluene, and xylene. 【0025】 Examples of ether-based solvents include diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether, diheptyl ether, cyclopentyl methyl ether, dimethoxyethane, tetrahydrofuran, tetrahydropyran, dioxane, diphenyl ether, and anisole. 【0026】 Examples of amide solvents include N-methylpyrrolidone, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpropionamide. 【0027】 Preferred solvents are toluene, tetrahydrofuran, or cyclopentyl methyl ether. In this case, the solubility of the resulting [A] compound can be improved. 【0028】 In this process, it is preferable to carry out the reaction in the presence of a basic compound in addition to the palladium complex, the compound represented by formula (1) described later, and the compound represented by formula (2) described later. In this case, the strong acid (HX) produced as a by-product of the reaction can be neutralized, and undesirable reactions caused by the strong acid, such as the decomposition of the catalyst, can be suppressed. 【0029】 Examples of basic compounds include inorganic salts such as sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, potassium phosphate, sodium phosphate, cesium phosphate, potassium hydrogen phosphate, sodium hydrogen phosphate, and tert-butoxy potassium. Among these, carbonates are preferred, and cesium carbonate is more preferred. Cesium carbonate has higher solubility in organic solvents than metal carbonates such as sodium carbonate and potassium carbonate, and can better suppress undesirable reactions caused by strong acids produced as by-products of the reaction. 【0030】 The amount of basic compound added is usually 0.5 moles to 100 moles per mole of compound [B], preferably 0.9 moles to 20 moles, and more preferably 1 moles to 10 moles. 【0031】 When an inorganic salt is added as a basic compound in this process, its solubility can be improved, so it is usually added to the reaction system as an aqueous solution. In this process, the reaction may also be carried out in a two-phase solvent consisting of an aqueous phase and an organic phase. In this case, a correlation transfer catalyst such as a quaternary ammonium salt may be added as needed. 【0032】 In this step, it is preferable to further add an organic acid. In this case, the catalytic reaction in this step can be promoted. Examples of organic acids include carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, pivalic acid, and benzoic acid, and sulfonic acids. From the viewpoint of solubility in organic solvents and ease of purification, carboxylic acids are preferred, and pivalic acid is more preferred. 【0033】 The amount of organic acid added is not particularly limited and can be determined as appropriate. When the reaction is carried out in the presence of a basic compound in this step, the amount of organic acid added is preferably 0.01 moles to 90 moles, and more preferably 0.1 moles to 70 moles, per mole of the basic compound. 【0034】 ([A] compound) Compound [A] is a compound having a first substructure in which the first carbon atom constituting the first aromatic ring structure and the second carbon atom constituting the second aromatic ring structure are directly connected by a single bond. The first aromatic ring structure is an aromatic ring structure derived from compound [B], and the second aromatic ring structure is an aromatic ring structure derived from compound [C]. More specifically, compound [A] is a compound in which the first carbon atom-hydrogen atom bond constituting the first aromatic ring structure in compound [B], described later, is directly functionalized with the second carbon atom-X bond constituting the second aromatic ring structure in compound [C], described later, thereby forming a first carbon atom-second carbon atom bond. 【0035】 Compound [A] can be suitably used as a functional material for electronics and communications. Because Compound [A] is manufactured by this method, it has an extremely low content of metal components other than palladium. Therefore, when Compound [A] is used as a functional material for electronics and communications, the performance degradation due to the presence of the above-mentioned metal components is minimal, and an improvement in performance can be expected. 【0036】 Compound [A] has an extremely low content of metal components other than palladium. In particular, since copper compounds are not used as catalyst components in this manufacturing method, an extremely low copper content can be achieved. The copper content in compound [A] is preferably 50 ppm or less, more preferably 10 ppm or less, and even more preferably 1 ppm or less. Furthermore, it is especially preferable that compound [A] is substantially free of copper components. "Substantially free of copper components" means that the copper components contained in compound [A] are below the detection limit. Methods for measuring the content of metal components, such as copper, include elemental analysis methods such as atomic absorption spectrometry, emission spectrometry, plasma emission spectrometry, X-ray fluorescence analysis, plasma mass spectrometry, glow discharge mass spectrometry, and ion chromatography. 【0037】 In this specification, "aromatic ring structure" includes "aromatic hydrocarbon ring structure" and "aromatic heterocyclic structure." Among aromatic ring structures, polycyclic structures that include aromatic hydrocarbon ring structures and aromatic heterocyclic structures are considered to be "aromatic heterocyclic structures." "Polycyclic" includes not only fused polycyclic structures in which two rings have two shared atoms, but also ring-assembly type polycyclic structures in which two rings do not have shared atoms and are linked by single bonds. 【0038】 The first and second aromatic ring structures will be explained in the sections ([B] Compound) and ([C] Compound) below, respectively. 【0039】 Examples of the first substructure mentioned above include the substructure represented by the following formula (6) or formula (7). 【0040】 [ka] 【0041】 In the above formulas (6) and (7), Ar 1 This is equivalent to equation (3) described later. Ar 2 This is equivalent to equation (4) described later. Ar 3 , R 1 And u are equivalent to equation (5) described later. 【0042】 Unless otherwise specified, "compound" in this specification means a compound in a broad sense, encompassing both "polymers" and "compounds" that are not polymers (i.e., compounds that do not have repeating units). 【0043】 [A] Compound may be a low molecular weight compound that is not a polymer (hereinafter also referred to as "[A1] compound") or a polymer having repeating units (hereinafter also referred to as "[A2] polymer). The term "low molecular weight compound" is used for convenience to distinguish between "compounds" in a broad sense that includes polymers and "compounds" in a narrow sense that does not include polymers, and is not intended to restrict the molecular weight of "low molecular weight compounds". 【0044】 [A1] Examples of compounds include low molecular weight compounds having a substructure represented by formula (6) or formula (7) above. 【0045】 [A1] The molecular weight of the compound is, for example, 200 to 2000, and preferably 230 to 1500. [A1] The molecular weight of the compound is, for example, 1 The desired molecular structure can be confirmed by 1H-NMR, and then determined from that structure. 【0046】 [A1] Examples of compounds include low-molecular-weight compounds represented by the following formulas (A-1) to (A-6). 【0047】 [ka] 【0048】 In formula (A-2) above, Me is a methyl group. In formula (A-5) above, Ph is a phenyl group. In formula (A-6) above, R is a 2-decyltetradecyl group. 【0049】 [A2] A polymer is a polymer having the above-mentioned first substructure as a repeating unit. Examples of [A2] polymers include polymers having the substructure represented by formula (6) or formula (7) as a repeating unit. 【0050】 [A2] The weight-average molecular weight (hereinafter also referred to as "Mw") in polystyrene terms, as measured by gel permeation chromatography (GPC) of the polymer, is preferably 2,000 to 1,000,000, and more preferably 3,000 to 600,000. 【0051】 [A2] The number-average molecular weight (hereinafter also referred to as "Mn") in polystyrene terms, as measured by gel permeation chromatography (GPC) of the polymer, is preferably 1,000 to 500,000, and more preferably 1,500 to 300,000. 【0052】 [A2] The molecular weight distribution of the polymer (hereinafter also referred to as "Mw / Mn") is preferably from 1.5 to 5.0, more preferably from 1.6 to 4.0. 【0053】 [A2] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer can be measured, for example, by a GPC system using tetrahydrofuran as an eluent ("HLC-8420GPC" manufactured by Tosoh Corporation) or a GPC system using chloroform as an eluent (pump: "PU-980" manufactured by JASCO Corporation, RI detector: "RI-1530" manufactured by JASCO Corporation, columns: "SHODEX K-801", "SHODEX K-803L", and "SHODEX K-805L" manufactured by Showa Denko K.K.). The molecular weight distribution (Mw / Mn) is a value calculated from the measured values of Mw and Mn described above. 【0054】 [A2] Examples of the polymer include polymers represented by the following formulas (A-7) to (A-10). 【0055】 【Chemical formula】 【0056】 [A2] Particularly preferred as the polymer is a polymer having a partial structure represented by the above formula (7) as a repeating unit. In other words, [A2] preferred as the polymer is a polymer having a repeating unit represented by the following formula (8) (hereinafter also referred to as "[A2-1] polymer"). 【0057】 【Chemical formula】 【0058】 In the above formula (8), Ar 1 is synonymous with formula (3) described later. Ar 2 is synonymous with formula (4) described later. Ar 3 , R 1 and u are synonymous with formula (5) described later. 【0059】 [A2-1]Specific examples of polymers include polymers represented by the above formulas (A-7) or (A-8). 【0060】 ([B] compound) [B] Compounds are compounds having a substructure in which a hydrogen atom is bonded to the first carbon atom that constitutes the first aromatic ring structure. 【0061】 The number of members in the first aromatic ring structure is, for example, 5 to 30, with 5 to 20 being preferred. "Number of members" refers to the number of atoms that make up the ring structure, and in the case of polycyclic compounds, it refers to the number of atoms that make up this polycyclic compound. 【0062】 Examples of the first aromatic ring structure include aromatic hydrocarbon ring structures with 6 to 30 members and aromatic heterocyclic ring structures with 5 to 30 members. 【0063】 Examples of the above-mentioned aromatic hydrocarbon ring structures include benzene structures; condensed polycyclic aromatic hydrocarbon ring structures such as naphthalene structures, indene structures, anthracene structures, fluorene structures, biphenylene structures, phenanthrene structures, pyrene structures, and perylene structures; and ring-assembled aromatic hydrocarbon ring structures such as biphenyl structures, terphenyl structures, binaphthalene structures, and phenylnaphthalene structures. 【0064】 Examples of the above-mentioned aromatic heterocyclic structures include oxygen-containing heterocyclic structures such as furan, pyran, benzofuran, and benzopyran structures; nitrogen-containing heterocyclic structures such as pyrrole, pyridine, pyrimidine, indole, quinoline, and diketopyrrolopyrrole structures; sulfur-containing heterocyclic structures such as thiophene and dibenzothiophene structures; silicon-containing heterocyclic structures such as silafluorene structures; and heterocyclic structures containing two or more heteroatoms such as oxazole and thiazole structures. 【0065】 The preferred first aromatic ring structure is a benzene structure, a biphenyl structure, a thiophene structure, a thiazole structure, an oxazole structure, a furan structure, a diketopyrrolopyrrole structure, or a structure in which two or more of these structures are linked by a single bond. 【0066】 Some of the hydrogen atoms in the above-described first aromatic ring structure may be substituted with substituents. However, the hydrogen atom bonded to the first carbon atom in the above-described first aromatic ring structure shall not be substituted with substituents. Examples of substituents include fluorine atoms, cyano groups, nitro groups, alkyl groups, fluorinated alkyl groups, alkoxy groups, fluorinated alkoxy groups, alkylthio groups, or fluorinated alkylthio groups. A "fluorinated alkyl group" refers to a group in which some or all of the hydrogen atoms in an alkyl group are substituted with fluorine atoms. The same applies to the other "fluorinated alkoxy groups" and "fluorinated alkylthio groups." 【0067】 The number of carbon atoms in the alkyl or fluorinated alkyl groups mentioned above is typically 1 to 30. "Number of carbon atoms" refers to the number of carbon atoms constituting the group. "Alkyl group" includes not only linear alkyl groups but also cycloalkyl groups. 【0068】 Examples of alkyl groups include chain-like alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, 2-methylbutyl group, 1-methylbutyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, and 2-decyltetradecyl group; and cycloalkyl groups such as cyclopentyl group, cyclohexyl group, and adamantyl group. 【0069】 The number of carbon atoms in the above-mentioned alkoxy group or fluorinated alkoxy group is usually 1 to 30. The term "alkoxy group" includes not only chain-like alkoxy groups but also cycloalkyloxy groups. 【0070】 Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy, trifluoromethoxy, pentafluoroethoxy, perfluorobutoxy, perfluorohexyloxy, perfluorooctyloxy, methoxymethyloxy, and 2-methoxyethyloxy. 【0071】 The number of carbon atoms in the alkylthio group or fluorinated alkylthio group is usually 1 to 30, and preferably 1 to 20. The term "alkylthio group" includes not only linear alkylthio groups but also cycloalkylthio groups. 【0072】 Examples of alkylthio groups include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, tert-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group, and trifluoromethylthio group. 【0073】 If the above first aromatic ring structure has two or more substituents, adjacent substituents may combine with each other to form a substituted or unsubstituted alicyclic structure together with the atomic chain to which they are bonded. The term "alicyclic structure" includes "aliphatic hydrocarbon ring structure" and "aliphatic heterocyclic structure." The substituents are the same as described above. 【0074】 The number of ring members in the alicyclic structure is, for example, 4 to 20, with 4 to 10 being preferred. 【0075】 Examples of alicyclic structures include aliphatic hydrocarbon ring structures with 4 to 20 ring members and aliphatic heterocyclic structures with 4 to 20 ring members. 【0076】 Examples of the above aliphatic hydrocarbon ring structures include monocyclic saturated alicyclic structures such as cyclobutane, cyclopentane, and cyclohexane; polycyclic saturated alicyclic structures such as norbornane, adamantane, tricyclodecane, and tetracyclododecane; monocyclic unsaturated alicyclic structures such as cyclobutene, cyclopentene, and cyclohexene; and polycyclic unsaturated alicyclic structures such as norbornene, tricyclodecene, and tetracyclododecene. 【0077】 Examples of the above-mentioned aliphatic heterocyclic structures include oxygen atom-containing heterocyclic structures such as dioxolane and dioxane structures, and sulfur atom-containing heterocyclic structures such as dithiolane and dithiane structures. 【0078】 When the first aromatic ring structure described above is an aromatic hydrocarbon ring structure, a fluorine atom is preferred as the substituent, and two or more fluorine atoms are more preferred. In this case, the reactivity of the [B] compound can be improved. 【0079】 When the first aromatic ring structure described above is an aromatic heterocyclic structure, a sulfur atom-containing heterocyclic structure is preferred, and a thiophene structure is more preferred. In this case, the reactivity of the [B] compound can be improved. 【0080】 [B] Examples of compounds include those represented by the following formula (3). 【0081】 [ka] 【0082】 In the above formula (3), Ar 1 is a substituted or unsubstituted aromatic ring structure. s is an integer greater than or equal to 1. 【0083】 Ar 1 The aromatic ring structure that gives the fragrance is the first aromatic ring structure described above. 【0084】 For s, 1 to 6 is preferable. 【0085】 Ar 1 Examples of [B] compounds (hereinafter also referred to as "[B1] compounds") in which the structure is an aromatic hydrocarbon ring include compounds represented by the following formulas (B1-1) to (B1-67). 【0086】 [ka] 【0087】 [ka] 【0088】 In the above formulas (B1-1) to (B1-67), R is a substituent other than a fluorine atom among the substituents listed above. 【0089】 [B1] The compound represented by the following formula (3-1) or (3-2) is preferred. In this case, the reactivity of the [B] compound can be improved. 【0090】 [ka] 【0091】 Ar 1 Examples of [B] compounds (hereinafter also referred to as "[B2] compounds") in which the compound has an aromatic heterocyclic structure include compounds represented by the following formulas (B2-1) to (B2-31). 【0092】 [ka] 【0093】 In the above formulas (B2-1) to (B2-31), R is the substituent described above. 【0094】 [B2] The compound represented by the following formula (3-3) or (3-4) is preferred. In this case, the reactivity of the [B] compound can be improved. 【0095】 [ka] 【0096】 In equation (3-3) above, the two R 2 Each of these is independently a hydrogen atom, a fluorine atom, a cyano group, a nitro group, an alkyl group, a fluorinated alkyl group, an alkoxy group, a fluorinated alkoxy group, an alkylthio group, or a fluorinated alkylthio group, or two R 2 These elements combine with each other to form a substituted or unsubstituted alicyclic structure along with the carbon chain to which they are bonded. 【0097】 In the above equation (3-4), R 2 This is equivalent to equation (3-3) above. Two R 3 Each of these is independently a hydrogen atom, a fluorine atom, a cyano group, a nitro group, an alkyl group, a fluorinated alkyl group, an alkoxy group, a fluorinated alkoxy group, an alkylthio group, or a fluorinated alkylthio group. 【0098】 [B] The amount of compound added can be determined as appropriate depending on the purpose. 【0099】 ([C] compound) [C] Compounds are compounds having a substructure in which a chlorine atom or a trifluoromethanesulfonic acid group is bonded to the second carbon atom constituting the second aromatic ring structure. 【0100】 In this manufacturing method, since a palladium complex and two types of phosphine compounds are used, aromatic compounds to which chlorine atoms or trifluoromethanesulfonic acid groups are bonded can be used as starting monomers in the direct arylation reaction. This expands the range of monomers that can be used as starting materials in the direct arylation reaction. 【0101】 The number of members in the second aromatic ring structure is, for example, 5 to 30, with 5 to 20 being preferred. Examples of the second aromatic ring structure include an aromatic hydrocarbon ring structure with 6 to 30 members and an aromatic heterocyclic ring structure with 5 to 30 members. Examples of the aromatic hydrocarbon ring structure and aromatic heterocyclic ring structure are the same as for the first aromatic ring structure. The substituents are also the same as for the first aromatic ring structure. 【0102】 The preferred second aromatic ring structure is a benzene structure, naphthalene structure, indene structure, anthracene structure, phenanthrene structure, fluorene structure, biphenyl structure, terphenyl structure, pyrene structure, perylene structure, dibenzothiophene structure, or silafluorene structure. 【0103】 Examples of [C] compounds include compounds represented by the following formula (4) (hereinafter also referred to as "[C1] compounds") or compounds represented by the following formula (5) (hereinafter also referred to as "[C2] compounds"). 【0104】 [ka] 【0105】 In formulas (4) and (5) above, X is a chlorine atom or a trifluoromethanesulfonic acid group (also known as a triflate group or OTf). 【0106】 In the above formula (4), Ar 2 X is a substituted or unsubstituted aromatic ring structure. t is an integer greater than or equal to 1. If t is greater than or equal to 2, multiple Xs are either identical or distinct from one another. 【0107】 In the above equation (5), two Ar 3 These are, independently, substituted or unsubstituted aromatic ring structures. 1 Each of these is independently a hydrogen atom, an alkyl group, or an aryl group, or two R 1 These are combined with each other to form a substituted or unsubstituted ring structure with the carbon atoms to which they are bonded. u is an integer of 1 or more. If u is 2 or more, multiple R 1They are the same or different. 【0108】 Ar 2 Or Ar 3 The aromatic ring structure that gives the effect is the second aromatic ring structure described above. 【0109】 The number of carbon atoms in an aryl group is usually 6 to 30, with 6 to 20 being preferred. Examples of aryl groups include phenyl groups and naphthyl groups. 【0110】 The term "ring structure" includes "alicyclic structures" and "aromatic ring structures." 【0111】 Two R's 1 Examples of ring structures formed by combining these elements with the carbon atoms to which they bond include cyclohexyl structures, cyclododecane structures, fluorene structures, and phthalide structures. 【0112】 For t, 1 to 6 is preferred, and 1 or 2 is more preferred. 【0113】 For u, 1 to 3 are preferred, with 1 being more preferred. 【0114】 If the [C] compound is a [C1] compound, a chlorine atom is preferred as X. If the [C] compound is a [C2] compound, a trifluoromethanesulfonic acid group is preferred as X. 【0115】 Examples of [C1] compounds include those represented by the following formulas (C1-1) to (C1-56). 【0116】 [ka] 【0117】 [ka] 【0118】 In the above formulas (C1-1) to (C1-56), X is equivalent to that in formula (4). R is the substituent described above. 【0119】 [C1] The compound represented by the following formula (4-1) is preferred. 【0120】 [ka] 【0121】 In formula (4-1) above, X is equivalent to that in formula (4) above. A and B are independently substituted or unsubstituted aromatic hydrocarbon ring structures. Y is a group represented by the following formulas (Y-1) to (Y-5). 【0122】 [ka] 【0123】 In the above equations (Y-1) to (Y-4), two R 4 Each of these is independently a hydrogen atom, a fluorine atom, an alkyl group, a fluorinated alkyl group, an alkoxy group, a fluorinated alkoxy group, an alkylthio group, or a fluorinated alkylthio group. 【0124】 Examples of [C2] compounds include trifluoromethanesulfonic acid diesters derived from bisphenols. Examples of bisphenols include bisphenol F, bisphenol A, bisphenol E, 4,4'-(1,3-dimethylbutylidene)diphenol (BisP-MIBK), bisphenol AP, bisphenol BP, 9,9-bis(4-hydroxyphenyl)fluorene, bisphenol Z, 4,4'-cyclododecylidenebisphenol, and bisphenol TMC. 【0125】 Examples of [C2] compounds include those represented by the following formulas (C2-1) to (C2-16). 【0126】 [ka] 【0127】 (Palladium complex) The palladium complex is not particularly limited as long as it is a palladium complex used as a catalyst in the cross-coupling reaction, and examples include palladium(O) complex and palladium(II) complex. Specifically, examples include palladium[tetrakis(triphenylphosphine)], dichlorobis(triphenylphosphine)palladium, palladium acetate, tris(dibenzylideneacetone)dipalladium, and bis(dibenzylideneacetone)palladium. Among these, tris(dibenzylideneacetone)dipalladium (Pd2(dba)3) is preferred from the viewpoint of ease of reaction operation and improvement of reaction rate. 【0128】 The amount of palladium complex added is not particularly limited as long as it is an effective amount as a catalyst, and can be determined as appropriate. The amount of palladium complex added is usually 0.0001 moles to 0.5 moles per mole of [B] compound, and preferably 0.0003 moles to 0.2 moles. 【0129】 (Phosphine compounds) The two phosphine compounds are the compound represented by the following formula (1) (hereinafter also referred to as "P(2-OMePh)3") and the compound represented by the following formula (2) (hereinafter also referred to as "XPhos"). 【0130】 [ka] 【0131】 In formula (1) above, Me is a methyl group. In formula (2) above, Cy is a cyclohexyl group and i-Pr is an isopropyl group. 【0132】 In this manufacturing method, by using P(2-OMePh)3 and XPhos together with the palladium complex, the reaction proceeds in which compound [B] and compound [C] react to produce compound [A]. If either P(2-OMePh)3 or XPhos is missing, the above reaction does not proceed, and compound [A] is not produced. It is presumed that in the reaction system, P(2-OMePh)3 and XPhos coordinate to the palladium atom as ligands for the palladium complex. 【0133】 The amount of P(2-OMePh)3 and XPhos added is typically 0.5 to 4 moles per mole of palladium atoms, preferably 1 to 3 moles, and more preferably 1 to 2 moles. 【0134】 [Other processes] Other steps include, for example, a step of washing the compound obtained in the above reaction step (washing step), and a step of purifying the compound obtained in the above reaction step (purification step). The specific methods for the washing step and the purification step are not particularly limited and can be carried out according to known methods. 【0135】 <Catalyst composition> The catalyst composition contains a palladium complex and two phosphine compounds (P(2-OMePh)3 and XPhos). The palladium complex and the two phosphine compounds are described in the <Manufacturing Method> section above. 【0136】 This catalyst composition allows for a wider selection of usable monomers in direct arylation reactions without the need for metal components other than palladium. Furthermore, it enables the synthesis of compound [A] in high yield. [Examples] 【0137】 The present invention will be described in detail below based on examples, but the present invention is not limited to these examples. The methods for measuring each physical property are shown below. 【0138】 [NMR Spectrum Measurement] The NMR spectra of the compounds from Synthesis Examples 1 and 2 and Examples 1-10 were measured by dissolving the compounds in a deuterated solvent, either deuterated chloroform or deuterated toluene, and using a nuclear magnetic resonance spectrometer (Bruker's "AVANCE III-400"). 【0139】 [Molecular weight measurement] The compounds obtained in Synthesis Examples 1 and 2 and Examples 1 to 6 are as follows: 1 The integrated values ​​of the 1H-NMR spectrum confirmed that a molecular structure with the desired molecular weight had been constructed. The molecular weights (number-average molecular weight and weight-average molecular weight) of the polymers obtained in Examples 7 and 8 were measured using a GPC system (HLC-8420GPC from Tosoh Corporation) with tetrahydrofuran as the eluent. The molecular weights (number-average molecular weight and weight-average molecular weight) of the polymers obtained in Examples 9 and 10 were measured using a GPC system (pump: PU-980 from JASCO Corporation, RI detector: RI-1530 from JASCO Corporation, column: SHODEX K-801, K-803L, and K-805L from Showa Denko K.K.) with chloroform as the eluent. 【0140】 <[C] Synthesis of Compounds> The following compounds represented by formulas (C-1) to (C-2) below (hereinafter also referred to as "compounds (C-1) to (C-2)") were synthesized as [C] compounds according to the method described below. 【0141】 [ka] 【0142】 [Synthesis Example 1] Synthesis of Compound (C-1) 0.029 mol of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter also referred to as "BPTMC") was added to a 500 mL four-necked flask containing a magnetic rotor, and the atmosphere inside was replaced with nitrogen to create a nitrogen atmosphere. 50 mL of dichloromethane and 0.29 mol of pyridine were added, and the mixture was cooled to 0°C in an ice bath. 0.087 mol of trifluoromethanesulfonic anhydride was then added dropwise. The four-necked flask was then returned to room temperature and the reaction was allowed to proceed for 4 hours with stirring. After the reaction was complete, the four-necked flask was cooled to 0°C, a 10% hydrochloric acid aqueous solution was added, and the mixture was washed three times with the 10% hydrochloric acid aqueous solution and three times with pure water. The organic layer was then concentrated using an evaporator. The resulting pale yellow oily liquid was purified by column chromatography (SiO2, toluene) to obtain compound (C-1) in 92% yield as a clear oily liquid. Compound (C-1) is 1,1-bis(4-(trifluoromethanesulfonyloxy)phenyl)-3,3,5-trimethylcyclohexane (hereinafter also referred to as "BPTMC-OTf"). 【0143】 The synthesis scheme for compound (C-1) is shown below. 【0144】 [ka] 【0145】 The NMR measurement results for compound (C-1) are shown below. 1 H-NMR (400MHz, CDCl3): δ=0.31(s,3H),0.88(t,J=13Hz,1H),1.00(s,6H),1.19(t,J=13Hz,1H),1.42(d,J=13Hz,1H),1.96(d,J=13Hz,1H),1. 98(br,1H),2.43(d,J=13Hz,1H),2.65(d,J=14Hz,1H),7.11(d,J=8.2Hz,2H),7.19(d,J=8.1Hz,2H),7.23-7.26(d,2H),7.40(d,J=8.2Hz,2H). 【0146】 [Synthesis Example 2] Synthesis of Compound (C-2) 0.058 mol of 1,1-bis(3-methyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter also referred to as "BCTMC") was added to a 500 mL four-necked flask containing a magnetic rotor, and the atmosphere inside was replaced with nitrogen to create a nitrogen atmosphere. 100 mL of dichloromethane and 0.58 mol of pyridine were added, and the mixture was cooled to 0°C in an ice bath. 0.17 mol of trifluoromethanesulfonic anhydride was then added dropwise. The four-necked flask was then returned to room temperature and the reaction was allowed to proceed for 4 hours with stirring. After the reaction was complete, the four-necked flask was cooled to 0°C, a 10% hydrochloric acid aqueous solution was added, and the mixture was washed three times with the 10% hydrochloric acid aqueous solution and three times with pure water. The organic layer was then concentrated using an evaporator. The resulting pale yellow oily liquid was purified by column chromatography (SiO2, toluene) to obtain compound (C-2) as a clear oily liquid in 97% yield. Compound (C-2) is 1,1-bis(3-methyl-4-(trifluoromethanesulfonyloxy)phenyl)-3,3,5-trimethylcyclohexane (hereinafter also referred to as "BCTMC-OTf"). 【0147】 The synthesis scheme for compound (C-2) is shown below. 【0148】 [ka] 【0149】 The NMR measurement results for compound (C-2) are shown below. 1 H-NMR (400MHz, CDCl3): δ=0.32(s,3H),0.86(t,J=13Hz,1H),1.00(s,6H),1.14(t,J=13Hz,1H),1.40(d,J=13Hz,1H),1.9 1(d,J=14Hz,1H),1.97(br,1H),2.31(s,3H),2.34(s,3H),2.42(d,J=14Hz,1H),2.63(d,J=14Hz,1H),7.03-7.27(m,6H). 【0150】 <[A] Synthesis of Compounds> Compounds represented by the following formulas (A-1) to (A-6) as [A1] compounds (hereinafter also referred to as "compounds (A-1) to (A-6)") and polymers represented by the following formulas (A-7) to (A-10) as [A2] polymers (hereinafter also referred to as "polymers (A-7) to (A-10)") were synthesized according to the following method. 【0151】 [ka] 【0152】 In formula (A-2) above, Me is a methyl group. In formula (A-5) above, Ph is a phenyl group. In formula (A-6) above, R is a 2-decyltetradecyl group. 【0153】 [Example 1] Synthesis of compound (A-1) After heating and drying the pressure-resistant reaction vessel containing the magnetic rotor, the internal atmosphere was replaced with nitrogen to create a nitrogen atmosphere. 1.3 μmol of tris(dibenzylideneacetone)dipalladium(0)-chloroform adduct, 5.0 μmol of tris(2-methoxyphenyl)phosphine, 5.0 μmol of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (hereinafter also referred to as "XPhos"), and 0.25 mmol of 4,4'-di-tert-butylbiphenyl were added as an internal standard for measuring the NMR yield after the reaction. After evacuating the inside of the reaction vessel with a vacuum pump, it was moved to a glove box, and 1.0 mmol of chlorobenzene, 0.50 mmol of 3,4-ethylenedioxythiophene, 1.5 mmol of cesium carbonate, 0.50 mmol of pivalic acid, and 1 mL of deuterium toluene were added. The reaction vessel was removed from the glove box and stirred at room temperature for 30 minutes. Then, the reaction mixture was heated to 100°C using an oil bath and reacted for 24 hours with stirring. After the reaction was complete, the oil bath was removed and the mixture was allowed to cool to room temperature. Subsequently, the yield of the product was determined by NMR and was found to be 98%. 【0154】 The synthesis scheme for compound (A-1) is shown below. 【0155】 [ka] 【0156】 The NMR measurement results for compound (A-1) are shown below. 1 H-NMR (400MHz, CDCl3): δ=4.37(s,4H),7.23(tt,J=7.5,1.1Hz,2H),7.34-7.41(m,4H),7.76(dd,J=8.4,1.1Hz,4H). 【0157】 [Example 2] Synthesis of compound (A-2) After heating and drying the pressure-resistant reaction vessel containing the magnetic rotor, the internal atmosphere was replaced with nitrogen to create a nitrogen atmosphere. 1.3 μmol of tris(dibenzylideneacetone)dipalladium(0)-chloroform adduct, 5.0 μmol of tris(2-methoxyphenyl)phosphine, 5.0 μmol of XPhos, and 0.25 mmol of 4,4'-di-tert-butylbiphenyl were added as an internal standard for measuring the NMR yield after the reaction. After evacuating the inside of the reaction vessel with a vacuum pump, it was moved to a glove box, and 1.0 mmol of 4-methoxychlorobenzene, 0.52 mmol of 3,4-ethylenedioxythiophene, 1.5 mmol of cesium carbonate, 0.50 mmol of pivalic acid, and 1 mL of deuterium toluene were added. The reaction vessel was removed from the glove box and stirred at room temperature for 30 minutes, then the reaction mixture was heated to 100°C using an oil bath and reacted for 24 hours with stirring. After the reaction was complete, the oil bath was removed and the mixture was allowed to cool to room temperature. Subsequently, the yield of the product was determined by NMR and found to be 98%. 【0158】 The synthesis scheme for compound (A-2) is shown below. In the synthesis scheme below, Me represents a methyl group. 【0159】 [ka] 【0160】 The NMR measurement results for compound (A-2) are shown below. 1 H-NMR (400MHz, CDCl3): δ=3.83(s,6H),4.34(s,4H),6.92(d,J=8.9Hz,4H),7.66(d,J=8.9Hz,4H). 【0161】 [Example 3] Synthesis of compound (A-3) After heating and drying the pressure-resistant reaction vessel containing the magnetic rotor, the internal atmosphere was replaced with nitrogen to create a nitrogen atmosphere. 1.3 μmol of tris(dibenzylideneacetone)dipalladium(0)-chloroform adduct, 5.0 μmol of tris(2-methoxyphenyl)phosphine, 5.0 μmol of XPhos, and 0.25 mmol of 4,4'-di-tert-butylbiphenyl were added as an internal standard for measuring the NMR yield after the reaction. After evacuating the inside of the reaction vessel with a vacuum pump, it was moved to a glove box, and 1.0 mmol of 4-chlorobenzotrifluoride, 0.50 mmol of 3,4-ethylenedioxythiophene, 1.5 mmol of cesium carbonate, 0.50 mmol of pivalic acid, and 1 mL of deuterium toluene were added. The reaction vessel was removed from the glove box and stirred at room temperature for 30 minutes, then the reaction mixture was heated to 100°C using an oil bath and reacted for 24 hours with stirring. After the reaction was complete, the oil bath was removed and the mixture was allowed to cool to room temperature. The yield of the product was then determined by NMR and was found to be 98%. 【0162】 The synthesis scheme for compound (A-3) is shown below. 【0163】 [ka] 【0164】 The NMR measurement results for compound (A-3) are shown below. 1 H-NMR (400MHz, CDCl3): δ=4.42(s,4H),7.62(d,J=8.2Hz,4H),7.86(d,J=8.2Hz,4H). 【0165】 [Example 4] Synthesis of compound (A-4) After heating and drying the pressure-resistant reaction vessel containing the magnetic rotor, the internal atmosphere was replaced with nitrogen to create a nitrogen atmosphere. 1.3 μmol of tris(dibenzylideneacetone)dipalladium(0)-chloroform adduct, 5.0 μmol of tris(2-methoxyphenyl)phosphine, 5.0 μmol of XPhos, and 0.25 mmol of 4,4'-di-tert-butylbiphenyl were added as an internal standard for measuring the NMR yield after the reaction. After evacuating the inside of the reaction vessel with a vacuum pump, it was moved to a glove box, and 1.0 mmol of 2,6-dimethylchlorobenzene, 0.50 mmol of 3,4-ethylenedioxythiophene, 1.5 mmol of cesium carbonate, 0.50 mmol of pivalic acid, and 1 mL of deuterium toluene were added. The reaction vessel was removed from the glove box and stirred at room temperature for 30 minutes, then the reaction mixture was heated to 100°C using an oil bath and reacted for 24 hours with stirring. After the reaction was complete, the oil bath was removed and the mixture was allowed to cool to room temperature. The yield of the product was then determined by NMR and found to be 85%. 【0166】 The synthesis scheme for compound (A-4) is shown below. 【0167】 [ka] 【0168】 The NMR measurement results for compound (A-4) are shown below. 1 H-NMR (400MHz, CDCl3): δ=2.29(s,12H),4.19(s,4H),7.12(d,J=7.6Hz,4H),7.18(dd,J=8.5,6.2Hz,2H). 【0169】 [Example 5] Synthesis of compound (A-5) After heating and drying the pressure-resistant reaction vessel containing the magnetic rotor, the internal atmosphere was replaced with nitrogen to create a nitrogen atmosphere. 1.3 μmol of tris(dibenzylideneacetone)dipalladium(0)-chloroform adduct, 5.0 μmol of tris(2-methoxyphenyl)phosphine, 5.0 μmol of XPhos, and 0.25 mmol of 4,4'-di-tert-butylbiphenyl were added as an internal standard for measuring the NMR yield after the reaction. After evacuating the inside of the reaction vessel with a vacuum pump, it was moved to a glove box, and 56.6 mg (0.50 mmol) of chlorobenzene, 0.50 mmol of 2-phenylthiazole, 1.0 mmol of cesium carbonate, 0.50 mmol of pivalic acid, and 1 mL of deuterium toluene were added. The reaction vessel was removed from the glove box and stirred at room temperature for 30 minutes, then the reaction mixture was heated to 100°C using an oil bath and reacted for 24 hours with stirring. After the reaction was complete, the oil bath was removed and the mixture was allowed to cool to room temperature. The yield of the product was then determined by NMR and was found to be 98%. 【0170】 The synthesis scheme for compound (A-5) is shown below. In the synthesis scheme below, Ph represents the phenyl group. 【0171】 [ka] 【0172】 The NMR measurement results for compound (A-5) are shown below. 1 H-NMR (400MHz, CDCl3): δ=7.35(tt,J=7.4,1.2Hz,1H),7.40-7.49(m,5H)7.62(d,J=8.0Hz,2H),7.98(dd,J=7.1,1.9Hz,2H),8.03(s,1H). 【0173】 [Example 6] Synthesis of compound (A-6) After heating and drying the pressure-resistant reaction vessel containing the magnetic rotor, the internal atmosphere was replaced with nitrogen to create a nitrogen atmosphere. 0.25 mmol of 3,6-dithienyl-2,5-bis(2-decyltetradecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione, 1.3 μmol of tris(dibenzylideneacetone)dipalladium(0)-chloroform adduct, 5.0 μmol of tris(2-methoxyphenyl)phosphine, 5.0 μmol of XPhos, and 0.13 mmol of 4,4'-di-tert-butylbiphenyl as an internal standard for measuring the NMR yield after the reaction were added. After evacuating the inside of the reaction vessel with a vacuum pump, the mixture was moved to a glove box, and 0.52 mmol of chlorobenzene, 0.75 mmol of cesium carbonate, 0.25 mmol of pivalic acid, and 1 mL of deuterium toluene were added. The reaction vessel was removed from the glove box and stirred at room temperature for 30 minutes. Then, the reaction mixture was heated to 100°C using an oil bath and reacted for 24 hours with stirring. After the reaction was complete, the oil bath was removed and the mixture was allowed to cool to room temperature. Subsequently, the yield of the product was determined by NMR and was found to be 90%. 【0174】 The synthesis scheme for compound (A-6) is shown below. In the synthesis scheme below, R is a 2-decyltetradecyl group. 【0175】 [ka] 【0176】 The NMR measurement results for compound (A-6) are shown below. 1 H-NMR(400MHz,C6D5CD3):δ=0.83-0.92(m,12H),1.11-1.54(m,80H),2.14(br,2H),4.15(d,J=7.4Hz,4 H),6.98-7.15(m,10H)7.62(d,J=8.0Hz,2H),7.44(d,J=8.4Hz,4H),8.03(s,1H),9.44(d,J=4.1Hz,2H). 【0177】 [Example 7] Synthesis of polymer (A-7) After heating and drying a pressure-resistant polymerization vessel containing a magnetic rotor, the internal atmosphere was replaced with nitrogen to create a nitrogen atmosphere. 5.0 mmol of BPTMC-OTf (monomer (C-1)) obtained in Synthesis Example 1, 5.0 mmol of 1,2,4,5-tetrafluorobenzene, 15 mmol of cesium carbonate, 5.0 mmol of pivalic acid, and 10 mL of tetrahydrofuran were added, and the mixture was bubbled with nitrogen for 10 minutes. Then, 0.050 mmol of tris(dibenzylideneacetone)dipalladium(0)-chloroform adduct, 0.20 mmol of tris(2-methoxyphenyl)phosphine, and 0.20 mmol of XPhos were added, and the container was sealed by stoppering. The reaction mixture was heated to 100°C using an oil bath and reacted with stirring for 6 hours. After the reaction was complete, the oil bath was removed and the mixture was allowed to cool to room temperature. Then, toluene was added and the mixture was washed three times with pure water. The organic layer after washing was filtered using filter paper and concentrated using an evaporator. The concentrated solution was then poured into methanol, and the solid was reprecipitated to obtain polymer (A-7) as a pale yellow solid. The yield of polymer (A-7) was 63%. The number-average molecular weight of polymer (A-7) on a polystyrene basis was 14,700, the weight-average molecular weight on a polystyrene basis was 27,600, and the molecular weight distribution was 1.9. 【0178】 The synthesis scheme for polymer (A-7) is shown below. 【0179】 [ka] 【0180】 The NMR measurement results for polymer (A-7) are shown below. 1 H-NMR (400MHz, CDCl3): δ=0.41(s,3H),0.95(br,1H),1.02(s,6H),1.27(br,1H),1.43(br,1H),2.05(br, 1H),2.06(br,1H),2.58(d,J=12Hz,1H),2.81(d,J=13Hz,1H),7.39(br,4H),7.45(br,2H),7.52(br,2H). 【0181】 [Example 8] Synthesis of polymer (A-8) After heating and drying a pressure-resistant polymerization vessel containing a magnetic rotor, the internal atmosphere was replaced with nitrogen to create a nitrogen atmosphere. 5.0 mmol of BCTMC-OTf (monomer (C-2)) obtained in Synthesis Example 2, 5.0 mmol of 1,2,4,5-tetrafluorobenzene, 15 mmol of cesium carbonate, 5.0 mmol of pivalic acid, and 10 mL of tetrahydrofuran were added, and the mixture was bubbled with nitrogen for 10 minutes. Then, 0.050 mmol of tris(dibenzylideneacetone)dipalladium(0)-chloroform adduct, 0.20 mmol of tris(2-methoxyphenyl)phosphine, and 0.20 mmol of XPhos were added, and the container was sealed by stoppering. The reaction mixture was heated to 100°C using an oil bath and reacted for 24 hours with stirring. After the reaction was complete, the oil bath was removed and the mixture was allowed to cool to room temperature. Then, toluene was added and the mixture was washed three times with pure water. The organic layer after washing was filtered using filter paper and concentrated using an evaporator. The concentrated solution was then poured into methanol, and the solid was reprecipitated to obtain polymer (A-8) as a pale yellow solid. The yield of polymer (A-8) was 75%. The number-average molecular weight of polymer (A-8) on a polystyrene basis was 15,100, the weight-average molecular weight on a polystyrene basis was 25,600, and the molecular weight distribution was 1.7. 【0182】 The synthesis scheme for polymer (A-8) is shown below. 【0183】 [ka] 【0184】 The NMR measurement results for polymer (A-8) are shown below. 1H-NMR (400MHz, CDCl3): δ=0.41(s,3H),0.91(t,J=12Hz,1H),1.02(s,6H),1.26(t,J=12Hz,1H),1.42(d,J=11Hz,1H),2.01(d,J= 14Hz,1H),2.08(br,1H),2.17(s,3H),2.24(s,3H),2.57(d,J=13Hz,1H),2.79(d,J=13Hz,1H),7.12-7.24(m,4H),7.36(br,2H). 【0185】 [Example 9] Synthesis of polymer (A-9) After heating and drying the Schlenk tube containing the magnetic rotor, the internal atmosphere was replaced with nitrogen to create a nitrogen atmosphere. 0.50 mmol of 2,7-dichloro-9,9-dioctylfluorene, 0.50 mmol of 4H,4'H-octafluorobiphenyl, 1.3 μmol of tris(dibenzylideneacetone)dipalladium(0)-chloroform adduct, 5.0 μmol of tris(2-methoxyphenyl)phosphine, and 5.0 μmol of XPhos were added. After evacuating the reaction vessel with a vacuum pump, it was moved to a glove box, and 1.5 mmol of cesium carbonate, 0.50 mmol of pivalic acid, and 1 mL of cyclopentyl methyl ether were added. The reaction vessel was removed from the glove box, a reflux condenser was attached, and the mixture was stirred at room temperature for 30 minutes. Then, the reaction mixture was incubated under reflux conditions with stirring using an oil bath for 24 hours. After the reaction was complete, the oil bath was removed, and the mixture was allowed to cool to room temperature. Chloroform was added to the reaction solution, and after washing with water, the chloroform solution was poured into methanol, and the solid was reprecipitated to obtain polymer (A-9) as a white solid. The yield of polymer (A-9) was 96%. The number-average molecular weight of polymer (A-9) on a polystyrene basis was 61,200, the weight-average molecular weight on a polystyrene basis was 189,700, and the molecular weight distribution was 3.1. 【0186】 The synthesis scheme for polymer (A-9) is shown below. 【0187】 [ka] 【0188】 The NMR measurement results for polymer (A-9) are shown below. 1 H-NMR (400MHz, CDCl3): δ=0.76(br,4H),0.79-0.86(m,6H),1.03-1.28(m,20H),2.07(br,4H),7.50-7.67(m,4H),7.94(d,J=8.1Hz,2H). 【0189】 [Example 10] Synthesis of polymer (A-10) After heating and drying a Schlenk tube containing a magnetic rotor, the internal atmosphere was replaced with nitrogen to create a nitrogen atmosphere. 0.50 mmol of 2,7-dichloro-9,9-dioctylfluorene, 0.50 mmol of 3,4-ethylenedioxythiophene, 1.3 μmol of tris(dibenzylideneacetone)dipalladium(0)-chloroform adduct, 5.0 μmol of tris(2-methoxyphenyl)phosphine, and 5.0 μmol of XPhos were added. After evacuating the reaction vessel with a vacuum pump, it was moved to a glove box, and 1.5 mmol of cesium carbonate, 0.50 mmol of pivalic acid, and 1 mL of toluene were added. The reaction vessel was removed from the glove box, a reflux condenser was attached, and the mixture was stirred at room temperature for 30 minutes. Then, the reaction mixture was incubated under reflux conditions with stirring using an oil bath for 24 hours. After the reaction was complete, the oil bath was removed, and the mixture was allowed to cool to room temperature. Chloroform was added to the reaction solution, and after washing with water, the chloroform solution was poured into methanol, and the solid was reprecipitated to obtain polymer (A-10) as a white solid. The yield of polymer (A-10) was 95%. The number-average molecular weight of polymer (A-10) on a polystyrene basis was 124,600, the weight-average molecular weight on a polystyrene basis was 311,300, and the molecular weight distribution was 2.5. 【0190】 The synthesis scheme for polymer (A-10) is shown below. 【0191】 [ka] 【0192】 The NMR measurement results for polymer (A-10) are shown below. 1 H-NMR (400MHz, CDCl3): δ=0.76(br,4H),0.78-0.86(m,6H),1.03-1.28(m,20H),2.05(br,4H),4.45(br,4H),7.66-7.73(m,4H),7.82(d,J=8.1Hz,2H). 【0193】 [Comparative Examples 1-6] The same procedure as in Examples 1-6 was followed, except that XPhos was not used as a ligand, and only 5.0 μmol of tris(2-methoxyphenyl)phosphine was used. As a result, no reaction proceeded in any of the systems, and the target compound was not obtained.

Claims

[Claim 1] A method for producing a compound having a first substructure in which a first carbon atom constituting a first aromatic ring structure and a second carbon atom constituting a second aromatic ring structure are directly connected by a single bond, A step of reacting a first compound having a substructure in which a hydrogen atom is bonded to the first carbon atom constituting the first aromatic ring structure, and a second compound having a substructure in which a chlorine atom or a trifluoromethanesulfonic acid group is bonded to the second carbon atom constituting the second aromatic ring structure, in the presence of a palladium complex, a compound represented by the following formula (1), and a compound represented by the following formula (2). Equipped with, A method for producing a compound in which the above-mentioned first aromatic ring structure is an aromatic hydrocarbon ring structure having a fluorine atom as a substituent, or a sulfur atom-containing heterocyclic structure. 【Chemistry 1】 (In formula (1), Me is a methyl group.) In formula (2), Cy is a cyclohexyl group and i-Pr is an isopropyl group. [Claim 2] A method for producing the compound according to claim 1, wherein the reaction step is carried out in the presence of a basic compound in addition to the palladium complex, the compound represented by formula (1), and the compound represented by formula (2). [Claim 3] The above-mentioned first compound is a compound represented by the following formula (3), A method for producing the compound according to claim 1 or claim 2, wherein the second compound is a compound represented by the following formula (4) or the following formula (5). 【Chemistry 2】 (In formula (3), Ar １ (This is an aromatic hydrocarbon ring structure having a fluorine atom as a substituent, or a sulfur atom-containing heterocyclic structure. s is an integer greater than or equal to 1.) 【Transformation 3】 (In formulas (4) and (5), X is a chlorine atom or a trifluoromethanesulfonic acid group.) In formula (4), Ar ２ X is a substituted or unsubstituted aromatic ring structure. t is an integer of 1 or greater. If t is 2 or greater, multiple Xs are either identical or different from one another. In equation (5), two Ar ３ These are, independently, substituted or unsubstituted aromatic ring structures. １ Each of these is independently a hydrogen atom, an alkyl group, or an aryl group, or two R １ These are combined with each other to form a substituted or unsubstituted ring structure with the carbon atoms to which they are bonded. u is an integer of 1 or more. If u is 2 or more, multiple R １ They are either the same or different. [Claim 4] A method for producing the compound according to claim 3, wherein the above-mentioned first substructure is a substructure represented by the following formula (6) or the following formula (7). 【Chemistry 4】 (In formulas (6) and (7), Ar １ is synonymous with the above formula (3). Ar ２ is synonymous with the above formula (4). Ar ３ , R １ and u are synonymous with the above formula (5).) [Claim 5] A method for producing the compound according to claim 3 or claim 4, wherein the compound represented by formula (3) above is a compound represented by the following formulas (3-1) to (3-4). 【Transformation 5】 (In equation (3-3), two R ２ Each of these is independently a hydrogen atom, a fluorine atom, a cyano group, a nitro group, an alkyl group, a fluorinated alkyl group, an alkoxy group, a fluorinated alkoxy group, an alkylthio group, or a fluorinated alkylthio group, or two R ２ These elements combine with each other to form a substituted or unsubstituted alicyclic structure along with the carbon chain to which they are bonded. In formula (3-4), R ２ This is equivalent to the above equation (3-3). The two R ３ Each of these is independently a hydrogen atom, a fluorine atom, a cyano group, a nitro group, an alkyl group, a fluorinated alkyl group, an alkoxy group, a fluorinated alkoxy group, an alkylthio group, or a fluorinated alkylthio group. [Claim 6] A method for producing the compound according to claim 3, claim 4, or claim 5, wherein the compound represented by the above formula (4) is the compound represented by the following formula (4-1). 【Transformation 6】 (In formula (4-1), X is equivalent to that in formula (4) above. A and B are independently substituted or unsubstituted aromatic hydrocarbon ring structures. Y is a group represented by the following formulas (Y-1) to (Y-5).) 【Transformation 7】 (In equations (Y-1) to (Y-4), two R ４ Each of these is independently a hydrogen atom, a fluorine atom, an alkyl group, a fluorinated alkyl group, an alkoxy group, a fluorinated alkoxy group, an alkylthio group, or a fluorinated alkylthio group. [Claim 7] A method for producing the compound according to any one of claims 3 to 6, wherein the compound represented by formula (5) above is a compound represented by the following formulas (C2-1) to (C2-16). 【Transformation 8】 [Claim 8] A catalyst composition used in direct arylation reactions, Palladium complex and, The compound represented by the following formula (1), The compound represented by the following formula (2) and It contains, A catalyst composition wherein the above direct arylation reaction is a method for producing the compound according to any one of claims 1 to 7. 【Chemistry 9】 (In formula (1), Me is a methyl group.) In formula (2), Cy is a cyclohexyl group and i-Pr is an isopropyl group.

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