Method for producing compound and catalyst composition

Abstract

To provide a method for producing a compound and a catalyst composition capable of expanding the range of selectable monomers in direct arylation reaction.SOLUTION: A method for producing a compound includes a step of carrying out a reaction between a first compound having a substructure where a hydrogen atom is bound to a first carbon atom forming a first aromatic ring structure, and a second compound having a substructure where a p-toluenesulfonyl group is bound to a second carbon atom forming a second aromatic ring structure, in the presence of a palladium complex and either a compound represented by formula (1) or a compound represented by formula (2).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a compound and a catalyst composition. [Background technology]

[0002] Chemical structures in which multiple aromatic rings (Ar) are directly bonded, such as polyarylene, are thermally stable and highly durable, and materials with this molecular structure are expected to have excellent properties not found in existing materials, such as high thermal deformation resistance, high oxidation resistance, high dimensional stability, high acid-base resistance, low water absorption, and low hydrolysis. Furthermore, because it is possible to impart functionality such as a high refractive index and electrical conductivity through molecular design, they are attracting widespread attention as next-generation materials in fields such as next-generation high-speed communication materials and the aerospace industry.

[0003] Coupling reactions such as the Suzuki-Miyaura coupling and the Migita-Kosugi-Still coupling are well-known synthetic reactions for linking multiple aromatic rings. However, these require the use of organometallic species such as organoboron compounds and organotin compounds as raw material monomers, which makes them unsuitable for industrial-scale production due to the multi-step manufacturing process and the need for waste disposal of by-product metal species. Furthermore, the metal components derived from these organometallic compounds remain in the material, which can degrade its properties.

[0004] As a production method to improve this, a method using a direct arylation reaction has been reported in which the bond (C-H bond) between the carbon atom constituting the aromatic ring structure contained in the monomer structure and the hydrogen atom directly bonded to this carbon atom is cleaved by a transition metal such as palladium, followed by coupling with an aromatic halide (see Patent Document 1 below).

[0005] Also reported is a method in which a hydroxy group directly bonded to an aromatic ring is converted to a trifluoromethanesulfonyloxy group as a leaving group, and this is then subjected to coupling (see Patent Document 2 below). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-251121 [Patent Document 2] Japanese Patent Application Publication No. 2023-128534 Summary of the Invention [Problem to be solved by the invention]

[0007] In the above Patent Document 1, H-Ar 1 X-Ar is used as a raw material monomer for coupling with -H. 2 -X (X is a halogen atom) is described. However, under the reaction conditions described in Patent Document 1, only compounds having a bromine atom as X reacted.

[0008] Furthermore, Patent Document 2 discloses that a compound having a trifluoromethanesulfonyloxy group (TfO group) in addition to a chlorine atom as X reacts. In particular, the reaction from the TfO group is an important method that enables synthesis from abundant primary raw materials having a phenol structure, such as bisphenol.

[0009] On the other hand, the TfO group is expensive, and it was desirable to be able to use the relatively inexpensive and versatile paratoluenesulfonyloxy group (TsO group).

[0010] However, there have been no reports to date of compounds containing the TsO group being used in this coupling reaction, making it necessary to develop a new reaction method.

[0011] The present invention has been made in light of the above-mentioned circumstances, and an object of the present invention is to provide a method for producing a compound and a catalyst composition that can expand the options for monomers that can be used in direct arylation polymerization (DArP). [Means for solving the problem]

[0012] The invention made to solve the above-mentioned problems is a method for producing a compound (hereinafter also referred to as "compound [A]") 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 linked by a single bond, the method comprising the step of reacting a first compound (hereinafter also referred to as "compound [B]") having a partial structure in which a hydrogen atom is bonded to the first carbon atom constituting the first aromatic ring structure with a second compound (hereinafter also referred to as "compound [C]") having a partial structure in which a paratoluenesulfonyloxy group is bonded to the second carbon atom constituting the second aromatic ring structure, in the presence of a palladium complex and a compound represented by the following formula (1) (hereinafter also referred to as "CM-Phos") or a compound represented by the following formula (2) (hereinafter also referred to as "BrettPhos") (hereinafter CM-Phos and BrettPhos are collectively referred to as "phosphine compounds") (hereinafter also referred to as "reaction step"). [ka] (In formula (1), Me is a methyl group. In formula (2), Cy is a cyclohexyl group, and i-Pr is an isopropyl group.

[0013] Another invention made to solve the above-mentioned problems is a catalyst composition for use in a direct arylation reaction, the catalyst composition containing a palladium complex and a compound represented by the above formula (1) or a compound represented by the above formula (2). [Effects of the Invention]

[0014] The production method and catalyst composition of the present invention can provide a production method and catalyst composition for compounds that can expand the selection of monomers that can be directly used in direct arylation reactions. DETAILED DESCRIPTION OF THE INVENTION

[0015] The production method and catalyst composition of the present invention will be described in detail below.

[0016] <Manufacturing method> The production method is a method for producing the compound [A] described below, and includes a step (reaction step) of reacting the compound [B] with the compound [C] in the presence of a palladium complex and CM-Phos or BrettPhos.

[0017] The production method may further include other steps in addition to the reaction step.

[0018] According to this production method, by using a specific phosphine compound as a ligand for the palladium catalyst in the reaction step, it becomes possible to carry out a reaction from a compound having a TsO group. Therefore, this production method can broaden the options for substrates that can be used in direct arylation reactions.

[0019] Furthermore, this production method allows compound [A] to be produced in good yield.

[0020] The compound [A] produced by this production method can be suitably used in a wide range of applications, including functional materials for electronics, communications, and displays, as well as new durable materials for batteries and power generation, and biomedical materials. The compound contains an extremely low amount of metal components other than palladium. Therefore, when using this compound, there is little performance degradation or side effects due to the presence of these metal components, and improved performance is expected.

[0021] The steps of the manufacturing method will be described below.

[0022] [Reaction process] In this step, compound [B] and compound [C] are reacted in the presence of a palladium complex and a specific phosphine compound. This step synthesizes compound [A], which will be described later. The reaction in this step is a direct arylation reaction in which the C-H bond in compound [B] is directly functionalized with compound [C].

[0023] The reaction temperature in this step is, for example, about 50° C. to 200° C., and preferably 60° C. to 160° C. The reaction time is, for example, about 0.1 to 200 hours, and preferably 1 to 30 hours.

[0024] The atmosphere in which this step is carried out is not particularly limited, but an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere, or a vacuum atmosphere capable of preventing deactivation of the catalyst is preferred.

[0025] This step is usually carried out in a solvent, such as a hydrocarbon solvent, an ether solvent, or an amide solvent.

[0026] Examples of hydrocarbon solvents include pentane, hexane, toluene, and xylene.

[0027] Examples of ether 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.

[0028] Examples of amide solvents include N-methylpyrrolidone, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpropionamide.

[0029] The solvent is preferably a hydrocarbon solvent, more preferably toluene or xylene, and even more preferably xylene, which allows for a good balance between catalytic activity and the solubility of the reaction substrate.

[0030] In this step, the reaction is preferably carried out in the presence of a basic compound in addition to the palladium complex and CM-Phos or BrettPhos, which neutralizes the strong acid (HX) by-product of the reaction and suppresses undesirable reactions caused by the strong acid, such as decomposition of the catalyst.

[0031] 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 potassium tert-butoxide. Among these, cesium carbonate is preferred. When the basic compound is cesium carbonate, it is preferred because it has better solubility in solvents than other inorganic salts.

[0032] The amount of the basic compound added is usually 0.5 to 100 moles, preferably 0.9 to 20 moles, and more preferably 1 to 10 moles, per mole of the compound [B].

[0033] When an inorganic salt is added as a basic compound in this step, it is usually added to the reaction system as an aqueous solution of the inorganic salt, since this can improve the solubility of the inorganic salt. In this step, the reaction may be carried out in a two-phase solvent consisting of an aqueous phase and an organic phase. In this case, a phase transfer catalyst such as a quaternary ammonium salt may be further added, if necessary.

[0034] In this step, it is preferable to further add an organic acid. In this case, the yield of the product obtained by the production method can be increased. Examples of organic acids include carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, pivalic acid, adamantic acid, and benzoic acid. As the organic acid, carboxylic acids are preferred, and pivalic acid is more preferred. When the organic acid is pivalic acid, the catalytic activity can be enhanced compared to other carboxylic acids, and a high reaction yield can be obtained.

[0035] The amount of organic acid to be added is not particularly limited and can be determined appropriately. When the reaction in this step is carried out in the presence of a basic compound, the amount of organic acid to be added is preferably 0.01 mol to 90 mol, more preferably 0.1 mol to 70 mol, per mol of the basic compound.

[0036] ([A] compound) The compound [A] is 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 linked by a single bond. The first aromatic ring structure is an aromatic ring structure derived from the compound [B], and the second aromatic ring structure is an aromatic ring structure derived from the compound [C]. More specifically, the compound [A] is a compound in which a first carbon atom-second carbon atom bond is formed by cleaving a second carbon atom-OTs bond constituting a second aromatic ring structure in the compound [C], which will be described later, relative to a first carbon atom-hydrogen atom bond constituting the first aromatic ring structure in the compound [B], which will be described later.

[0037] Compound [A] can be suitably used as a functional material for electronics and communications. Because Compound [A] is produced by this production method, the content of metal components other than palladium is extremely low. Therefore, when Compound [A] is used as a functional material for electronics and communications, performance degradation due to the inclusion of the above metal components is minimal, and improved performance is expected.

[0038] The compound [A] has an extremely low content of metal components other than palladium. In particular, because this production method does not use boron compounds or tin compounds as in conventional coupling methods, the content of these metal components can be extremely low. The content of boron and tin components in the compound [A] is preferably 50 ppm or less, more preferably 10 ppm or less, and even more preferably 1 ppm or less. It is particularly preferable that the compound [A] is substantially free of boron and tin components. "Substantially free of metal components" means that the boron and tin components contained in the compound [A] are below the detection limit. Examples of methods for measuring the content of metal components, such as boron and tin components, include elemental analysis methods such as atomic absorption spectrometry, optical emission spectrometry, plasma optical emission spectrometry, X-ray fluorescence spectrometry, plasma mass spectrometry, glow discharge mass spectrometry, and ion chromatography.

[0039] In this specification, the term "aromatic ring structure" includes an "aromatic hydrocarbon ring structure" and an "aromatic heterocyclic structure." Among aromatic ring structures, polycyclic structures containing an aromatic hydrocarbon ring structure and an aromatic heterocyclic structure are considered to fall under the category of "aromatic heterocyclic structure." The term "polycyclic structure" includes not only fused polycyclic structures in which two rings share two common atoms, but also ring assembly polycyclic structures in which two rings do not share a common atom and are connected by a single bond.

[0040] The first aromatic ring structure and the second aromatic ring structure will be explained later in the sections (Compound [B]) and (Compound [C]), respectively.

[0041] An example of the first partial structure is a partial structure represented by the following formula (6).

[0042] [ka]

[0043] In the above formula (6), Ar 1 is the same as formula (4) described later. 2 is the same as equation (5) described later.

[0044] The compound [A] may be a compound having a partial structure represented by the above formula (6).

[0045] The molecular weight of the compound [A] is, for example, 200 to 2000, and preferably 230 to 1500. The molecular weight of the compound [A] is, for example, 1 It can be measured by evaluating whether the desired molecular structure is formed using H-NMR.

[0046] Examples of the compound [A] include compounds represented by the following formulas (A-1) to (A-7).

[0047] [ka]

[0048] In the above formulas (A-3) and (A-4), Ph is a phenyl group.

[0049] ([B] compound) The compound [B] is a compound having a partial structure in which a hydrogen atom is bonded to the first carbon atom constituting the first aromatic ring structure.

[0050] The number of ring members in the first aromatic ring structure is, for example, 5 to 30, and preferably 5 to 20. The "number of ring members" refers to the number of atoms constituting the ring structure, and in the case of a polycycle, refers to the number of atoms constituting the polycycle.

[0051] Examples of the first aromatic ring structure include an aromatic hydrocarbon ring structure having 6 to 30 ring members and an aromatic heterocyclic structure having 5 to 30 ring members.

[0052] Examples of the aromatic hydrocarbon ring structure include a benzene structure; condensed polycyclic aromatic hydrocarbon ring structures such as a naphthalene structure, an indene structure, an anthracene structure, a fluorene structure, a biphenylene structure, a phenanthrene structure, a pyrene structure, and a perylene structure; and ring-assembly aromatic hydrocarbon ring structures such as a biphenyl structure, a terphenyl structure, a binaphthalene structure, and a phenylnaphthalene structure.

[0053] Examples of the aromatic heterocyclic structure include oxygen atom-containing heterocyclic structures such as a furan structure, a pyran structure, a benzofuran structure, and a benzopyran structure; nitrogen atom-containing heterocyclic structures such as a pyrrole structure, a pyridine structure, a pyrimidine structure, an indole structure, a quinoline structure, and a diketopyrrolopyrrole structure; sulfur atom-containing heterocyclic structures such as a thiophene structure and a dibenzothiophene structure; silicon atom-containing heterocyclic structures such as a silafluorene structure; and heterocyclic structures containing two or more heteroatoms such as an oxazole structure and a thiazole structure.

[0054] The first aromatic ring structure is preferably a benzene structure, a biphenyl structure, a thiophene structure, a thiazole structure, or a structure in which two or more of these structures are bonded together via a single bond.

[0055] Some of the hydrogen atoms in the first aromatic ring structure may be substituted with a specific substituent. However, the hydrogen atom bonded to the first carbon atom in the first aromatic ring structure must not be substituted with a substituent. Examples of the specific substituent include 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. 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 other "fluorinated alkoxy groups" and "fluorinated alkylthio groups."

[0056] The number of carbon atoms in the alkyl group or fluorinated alkyl group is usually 1 to 30. The "number of carbon atoms" refers to the number of carbon atoms constituting the group. The "alkyl group" includes not only chain alkyl groups but also cycloalkyl groups.

[0057] Examples of the alkyl group include chain alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, 2-methylbutyl, 1-methylbutyl, n-hexyl, isohexyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, heptyl, octyl, isooctyl, 2-ethylhexyl, 3,7-dimethyloctyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, and 2-decyltetradecyl; and cycloalkyl groups such as cyclopentyl, cyclohexyl, and adamantyl.

[0058] The number of carbon atoms in the alkoxy group or fluorinated alkoxy group is usually 1 to 30. The term "alkoxy group" includes not only chain alkoxy groups but also cycloalkyloxy groups.

[0059] Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, a cyclohexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, a 3,7-dimethyloctyloxy group, a lauryloxy group, a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, a perfluorooctyloxy group, a methoxymethyloxy group, and a 2-methoxyethyloxy group.

[0060] 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 chain alkylthio groups but also cycloalkylthio groups.

[0061] Examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isobutylthio group, a tert-butylthio group, a pentylthio group, a hexylthio group, a cyclohexylthio group, a heptylthio group, an octylthio group, a 2-ethylhexylthio group, a nonylthio group, a decylthio group, a 3,7-dimethyloctylthio group, a laurylthio group, and a trifluoromethylthio group.

[0062] When the first aromatic ring structure has two or more substituents, adjacent substituents may be combined 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 those described above.

[0063] The number of ring members in the alicyclic structure is, for example, 4 to 20, and preferably 4 to 10.

[0064] Examples of the alicyclic structure include an aliphatic hydrocarbon ring structure having 4 to 20 ring members and an aliphatic heterocyclic structure having 4 to 20 ring members.

[0065] Examples of the aliphatic hydrocarbon ring structure include monocyclic saturated alicyclic structures such as a cyclobutane structure, a cyclopentane structure, and a cyclohexane structure; polycyclic saturated alicyclic structures such as a norbornane structure, an adamantane structure, a tricyclodecane structure, and a tetracyclododecane structure; monocyclic unsaturated alicyclic structures such as a cyclobutene structure, a cyclopentene structure, and a cyclohexene structure; and polycyclic unsaturated alicyclic structures such as a norbornene structure, a tricyclodecene structure, and a tetracyclododecene structure.

[0066] Examples of the aliphatic heterocyclic structure include oxygen atom-containing heterocyclic structures such as dioxolane structure and dioxane structure, and sulfur atom-containing heterocyclic structures such as dithiolane structure and dithiane structure.

[0067] When the first aromatic ring structure is an aromatic hydrocarbon ring structure, the substituent is preferably a fluorine atom, and more preferably two or more fluorine atoms, which can improve the reactivity of the compound [B].

[0068] When the first aromatic ring structure is an aromatic heterocyclic structure, the aromatic heterocyclic structure is preferably a sulfur atom-containing heterocyclic structure, more preferably a thiophene structure, which can improve the reactivity of the compound [B].

[0069] An example of the compound [B] is a compound represented by the following formula (4).

[0070] [ka]

[0071] In the above formula (4), Ar 1 is a substituted or unsubstituted aromatic ring structure, and s is an integer of 1 or more.

[0072] Ar 1 The aromatic ring structure that gives the above formula (I) is the first aromatic ring structure.

[0073] s is preferably 1 to 6.

[0074] Ar 1 In the case where is an aromatic hydrocarbon ring structure, examples of the compound [B] (hereinafter also referred to as "compound [B1]") include compounds represented by the following formulae (B1-1) to (B1-66).

[0075] [ka]

[0076] [ka]

[0077] In the above formulas (B1-1) to (B1-66), R is a substituent other than a fluorine atom, among the substituents explained in the above first aromatic ring structure.

[0078] The compound [B1] is preferably a compound represented by the following formula (4-1) or (4-2), which can improve the reactivity of the compound [B].

[0079] [ka]

[0080] Ar 1 In the case where is an aromatic heterocyclic structure, examples of the compound [B] (hereinafter also referred to as "compound [B2]") include compounds represented by the following formulae (B2-1) to (B2-31).

[0081] [ka]

[0082] In the above formulas (B2-1) to (B2-31), R is a substituent as explained in the first aromatic ring structure above.

[0083] The compound [B2] is preferably a compound represented by the following formula (4-3) or (4-4), which can improve the reactivity of the compound [B].

[0084] [ka]

[0085] In the above formula (4-3), two R 2 are each 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 are combined with each other to form a substituted or unsubstituted alicyclic structure together with the carbon chain to which they are attached.

[0086] In the above formula (4-4), R 2 is R in the above formula (4-3) 2 Also, Ph is a phenyl group.

[0087] The amount of the compound [B] to be added can be determined appropriately depending on the purpose.

[0088] ([C] compound) The compound [C] is a compound having a partial structure in which a paratoluenesulfonic acid group (TsO group) is bonded to the second carbon atom constituting the second aromatic ring structure.

[0089] In this production method, a palladium complex and a specific phosphine compound are used, and therefore, an aromatic compound having a p-toluenesulfonic acid group bonded thereto can be used as a raw material monomer in the direct arylation reaction, thereby expanding the range of monomers that can be used as raw materials in the direct arylation reaction.

[0090] The number of ring members in the second aromatic ring structure is, for example, 5 to 30, and preferably 5 to 20. Examples of the second aromatic ring structure include an aromatic hydrocarbon ring structure having 6 to 30 ring members and an aromatic heterocyclic structure having 5 to 30 ring members. Examples of the aromatic hydrocarbon ring structure and the aromatic heterocyclic structure are the same as those for the first aromatic ring structure. Furthermore, the substituents are also the same as those for the first aromatic ring structure.

[0091] The second aromatic ring structure is preferably a benzene structure, a naphthalene structure, an indene structure, an anthracene structure, a phenanthrene structure, a fluorene structure, a biphenyl structure, a terphenyl structure, a pyrene structure, a perylene structure, a dibenzothiophene structure, or a silafluorene structure.

[0092] The compound [C] may be a compound represented by the following formula (5).

[0093] [ka]

[0094] In the above formula (5), X is a paratoluenesulfonic acid group (TsO group).

[0095] In the above formula (5), Ar 2 is a substituted or unsubstituted aromatic ring structure, and t is an integer of 1 or greater.

[0096] Ar 2 The aromatic ring structure that gives the above formula is the second aromatic ring structure.

[0097] t is preferably 1 to 6, and more preferably 1 or 2.

[0098] Examples of the compound [C] include compounds represented by the following formulas (C-1) to (C-55).

[0099] [ka]

[0100] [ka]

[0101] In the above formulas (C-1) to (C-55), X has the same meaning as in the above formula (5), and R is a substituent as explained in the above first aromatic ring structure.

[0102] In this production method, the compound having a second aromatic ring structure may be a mixture of the compound [C] and an aromatic compound substituted with a halogen atom such as chlorine, bromine, or iodine, or an aromatic compound substituted with a TfO group.

[0103] This makes it possible to obtain the compound [A] having aromatic rings derived from compounds having multiple types of leaving groups, together with the compound [C].

[0104] (Palladium complex) The palladium complex is not particularly limited as long as it is a palladium complex that can be used as a catalyst in a cross-coupling reaction, and examples thereof include palladium(0) complexes and palladium(II) complexes. Specific examples include palladium chloride, palladium acetate, 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 viewpoints of ease of reaction operation and improved reaction rate.

[0105] The amount of the palladium complex to be added is not particularly limited as long as it is an effective amount as a catalyst, and can be determined appropriately. The amount of the palladium complex to be added is usually 0.0001 mol to 0.5 mol, and preferably 0.0003 mol to 0.2 mol, per 1 mol of the compound [B].

[0106] (Phosphine compounds) The phosphine compound is a compound represented by the following formula (1) (CM-Phos) or a compound represented by the following formula (2) (BrettPhos).

[0107] [ka]

[0108] In the above formulas (1) and (2), Me is a methyl group, Cy is a cyclohexyl group, and i-Pr is an isopropyl group.

[0109] In this production method, by using CM-Phos or BrettPhos together with a palladium complex, a reaction between compound [B] and compound [C] occurs to produce compound [A]. If neither CM-Phos nor BrettPhos is present in the reaction system, the reaction does not proceed at all. Furthermore, even if the reaction proceeds when using other phosphine compounds, the yield of compound [A] is extremely low. It is presumed that CM-Phos or BrettPhos coordinates to the palladium atom as a ligand of the palladium complex.

[0110] In this production method, a compound represented by the following formula (3) (hereinafter also referred to as "P(2-OMePh)3") can also be used together with CM-Phos or BrettPhos. In this case, by combining with known techniques (e.g., Macromolecules 2013, 46, 370), an aromatic compound substituted with a halogen atom such as bromine or iodine can be added as a compound having a second aromatic ring structure together with the above-mentioned [C] compound, and the reaction can be carried out. [ka]

[0111] In the above formula (3), Me is a methyl group.

[0112] The amount of each of CM-Phos, BrettPhos, and P(2-OMePh)3 added is usually 0.5 to 4 mol, preferably 1 mol to 3 mol, and more preferably 1 to 2 mol, per mol of palladium atom.

[0113] [Other processes] Examples of other steps include a step of washing the compound obtained by the reaction step (washing step), a step of purifying the compound obtained by the reaction step (purification step), etc. The specific methods for the washing step and the purification step are not particularly limited, and can be carried out according to known methods.

[0114] <Catalyst composition> The catalyst composition contains a palladium complex and CM-Phos or BrettPhos, which are described above in the "Production Method" section.

[0115] The catalyst composition can expand the selection of available monomers in the direct arylation reaction without using any metal component other than palladium, and can also synthesize compound [A] in good yield.

[0116] The catalyst composition preferably further contains P(2-OMePh)3. In this case, an aromatic compound substituted with a halogen atom such as bromine or iodine can be added as a compound having a second aromatic ring structure together with the compound [C] described above, and the reaction can be carried out. [Example]

[0117] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The methods for measuring the various physical properties are shown below.

[0118] [NMR spectrum measurement] The NMR spectra of the compounds of Examples 1 and 6 to 9 were measured by dissolving the compounds in deuterated chloroform or deuterated toluene, which are heavy solvents, using a nuclear magnetic resonance spectrometer (Bruker's AVANCEIII-400).

[0119] [Molecular weight measurement] For Examples 1 to 11, 1 The integrated value of H-NMR confirmed that a molecular structure with the desired molecular weight had been constructed.

[0120] <Synthesis of Compound [A]> According to the following method, compounds represented by the following formulas (A-1) to (A-7) (hereinafter also referred to as "compounds (A-1) to (A-7)") were synthesized as compound [A].

[0121] [ka]

[0122] In the above formulas (A-3) and (A-4), Ph is a phenyl group.

[0123] [Example 1] Synthesis of Compound (A-1) and Compound (A-2) After heating and drying a pressure-resistant reaction vessel containing a magnetic rotor, the internal atmosphere was replaced with argon. To this vessel, 10.0 μmol of tris(dibenzylideneacetone)dipalladium(0)-chloroform adduct, 40.0 μmol of 2-[2-(dicyclohexylphosphino)phenyl-1,methyl-1H-indole (CM-Phos)], and 0.25 mmol of 4,4'-di-tert-butylbiphenyl (as an internal standard for measuring NMR yields after the reaction) were added. The reaction vessel was then depressurized with a vacuum pump, then transferred to an argon-filled glove box. 1.0 mmol of phenyl paratoluenesulfonate, 0.50 mmol of 3,4-ethylenedioxythiophene, 1.5 mmol of cesium carbonate, 0.50 mmol of pivalic acid, and 1 mL of xylene were added. The reaction vessel was removed from the glove box and stirred at room temperature for 30 minutes. The reaction mixture was then heated to 140°C in an oil bath and allowed to react 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 it was found to be 8% for compound (A-1) and 89% for compound (A-2). Furthermore, since one of the two C-H bonds in compound [B] (3,4-ethylenedioxythiophene) reacted in compound (A-1) and two in compound (A-2), the reaction rate of the C-H bonds in compound [B] was calculated to be 93% based on the respective yields.

[0124] The synthesis scheme of the compound (A-1) and the compound (A-2) is shown below.

[0125] [ka]

[0126] Compound (A-1) and Compound (A-2) 1 The results of H-NMR measurement are shown below. ·Compound (A-1) 1 H-NMR (400MHz, CDCl3): δ=4.22-4.28(m,2H),4.32-4.38(m,2H),6.30(s,1H),7.23(t,J=7.5Hz,1H),7.35-7.41(m,2H),7.73(d,J=8.4Hz,2H). ·Compound (A-2) 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).

[0127] [Example 2] Phosphine Compound Modification-1 of Example 1 The same procedure as in Example 1 was carried out, except that 40.0 μmol of 2-(dicyclohexylphosphino)-3,6-dimethoxy-2',4',6'-triisopropyl-1,1'-biphenyl (BrettPhos) was used instead of CM-Phos as the ligand. The yield of the product was determined by NMR, and it was 14% for compound (A-1) and 77% for compound (A-2). The reaction rate of the C-H bond in [B] compound (3,4-ethylenedioxythiophene) was 84%.

[0128] [Example 3] Phosphine Compound Modification-2 of Example 1 The same procedure as in Example 1 was carried out, except that 40.0 μmol of tris(2-methoxyphenyl)phosphine was used in addition to CM-Phos as the ligand. The yield of the product was determined by NMR, and it was found that compound (A-1) was 9% and compound (A-2) was 85%. The reaction rate of the C-H bond of compound [B] (3,4-ethylenedioxythiophene) was 90%.

[0129] [Example 4] Phosphine Compound Modification-3 of Example 2 The same procedure as in Example 2 was carried out, except that 40.0 μmol of tris(2-methoxyphenyl)phosphine was used in addition to BrettPhos as the ligand. The yield of the product was determined by NMR, and it was found that compound (A-1) was 29% and compound (A-2) was 45%. The reaction rate of the C-H bond of compound [B] (3,4-ethylenedioxythiophene) was 60%.

[0130] [Example 5] Carboxylic acid change of Example 1-1 The same procedure as in Example 1 was carried out, except that adamantic acid (0.50 mmol) was used instead of pivalic acid as the carboxylic acid. The yields of the products were determined by NMR, and were found to be 8% for compound (A-1) and 71% for compound (A-2). The reaction rate of the C-H bond in compound [B] (3,4-ethylenedioxythiophene) was 75%.

[0131] [Example 6] Carboxylic acid change of Example 1-2 The same procedure as in Example 1 was carried out, except that acetic acid (0.50 mmol) was used instead of pivalic acid as the carboxylic acid. The yields of the products were determined by NMR, and were found to be 22% for compound (A-1) and 51% for compound (A-2). The reaction rate of the C-H bond in compound [B] (3,4-ethylenedioxythiophene) was 62%.

[0132] [Example 7] Change of basic compound in Example 1 The same procedure as in Example 1 was carried out, except that potassium phosphate (1.5 mmol) was used as the basic compound instead of cesium carbonate. The yields of the products were determined by NMR, and were found to be 15% for compound (A-1) and 61% for compound (A-2). The reaction rate of the C-H bond in compound [B] (3,4-ethylenedioxythiophene) was 69%.

[0133] [Example 8] Synthesis of compound (A-3) The same procedure as in Example 1 was carried out, except that 2-phenylthiophene (0.50 mmol) was used as compound [B] instead of 3,4-ethylenedioxythiophene (0.50 mmol), and the amount of cesium carbonate used was changed from 1.5 mol to 1.00 mmol. The yield of the product was determined by NMR, and compound (A-3) was found to be 43%. Furthermore, since compound [B] (2-phenylthiophene) has only one C-H bond, the reaction rate of the C-H bond was also calculated to be 43% from the yield of compound (A-3).

[0134] The synthesis scheme of compound (A-3) is shown below.

[0135] [ka]

[0136] The NMR measurement results of the compound (A-3) are shown below. ·Compound (A-3) 1 H-NMR (400MHz, CDCl3): δ=7.29(t,J=7.3Hz,4H),7.30(s,2H),7.39(t,J=7.3Hz,4H),7.64(d,J=7.3Hz,4H).

[0137] [Example 9] Synthesis of compound (A-4) The same procedure as in Example 1 was carried out, except that 2-phenylthiazole (0.50 mmol) was used instead of 3,4-ethylenedioxythiophene (0.50 mmol) as compound [B], and the amount of cesium carbonate used was changed from 1.5 mmol to 1.00 mmol. The yield of the product was determined by NMR, and compound (A-4) was found to be 31%. As in Example 8, the reaction rate of the C-H bond in compound [B] (2-phenylthiazole) was also calculated to be 31%.

[0138] The synthesis scheme of compound (A-4) is shown below.

[0139] [ka]

[0140] The NMR measurement results of the compound (A-4) are shown below. ·Compound (A-4) 1 H-NMR (400MHz, CDCl3): δ=7.35(tt,J=7.4,1.2Hz,1H),7.40-7.49(m,5H),7.59-7.64(m,2H),7.98(dd,J=8.1,1.4Hz,2H),8.03(s,1H).

[0141] [Example 10] Synthesis of Compound (A-5) The same procedure as in Example 1 was carried out, except that pentafluorobenzene (0.50 mmol) was used instead of 3,4-ethylenedioxythiophene (0.50 mmol) as compound [B], and the amount of cesium carbonate used was changed from 1.5 mmol to 1.00 mmol. The yield of the product was determined by NMR, and compound (A-5) was found to be 31%. As in Example 8, the reaction rate of the C-H bond in compound [B] (pentafluorobenzene) was also calculated to be 31%.

[0142] The synthesis scheme of compound (A-5) is shown below.

[0143] [ka]

[0144] The NMR measurement results of the compound (A-5) are shown below. ·Compound (A-5) 1 H-NMR (400MHz, CDCl3): δ=7.40-7.44(m,2H),7.44-7.55(m,3H) 19 F-NMR (377MHz, CDCl3): δ=-163.0--162.8(m,2F),-155.6(t,J=20.9Hz,1F),-143.2(dd,J=22.9,8.2Hz,2F).

[0145] [Example 11] Synthesis of Compound (A-6) and Compound (A-7) The same procedure as in Example 1 was carried out, except that 4H,4'H-octafluorobiphenyl (0.50 mmol) was used instead of 3,4-ethylenedioxythiophene (0.50 mmol) as compound [B]. The yields of the products were determined by NMR, and were found to be 25% for compound (A-6) and 16% for compound (A-7). Similarly to Example 1, the reaction rate of the C-H bond in compound [B] (4H,4'H-octafluorobiphenyl) was calculated to be 29%.

[0146] The synthesis scheme of the compound (A-6) and the compound (A-7) is shown below.

[0147] [ka]

[0148] The NMR measurement results of the compound (A-6) and the compound (A-7) are shown below. ·Compound (A-6) 1 H-NMR (400MHz, CDCl3): δ=7.48-7.55(m,6H). 19 F-NMR (377MHz, CDCl3): δ=-142.9--142.7(m,2F),-138.8--138.6(m,2F),-138.3--138.0(m,2F),-137.8--137.6(m,2F). ·Compound (A-7) 1 H-NMR(400MHz, CDCl3):δ=7.48-7.58(m,10H). 19 F-NMR (377MHz, CDCl3): δ=-143.0--142.8(m,4F),-138.6--138.4(m,4F).

[0149] [Comparative Example 1] The same procedure as in Example 1 was carried out, except that tris(2-methoxyphenyl)phosphine (40.0 μmol) was used as the ligand instead of CM-Phos (40.0 μmol). The yield of the product was determined by NMR, and it was found that the reaction did not proceed at all, and the target compound was not obtained.

[0150] Comparative Example 2 The same procedure as in Example 1 was carried out, except that tris(2-methoxyphenyl)phosphine (40.0 μmol) and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (XPhos) (40.0 μmol) were used as the ligand instead of CM-Phos (40.0 μmol). The yield of the product was determined by NMR, and it was found that compound (A-1) was 23% and compound (A-2) was 4%. As in Example 1, the reaction rate of the C-H bond of compound [B] (3,4-ethylenedioxythiophene) was calculated to be 16%.

Claims

1. 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 linked by a single bond, the method comprising: A method for producing a compound, 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 paratoluenesulfonyloxy group is bonded to the second carbon atom constituting the second aromatic ring structure, in the presence of a palladium complex and a compound represented by the following formula (1) or a compound represented by the following formula (2): 【Chemical 1】 (In formulas (1) and (2), Me is a methyl group, Cy is a cyclohexyl group, and i-Pr is an isopropyl group.)

2. 2. The method for producing the compound according to claim 1, wherein the reaction step is carried out in the presence of a compound represented by the following formula (3) in addition to the palladium complex and the compound represented by the formula (1) or the compound represented by the formula (2): 【Chemistry 2】 (In formula (3), Me is a methyl group.)

3. The 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 and the compound represented by formula (1) or the compound represented by formula (2).

4. 3. The method for producing a compound according to claim 2, wherein the reaction is carried out in the presence of a basic compound in addition to the palladium complex, the compound represented by formula (1) or the compound represented by formula (2), and the compound represented by formula (3).

5. The first compound is a compound represented by the following formula (4): The method for producing a compound according to any one of claims 1 to 4, wherein the second compound is a compound represented by the following formula (5): 【Chemistry 3】 (In formula (4), Ar １ is a substituted or unsubstituted aromatic ring structure, and s is an integer of 1 or more. 【Chemistry 4】 In formula (5), X is a paratoluenesulfonyloxy group. ２ is a substituted or unsubstituted aromatic ring structure; and t is an integer of 1 or more.

6. The method for producing a compound according to claim 5, wherein the first partial structure is a partial structure represented by the following formula (6): 【Chemistry 5】 (In formula (6), Ar １ has the same meaning as in formula (4). ２ is the same as the above formula (5).

7. The method for producing a compound according to claim 5, wherein the compound represented by formula (4) is a compound represented by the following formulas (4-1) to (4-4): 【Chemistry 6】 (In formula (4-3), two R ２ are each 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 are combined with each other to form a substituted or unsubstituted alicyclic structure together with the carbon chain to which they are attached. In formula (4-4), R ２ is R in the above formula (4-3). ２ and Ph is a phenyl group.

8. 1. A catalyst composition for use in a direct arylation reaction, comprising: a palladium complex; a compound represented by the following formula (1) or a compound represented by the following formula (2); A catalyst composition comprising: 【Chemistry 7】 (In formula (1), Me is a methyl group. In formula (2), Cy is a cyclohexyl group, and i-Pr is an isopropyl group.

9. The catalyst composition according to claim 8, further comprising a compound represented by the following formula (3): 【Chemistry 8】

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