Method for producing homocoupling reaction products

Abstract

The present invention addresses the problem of providing a method for producing a homo-coupling reaction product, whereby it becomes possible to substantially eliminate the use of an organic solvent, to carry out a reaction under a mild reaction condition by a simple reaction operation, to use a broad range of organic halogen compounds as starting materials, to produce a reaction product within a short time with high yield, and to produce a reaction product having a higher molecular weight. As a solution for the problem, a method for producing a homo-coupling reaction product of an organic halogen compound represented by formula (I): A1-Xm (wherein A1 represents any one of an m-valent aromatic hydrocarbon group which may have a substituent, an m-valent aromatic heterocyclic group which may have a substituent, an m-valent heterocyclic group which may have a substituent, an m-valent aliphatic hydrocarbon group which may have a substituent, and an m-valent unsaturated aliphatic hydrocarbon group which may have a substituent; X represents any one of a chlorine atom, a bromine atom and an iodine atom, in which, when there are a plurality of X's, the X's may be the same as or different from each other; and m represents the number of X's and is an integer of 1 or more) is provided, in which the organic halogen compound represented by formula (I) is reacted by a mechano-chemical method in the presence of a nickel catalyst under the following condition (a) and / or the following condition (b). Condition (a): the amount of a solvent to be used is 0.8 mL or less relative to 1 mmol of the organic halogen compound. Condition (b): a hetero-atom-containing compound is present.

Description

[Technical Field]

[0001] The present invention relates to a novel method for producing a homocoupling reaction product. [Background technology]

[0002] Homocoupling reactions are known as a method for synthesizing functional materials, such as pharmaceuticals, liquid crystal compounds, organic electroluminescent compounds, organic thin-film solar cells, polymer compounds, oligomers, coloring materials, energy ray absorbing materials, information recording materials, wavelength conversion materials, indicator materials, sensor materials, organic light-emitting diodes (OLEDs), and organic semiconductor materials. Homocoupling reactions are reactions that bond molecules of the same type and are used to synthesize a variety of compounds. In particular, the homocoupling reaction of halogen compounds in the presence of a nickel catalyst (the Yamamoto homocoupling reaction) is used to synthesize compounds through carbon-carbon bond-forming reactions and in the polymerization of π-conjugated polymers.

[0003] Non-Patent Document 1 discloses a reaction in which aromatic halogen compounds are homo-coupled with each other using a zero-valent nickel complex, which is accompanied by a dehalogenation reaction, to produce a biaryl compound. Non-Patent Documents 2 and 3 disclose that polypyridines and the like can be synthesized in high yield by carrying out dehalogenation polycondensation through a homocoupling reaction using an aromatic dihalogen compound and a zero-valent nickel catalyst, and that the dehalogenation polycondensation is applicable to a very wide range of monomers. Patent Document 1 discloses a method for producing a cyclic aromatic compound, in which a zero-valent nickel catalyst is mixed with a m-dihalogenated benzene such as 1,3-dibromobenzene, and the m-dihalogenated benzene is polymerized by a Yamamoto coupling reaction to obtain a cyclic aromatic compound. Patent Document 2 discloses a method for producing a copolymer by polymerizing a dihalogen compound monomer (A) and a dihalogen compound macromer (B) in the presence of zinc (C) and a divalent nickel complex (D) catalyst. Patent Document 3 discloses a cross-coupling reaction method in which an organic compound (A) having a leaving group and a melting point of 30°C or higher is reacted with an organic compound (B) having a melting point of 30°C or higher and capable of reacting with an organic compound having a leaving group, in the presence of a catalyst, under conditions where the amount of organic solvent present is 0.7 mL or less per 1 mmol of the total of organic compound (A) and organic compound (B), and the temperature is 60 to 500°C, by a mechanochemical method in which mechanical energy is applied to organic compound (A) and organic compound (B). [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] MFSemmelhack, et al, J.Am.Chem.Soc.,1971,Vol.93,No.22,5908-5910 [Non-patent document 2] T, Yamamoto, et al, Chem.Lett.,1988,Vol.17,No.1,153-154, [Non-patent document 3] T. Yamamoto, et al, Macromolecules,1992,Vol.25,No.4,1214-1223 [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-32083 [Patent Document 2] Japanese Patent Application Publication No. 2019-19226 [Patent Document 3] International Publication No. 2022 / 092260 Summary of the Invention [Problem to be solved by the invention]

[0006] Homocoupling reactions generally require a relatively large amount of organic solvent because the starting compounds are dissolved in the organic solvent. However, in recent years, the use of large amounts of organic solvent has been associated with concerns about the working environment and safety of workers, global environmental protection, and the environmental impact of treating the organic solvent after use. Furthermore, due to factors such as the stability of the nickel catalyst used, strict reaction conditions were required, the reaction time was long, and the reaction procedures were complicated. Furthermore, the yield was unsatisfactory.

[0007] The problem to be solved by the present invention is to provide a method for producing a homocoupling reaction product, which can substantially do without using an organic solvent, can carry out the reaction under mild reaction conditions and with a simple reaction operation, can use a wide range of organic halogen compounds as raw materials, can produce a reaction product in high yield in a short time, and can produce a reaction product with a high molecular weight. [Means for solving the problem]

[0008] As a result of extensive research, the present inventors have discovered that the above-mentioned problems can be solved by carrying out a homocoupling reaction by a mechanochemical method under specific conditions, and have thus completed the present invention. That is, the present invention provides the following method for producing a homocoupling reaction product. [Term 1] Formula (I); A 1 -X m (I) (In formula (I), A 1 represents any one of an m-valent aromatic hydrocarbon group which may have a substituent, an m-valent aromatic heterocyclic group which may have a substituent, an m-valent heterocyclic group which may have a substituent, an m-valent aliphatic hydrocarbon group which may have a substituent, or an m-valent unsaturated aliphatic hydrocarbon group which may have a substituent. X represents any one of chlorine, bromine, and iodine, and when there are a plurality of X's, they may be the same or different. m is the number of Xs and represents an integer of 1 or greater.) in the presence of a nickel catalyst under condition (a) and / or condition (b); Condition (a): The amount of solvent used is 0.8 mL or less per 1 mmol of organic halogen compound. Condition (b): in the presence of a heteroatom-containing compound; a method for producing a homocoupling reaction product of an organic halogen compound represented by formula (I) by reacting the above by a mechanochemical method. [Item 2] In the formula (I), m is 1 or more and 4 or less, The homocoupling reaction product is represented by formula (A), formula (P1), formula (P2) or formula (P3); Formula (A); A 1 -A 1 (A) (In formula (A), A 1 may be the same or different.) a homocoupling reaction product represented by Formula (P1); [ka] (In formula (P1), a plurality of A 1 may be the same or different, and n1 is an integer of 2 or greater.) a linear homocoupling reaction polymerization product, a cyclic homocoupling reaction polymerization product, or an intramolecular homocoupling reaction product having a repeating unit represented by the formula: formula(P2); [ka] (In formula (P2), a plurality of A 1 may be the same or different, and n2 is an integer of 2 or greater.) A polymer having a unit represented by Formula (P3); [ka] (In formula (P3), a plurality of A 1 may be the same or different, and n3 is an integer of 2 or greater.) A polymer having a unit represented by Item 2. A method for producing a homocoupling reaction product according to Item 1, [Item 3] The method for producing a homocoupling reaction product according to Item 1 or 2, wherein the melting point of the solvent is 30°C or lower and / or the melting point of the heteroatom-containing compound is 50°C or higher. [Item 4] The method for producing a homocoupling reaction product according to any one of Items 1 to 3, wherein a reducing agent is further present during the reaction by the mechanochemical method. [Item 5] The method for producing a homocoupling reaction product according to any one of Items 1 to 4, wherein the reaction is carried out at a temperature of 60°C or higher by the mechanochemical method. [Effects of the Invention]

[0009] The present invention provides a method for producing a homocoupling reaction product, which can substantially eliminate the use of organic solvents, can carry out the reaction under mild reaction conditions and with simple reaction procedures, can use a wide range of organic halogen compounds as raw materials, can produce a reaction product in high yield in a short period of time, and can produce a reaction product with a high molecular weight. DETAILED DESCRIPTION OF THE INVENTION

[0010] [Method of producing homocoupling reaction product] The method for producing the homocoupling reaction product of the present invention comprises reacting a compound represented by formula (I); A 1 -X m (I) (In formula (I), A 1 represents any one of an m-valent aromatic hydrocarbon group which may have a substituent, an m-valent aromatic heterocyclic group which may have a substituent, an m-valent heterocyclic group which may have a substituent, an m-valent aliphatic hydrocarbon group which may have a substituent, or an m-valent unsaturated aliphatic hydrocarbon group which may have a substituent. X represents any one of chlorine, bromine, and iodine, and when there are a plurality of X's, they may be the same or different. m is the number of Xs and represents an integer of 1 or greater.) in the presence of a nickel catalyst under condition (a) and / or condition (b); Condition (a): The amount of solvent used is 0.8 mL or less per 1 mmol of organic halogen compound. Condition (b): in the presence of a heteroatom-containing compound; This is a method for producing a homocoupling reaction product by reacting the above-mentioned compounds by a mechanochemical method. The method for producing a homocoupling reaction product of the present invention may be a method for producing a homocoupling reaction product in which the reaction is carried out by a mechanochemical method under only the above condition (a). The method for producing a homocoupling reaction product of the present invention may be a method for producing a homocoupling reaction product in which the reaction is carried out by a mechanochemical method under only the above condition (b). The method for producing a homocoupling reaction product of the present invention may be a method for producing a homocoupling reaction product that satisfies both the above-mentioned condition (a) and the above-mentioned condition (b) and that involves the reaction by a mechanochemical method.

[0011] <Organic halogen compounds> In the method for producing a homocoupling reaction product of the present invention, the organic halogen compound may be a compound of formula (I); A 1 -X m (I) (In formula (I), A 1 represents any one of an m-valent aromatic hydrocarbon group which may have a substituent, an m-valent aromatic heterocyclic group which may have a substituent, an m-valent heterocyclic group which may have a substituent, an m-valent aliphatic hydrocarbon group which may have a substituent, or an m-valent unsaturated aliphatic hydrocarbon group which may have a substituent. X represents any one of chlorine, bromine, and iodine, and when there are a plurality of X's, they may be the same or different. m is the number of Xs and represents an integer of 1 or greater.) Examples of the compound include compounds represented by the following formula: The organic halogen compound represented by formula (I) can be used alone or in combination of two or more. The organic halogen compound represented by formula (I) can be used as a commercially available product either as is or after purification.

[0012] (A in formula (I) 1 basis) A 1 The number of carbon atoms in the m-valent aromatic hydrocarbon group which may have a substituent in the group is not particularly limited, and is, for example, 6 to 60, preferably 6 to 40, and more preferably 6 to 30. In the m-valent aromatic hydrocarbon group, m is an integer of 1 or more, for example, 1 to 10, preferably 1 to 6, and more preferably 1 to 4. A 1 In the m-valent aromatic hydrocarbon group which may have a substituent in the group, examples of the monovalent aromatic hydrocarbon group where m=1 include a phenyl group, a naphthyl group, an anthracenyl group (or anthracene group), a phenanthrenyl group (or phenanthrene group), a biphenyl group, a terphenyl group, a pyrenyl group (or pyrene group), a perylenyl group (or perylene group), a triphenylenyl group (or triphenylene group), a fluorenyl group, and a spirobifluorenyl group. Also, A 1 In the m-valent aromatic hydrocarbon group which may have a substituent in the group, examples of the m-valent aromatic hydrocarbon group where m is an integer of 2 or more include those in which m-1 hydrogen atoms have been removed from the aromatic ring in the above-mentioned monovalent aromatic hydrocarbon group.

[0013] A 1 The number of carbon atoms in the m-valent aromatic heterocyclic group which may have a substituent in the group is not particularly limited, and is, for example, 4 to 60, preferably 4 to 40, and more preferably 4 to 30. A 1 In the m-valent aromatic heterocyclic group in the group, m is an integer of 1 or more, for example, 1 to 10, preferably 1 to 6, and more preferably 1 to 4. A 1In the m-valent aromatic heterocyclic group optionally having a substituent in the group, examples of the monovalent aromatic heterocyclic group where m=1 include sulfur-containing heteroaryl groups such as a thiophenyl group (thiophene group or thienyl group), a benzothienyl group (benzothiophene group), and a dibenzothienyl group (dibenzothiophene group); oxygen-containing heteroaryl groups such as a furanyl group (or furan group), a benzofuranyl group (benzofuran group), a dibenzofuranyl group (dibenzofuran group), a phenyldibenzofuranyl group, and a dibenzofuranylphenyl group; a pyridyl group (or pyridine group), a pyrimidinyl group (or pyrimidine group), a pyridyl group (or pyridine group), a pyridyl group (or pyrimidine group), a pyridyl group (or pyridine group), a pyridyl group (or pyrimidine group), a pyridyl group (or pyridine group), a pyridyl group (or pyridine group), a pyridyl group (or pyrimidine group), a pyridyl group (or pyridine group), a pyridyl group (or pyridine group), a pyridyl group (or pyridine group), a pyridyl group (or pyridyl ... These include nitrogen-containing heteroaryl groups such as a pyrazine group (or pyrazine group), a quinolyl group (or quinoline group), an isoquinolyl group (or isoquinoline group), a carbazolyl group (or carbazole group), a 9-phenylcarbazolyl group, an acridinyl group (or acridine group), a quinazolyl group (or quinazoline group), a quinoxalyl group (or quinoxaline group), a 1,6-naphthyridinyl group, a 1,8-naphthyridinyl group, and a porphyrin group (or porphyrin ring); and heteroaryl groups containing two or more types of heteroatoms (for example, nitrogen and sulfur), such as a benzothiazolyl group (or benzothiazole group) and a benzothiadiazole group.Further, a pyrrole group, a silole group, a borole group, a phosphole group, a selenophene group, a germole group, an indole group, an indene group, a benzosilole group, a benzoborole group, a benzophosphole group, a benzoselenophene group, a benzogermole group, a dibenzosilole group, a dibenzoborole group, a dibenzophosphole group, a dibenzoselenophene group, a dibenzogermole group, a dibenzothiophene 5-oxide group, a 9H-fluoren-9-one group, a dibenzothiophene 5,5-dioxide group, an azabenzothiophene group, an azabenzofuran group, an azaindole group, an azaindene group, an azabenzosilole group, an azabenzoborole group, an azabenzophosphole group, an azabenzoselenophene group, an azabenzogermole group, an azadibenzothiophene group, an azadibenzofuran group, Examples thereof include an azacarbazole group, an azafluorene group, an azadibenzosilole group, an azadibenzoborole group, an azadibenzophosphole group, an azadibenzoselenophene group, an azadibenzogermole group, an azadibenzothiophene 5-oxide group, an aza-9H-fluoren-9-one group, an azadibenzothiophene 5,5-dioxide group, a pyridazine group, a triazine group, a phenanthroline group, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an isoxazole group, a thiazole group, an isothiazole group, an oxadiazole group, a thiadiazole group, a benzopyrazole group, a benzimidazole group, a benzoxazole group, a benzoxadiazole group, a 5,6,7,8-tetrahydroisoquinoline group, and a 5,6,7,8-tetrahydroquinoline group. Also, A 1 In the m-valent aromatic heterocyclic group optionally having a substituent in the group, examples of the m-valent aromatic heterocyclic group where m is an integer of 2 or more include those in which m-1 hydrogen atoms have been removed from the aromatic ring in the above-mentioned monovalent aromatic heterocyclic group. Other examples include a benzo[1,2-c:4,5-c']bis[1,2,5]thiadiazole skeleton (benzobisthiadiazole group), a thienylenyl group (or a thiophenediyl group), a phenyldibenzothienylenyl group, a dibenzothienylenylphenyl group, and a pyridylenyl group (or a pyridinediyl group).

[0014] A 1The number of carbon atoms in the m-valent aliphatic hydrocarbon group which may have a substituent in the group is not particularly limited, and is, for example, 2 to 60, preferably 3 to 40, and more preferably 5 to 30. A 1 In the m-valent aliphatic hydrocarbon group in the group, m is an integer of 1 or more, for example, 1 to 10, preferably 1 to 6, and more preferably 1 to 4. A 1 In the m-valent aliphatic hydrocarbon group which may have a substituent in the group, examples of the monovalent aliphatic hydrocarbon group where m=1 include saturated aliphatic hydrocarbon groups such as alkyl groups and cycloolefin groups. Also, A 1 In the m-valent aliphatic hydrocarbon group which may have a substituent in the group, examples of the m-valent aliphatic hydrocarbon group where m is an integer of 2 or greater include those in which m-1 hydrogen atoms have been removed from the above-mentioned monovalent aliphatic hydrocarbon group. A 1 The m-valent aliphatic hydrocarbon group, which may have a substituent in the group, may contain a heteroatom (e.g., nitrogen, oxygen, phosphorus, sulfur, etc.) in the main chain or in the substituent. Examples of the substituent containing a heteroatom include the above-mentioned aromatic heterocyclic groups such as the thiophenyl group, furanyl group, and pyrrole group, and saturated heterocyclic groups such as the tetrahydrothienyl group, tetrahydrofuranyl group, pyrrolidinyl group, piperazyl group, and morpholyl group.

[0015] A 1 The number of carbon atoms in the m-valent unsaturated aliphatic hydrocarbon group which may have a substituent in the group is not particularly limited, and is, for example, 2 to 60, preferably 3 to 40, and more preferably 5 to 30. A 1 In the m-valent unsaturated aliphatic hydrocarbon group in the group, m is an integer of 1 or more, for example, 1 to 10, preferably 1 to 6, and more preferably 1 to 4. A 1 In the m-valent unsaturated aliphatic hydrocarbon group which may have a substituent in the group, examples of the monovalent aromatic hydrocarbon group where m=1 include an alkenyl group and an alkynyl group. Also, A 1In the m-valent unsaturated aliphatic hydrocarbon group which may have a substituent in the group, examples of the m-valent unsaturated aliphatic hydrocarbon group where m is an integer of 2 or more include those in which m-1 hydrogen atoms have been removed from the above-mentioned monovalent unsaturated aliphatic hydrocarbon group. A 1 The m-valent unsaturated aliphatic hydrocarbon group, which may have a substituent in the group, may contain a heteroatom (e.g., nitrogen, oxygen, phosphorus, sulfur, etc.) in the main chain or in the substituent. Examples of the substituent containing a heteroatom include the above-mentioned aromatic heterocyclic groups such as the thiophenyl group, furanyl group, and pyrrole group, and saturated heterocyclic groups such as the tetrahydrothienyl group, tetrahydrofuranyl group, pyrrolidinyl group, piperazyl group, and morpholyl group.

[0016] In the organic halogen compound represented by formula (I), A in formula (I) 1 Examples of the group include the following groups. phenyl groups (e.g., alkyl (e.g., methyl)phenyl groups, dialkyl (e.g., dimethyl)phenyl groups, alkoxy (e.g., methoxy)phenyl groups, dialkylamino (e.g., dimethylamino)phenyl groups, diaryl (e.g., diphenyl)aminophenyl groups, perfluoroalkyl (e.g., trifluoromethyl)phenyl groups, alkyl (e.g., ethyl)oxycarbonylphenyl groups, alkanoyl (e.g., acyl)phenyl groups, etc.), alkylene groups, phenyl groups bridged with linking groups such as ether groups and ester groups; naphthyl groups such as naphthyl groups, aryl (e.g., phenyl, etc.) naphthyl groups, naphthyl groups having alkylene (e.g., ethylene, etc.) bridges, and naphthyl groups having arylene (e.g., phenylene, etc.) bridges; phenanthrenyl group; anthracenyl groups such as an anthracenyl group, an aryl (e.g., phenyl, etc.) anthracenyl group, a diaryl (e.g., dinaphthyl, etc.) anthracenyl group, and a diarylboryl (e.g., bis(trialkylphenyl)boryl, etc.) anthracenyl group; pyrenyl groups such as pyrenyl groups and alkyl (e.g., tert-butyl, etc.) pyrenyl groups; biphenyl groups, such as biphenyl groups, biphenyl groups having alkylene (e.g., propylene, isopropylene, etc.) bridges; terphenyl groups such as terphenyl groups, tetraaryl (e.g., tetraphenyl, etc.) terphenyl groups; Triphenylenyl group; Fluorenyl group, spirobifluorenyl group; 2-aryl (e.g., phenyl, etc.) ethenylphenyl group, 1,2,2-triaryl (e.g., triphenyl, etc.) ethenylphenyl group, 2-aryl (e.g., phenyl, etc.) ethenylphenyl group; aryl (e.g., phenyl, etc.) substituted carbazolyl groups; anthracene-9.10-dione group; Aryl (e.g., phenyl, etc.)-substituted thienyl groups, thiophene groups, benzothiadiazole groups; Groups having a valence of 2 or more, such as a phenylene group, an aryl (e.g., bis(3,5-methylphenyl)) porphyrin ring, a pyrene-tetrayl group, and a benzo[1,2-c:4,5-c']bis[1,2,5]thiadiazole skeleton (benzobisthiadiazole group).

[0017] A 1 The substituents that the m-valent aromatic hydrocarbon group optionally having a substituent, the m-valent aromatic heterocyclic group optionally having a substituent, the m-valent aliphatic hydrocarbon group optionally having a substituent, or the m-valent unsaturated aliphatic hydrocarbon group optionally having a substituent in the group are not particularly limited as long as the homocoupling reaction targeted by the present invention can be carried out. Examples of the substituent include alkyl groups having 1 to 24 carbon atoms, preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 8 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, and octyl groups); alkoxy groups having 1 to 24 carbon atoms, preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 8 carbon atoms (e.g., methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and isobutoxy groups); tert-butoxy group, pentyloxy group, hexyloxy group, octyloxy group, etc.); cycloalkyl groups having 3 to 24 carbon atoms, preferably 3 to 18, more preferably 3 to 12, and even more preferably 3 to 8 carbon atoms (for example, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, etc.); alkenyl groups having 1 to 24 carbon atoms, preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 8 carbon atoms (for example, ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, octyloxy group, etc.). alkynyl groups having 1 to 24, preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 8 carbon atoms (e.g., ethynyl, propynyl, butynyl, pentynyl, hexynyl, octynyl, and the like); aryl groups having 5 to 24, preferably 5 to 18, more preferably 5 to 12, and even more preferably 5 to 8 carbon atoms (e.g., phenyl, naphthyl, biphenyl, and the like); arylalkyl groups having 7 to 24, preferably 7 to 19, more preferably 7 to 13, and even more preferably 7 to 9 carbon atoms (e.g., monophenyl, an aryloxy group having 5 to 24, preferably 5 to 18, more preferably 5 to 12, and even more preferably 5 to 8 carbon atoms (e.g., a phenoxy group, a naphthyloxy group, a biphenyloxy group, etc.); a heteroaryl group having 4 to 24, preferably 4 to 18, more preferably 4 to 12, and even more preferably 4 to 8 carbon atoms (e.g., a thiophenyl group, a furanyl group, a carbazole group, a benzothiophenyl group, a benzofuranyl group, an indolyl group, a pyrrolyl group, a pyridyl group, etc.);Examples of such groups include at least one selected from the group consisting of acyl groups having 1 to 24, preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 8 carbon atoms (e.g., acetyl, propionyl, butanoyl, pentanoyl, heptanoyl, and groups in which the carbonyl group contained in such acyl groups is substituted with an ester or amide group); amino groups having 1 to 24, preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 8 carbon atoms (e.g., diphenylamino, dimethylamino); fluorine, fluorine-containing groups such as fluorine-containing hydrocarbon groups having 1 to 30, preferably 1 to 12, carbon atoms; cyano, nitro, and the like; The substituents may be crosslinked to each other, or the substituents may together form a cyclic structure (aromatic group). The substituent may further have a substituent.

[0018] (X group in formula (I)) The X group represents any one of chlorine, bromine, and iodine, and when there are multiple Xs, they may be the same or different. Appropriate groups can be used depending on reactivity and the like. The number m of X groups in formula (I) is not particularly limited as long as it is an integer of 1 or more and is within a range in which a homocoupling reaction can be carried out, and can be, for example, 10 or less, preferably 8 or less, more preferably 6 or less, and even more preferably 4 or less.

[0019] <Nickel catalyst> Nickel used in the method for producing a homocoupling reaction product of the present invention catalyst The nickel catalyst is not particularly limited as long as it can catalyze (promote) the homocoupling reaction of a halogen compound. The nickel catalyst is preferably a zero-valent nickel catalyst containing zero-valent nickel or a divalent nickel catalyst containing divalent nickel. The nickel catalyst is more preferably a catalyst capable of forming zero-valent nickel (Ni(0)) in the reaction system. Examples of the nickel catalyst include one or more selected from the group consisting of a zero-valent nickel complex having Ni(0), a divalent nickel complex having Ni(II), a salt of zero-valent Ni, and a salt of divalent Ni. A mixture of one or more zero-valent nickel catalysts and one or more divalent nickel catalysts may also be used. When a divalent nickel complex is used, it can be used in combination with a reducing agent described below. The nickel catalyst can be used alone or in combination of two or more. Commercially available nickel catalysts can be used directly or after purification due to their availability. If necessary, the nickel catalyst can be supported on a carrier such as alumina, carbon, silica, or zeolite.

[0020] Examples of zero-valent nickel catalysts include bis(1,5-cyclooctadiene)nickel(0) [Ni(cod)2] 、 Examples thereof include one or more selected from the group consisting of tetrakis(triphenylphosphine)nickel(0), tetracarbonylnickel(0), dicarbonylbis(triphenylphosphine)nickel(0), and hydrates thereof.

[0021] Examples of divalent nickel catalysts include dichloro[bis(triphenylphosphine)]nickel(II) [Ni(PPh3)2Cl2], dibromo[bis(triphenylphosphine)]nickel(II) [Ni(PPh3)2Br2], dichloro[bis(diphenylphosphino)methane]nickel(II) [Ni(dppm)Cl2], dibromo[bis(diphenylphosphino)methane]nickel(II) [Ni(dppm)Br2], dichloro[1,2-bis(diphenylphosphino)ethane]nickel(II) [Ni(dppe)Cl2], dibromo[1,2-bis(diphenylphosphino)ethane]nickel(II) [Ni(dppe)Br2], dichloro[1,3-bis(diphenylphosphino)propane]nickel(II) [Ni(dppp)Cl2], and dibromo[1,3-bis(diphenylphosphino)propane]nickel(II). [Ni(dppp)Br2], dichloro[1,1'-bis(diphenylphosphino)iron]nickel(II) [Ni(dppf)Cl2], dibromo[1,1'-bis(diphenylphosphino)iron]nickel(II) [Ni(dppf)Br2], dichloro[1,4-bis(diphenylphosphino)butane]nickel(II), dibromo[1,4-bis(diphenylphosphino)butane]nickel(II), dichlorobis(tributylphosphine)nickel(II), dibromobis(tributylphosphine)nickel(II), dichlorobis(trimethylphosphine)nickel(II), dibromobis(trimethylphosphine)nickel(II), dichloro(ethylenediamine)nickel, dibromo(ethylenediamine)nickel, dichloro(N,N,N',N'-tetramethylethylenediamine)nickel(II), dibromo(N,N,N',N'-Tetramethylethylenediamine)nickel(II), dichloro[bis(tri-n-butylphosphine)]nickel(II), dibromo[bis(tri-n-butylphosphine)]nickel(II), dichloro[bis(cyclohexyldiphenylphosphine)]nickel(II), dibromo[bis(cyclohexyldiphenylphosphine)]nickel(II), dichloro[bis(tricyclohexylphosphine)]nickel(II), dibromo[bis(tricyclohexylphosphine)]nickel(II), dichloro[bis(trianisoylphosphine)]nickel(II), dibromo[bis(trianisoylphosphine)]nickel(II), dichloro[2,3-bis(2,6-diisopropylphenylimino)butane]nickel(II), dibromo[2,3-bis(2,6-diisopropylphenylimino)butane]nickel(II), chloro(2-methylphenyl)bis(triphenylphosphine)nickel(II), bromo(2-methylphenyl)bis(triphenylphosphine)nickel(II), chloro[bis[(2-dimethylamino)phenyl]amine]nickel(II), bromo[bis[(2-dimethylamino)phenyl]amine]nickel(II), chloro(cyclopentadienyl)(triphenylphosphine)nickel(II), bromo(cyclopentadienyl)(triphenylphosphine)nickel(II), chloro(ethylcyclopentadienyl)(triphenylphosphine)nickel(II), bromo(ethylcyclopentadienyl)(triphenylphosphine)nickel(II), chloro(2-methylphenyl)bis(triphenylphosphine)nickel(II), bromo(2-methylphenyl)bis(triphenylphosphine)nickel(II), chloro(1-naphthyl)bis(triphenylphosphine)nickel(II), bromo(1-naphthyl)bis(triphenylphosphine)nickel(II), bis( (isopropylcyclopentadienyl)nickel, bis(methylcyclopentadienyl)nickel(II), nickel acetylacetonate(II), methallylnickel chloride dimer, hexaaminenickel(II) bromide, bis(trifluoromethanesulfonimide)nickel(II), hexafluoroacetylacetonatenickel(II), bis(4-diethylaminodithiobenzyl)nickel(II), N,N'-bis(salicylidene)ethylenediaminonickel(II), bis(cyclopentadienyl)nickel(II), salts Nickel(II) chloride, nickel(II) bromide, nickel(II) iodide, nickel(II) fluoride, nickel(II) nitrate, nickel(II) sulfate, nickel(II) carbonate, nickel(II) boride, nickel(II) borate, nickel(II) hypophosphite, ammonium nickel(II) sulfate, nickel(II) hydroxide, nickel(II) formate, nickel(II) acetate, nickel(II) trifluoroacetate, nickel(II) citrate, nickel(II) oxalate, nickel(II) cyclohexanebutyrate, nickel(II) benzoate, ,vinegarExamples of the nickel ionomer include one or more selected from the group consisting of nickel(II) tearate, nickel(II) sulfamate, nickel(II) thiocyanate, nickel(II) trifluoromethanesulfonate, and hydrates thereof.

[0022] In the method for producing a homocoupling reaction product of the present invention, the amount of nickel catalyst used is not particularly limited. It is, for example, 0.01 mol or more, preferably 0.05 mol or more, more preferably 0.1 mol or more, and even more preferably 0.5 mol or more per mol of the organic halogen compound, and is, for example, 50 mol or less, preferably 30 mol or less, more preferably 20 mol or less, and even more preferably 10 mol or less. For example, if the amount is less than 0.01 mol or more than 50 mol per mol of the organic halogen compound, the reaction may not proceed smoothly.

[0023] <Solvent> Condition (a) in the method for producing a homocoupling reaction product of the present invention is a condition in which the amount of solvent used is 0.8 mL or less per 1 mmol of organic halogen compound. Such conditions can be said to be conditions in which substantially no solvent is used. In the present invention, "conditions in which substantially no solvent is used" refers to any of the following: an embodiment in which no solvent is used at all; an embodiment in which no solvent is actively used; and an embodiment in which a solvent is used but in such a small amount that the solvent effect is not exerted.

[0024] In the method for producing a homocoupling reaction product of the present invention, the solvent in condition (a) is not particularly limited. The solvent is a liquid at room temperature (25°C ± 5°C) that does not react with the substrate, the organohalogen compound represented by formula (I). For example, a solvent used in a homocoupling reaction carried out in a solution system can be used. For example, oxygen-containing organic solvents such as methanol, ethanol, n-propanol, isopropanol, 1-butanol, 1,1-dimethylethanol, tert-butanol, 2-methoxyethanol, ethylene glycol, polyethylene glycol, polypropylene glycol, diethyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, tetrahydrofuran, tetrahydropyran, cyclopentyl methyl ether, dimethoxyethane, 1,4-dioxane, anisole, acetoxy-2-ethoxyethane, propylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, polyethylene glycol diethyl ether, 1-methoxy-1,1,2,2-tetrafluoroethane, 1-ethoxy-1,1,2,2-tetrafluoroethane, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, and acetic acid; benzene, toluene, xylene, and mesitylene. 、 Examples of the solvent include one or more selected from the group consisting of aromatic solvents such as durene and decalin; aliphatic organic solvents such as hexane, pentane, and heptane; halogenated hydrocarbon organic solvents such as dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, and 1,2-dichlorobenzene; nitrogen-containing organic solvents such as acetonitrile, N,N'-dimethylformamide, N,N'-dimethylacetamide, N-methyl-2-pyrrolidone, and pyridine; sulfur-containing organic solvents such as dimethyl sulfoxide; and water. The solvent is preferably a solvent having a melting point of 30°C or less, and particularly preferably an organic solvent having a melting point of 30°C or less.

[0025] In the method for producing a homocoupling reaction product of the present invention, a solvent can be used as a liquid grinding aid (LIQUID Assisted Grinding: LAG) during the mechanochemical reaction. The liquid grinding aid is preferably at least one selected from the group consisting of oxygen-containing organic solvents such as 2-methoxyethanol, ethylene glycol, diethyl ether, dibutyl ether, t-butyl methyl ether, tetrahydrofuran, 1,4-dioxane, propylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethyl ether, dibutyl ether, tetrahydrofuran, ethylene glycol, polypropylene glycol, polyethylene glycol dimethyl ether, and polyethylene glycol diethyl ether; nitrogen-containing organic solvents such as N,N'-dimethylformamide, N,N'-dimethylacetamide, N-methyl-2-pyrrolidone, and pyridine; and sulfur-containing organic solvents such as dimethyl sulfoxide. Particularly preferably, one or more selected from the group consisting of 2-methoxyethanol, ethylene glycol, diethyl ether, dibutyl ether, t-butyl methyl ether, tetrahydrofuran, N',N'-dimethylformamide, N,N'-dimethylacetamide, N-methyl-2-pyrrolidone, pyridine, and dimethyl sulfoxide can be used.

[0026] In the method for producing a homocoupling reaction product of the present invention, the amount of solvent used is 0.8 mL or less, preferably 0.5 mL or less, and more preferably 0.3 mL or less, per 1 mmol of organic halogen compound. In the method for producing a homocoupling reaction product of the present invention, the amount of solvent used can be 0 mL (no solvent used). Generally, in a homocoupling reaction carried out in a solution system, an organic solvent is used in an amount of 1 mL or more per 1 mmol of the total of the reaction raw materials. In the present invention, the amount of solvent, particularly the organic solvent, used is 0.8 mL or less per 1 mmol of the organic halogen compound. Therefore, at the start of the reaction, components such as the organic halogen compound and the nickel catalyst usually exist in a state where at least a part of them is not dissolved in the solvent, etc., and in some cases, they are not dissolved at all in the solvent, etc., and exist in a solid state, and react.

[0027] <Heteroatom-containing compounds> Condition (b) in the method for producing a homocoupling reaction product of the present invention is a condition in the presence of a heteroatom-containing compound. Heteroatoms refer to atoms other than carbon and hydrogen. In the present invention, heteroatoms are preferably nitrogen atoms, phosphorus atoms, boron atoms, and oxygen atoms. In the method for producing a homocoupling reaction product of the present invention, the heteroatom-containing compound in condition (b) is not particularly limited. Preferably, the heteroatom-containing compound has a melting point of 50°C or higher. Examples of heteroatom-containing compounds include bipyridine-based compounds such as bipyridine, 4,4'-bis(di-tert-butyl)-2,2'-bipyridine, and phenanthroline; aryl phosphines such as triphenylphosphine, tri(o-tolyl)phosphine, tri(2-furyl)phosphine, tert-butyldiphenylphosphine, tris(2,5-xylyl)phosphine, and tri(mesityl)phosphine; alkyl phosphine compounds such as trimethylphosphine, tributylphosphine, tri(isopropyl)phosphine, tri(tert-butyl)phosphine, and tri(cyclohexyl)phosphine; 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (SPhos), 2-(dicyclohexylphosphino)-2'-(N,N-dimethylamino)biphenyl (DavePhos) ), 2-(di-tert-butylphosphino)-2',4',6'-triisopropyl-3,6-dimethoxy-1,1'-biphenyl (tBuBrettPhos), 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, 2-dicyclohexylphosphino-2'-methylbiphenyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 2-(di-tert-butylphosphino)-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphino-3,6-dimethoxy-2',4',6'-triisopropylbiphenyl, 2-(dicyclohexylphosphino)biphenyl, 2-(di-tert-butylphosphino)-2'-(N,N-dimethylamino)biphenyl and other Buchwald phosphine ligand compounds;2-(di-tert-butylphosphino)biphenyl, 2-(dicyclohexylphosphino)biphenyl, 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,2-bis(diphenylphosphino)propane, 1,2-bis(dicyclohexylphosphino)ethane, 1,2-bis(diphenylphosphino)butane, 1,4-bis(diphenylphosphino)butane, 2,2-dimethyl-1,3-bis(diphenylphosphino)propane, 1,1'-bis(diphenylphosphino)ferrocene, 1,2-bis Examples of suitable compounds include bidentate phosphine compounds such as bis(diphenylphosphino)ferrocene; N-heterocarbene compounds such as 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydro-1H-imidazolium chloride, 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride, and 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-1H-imidazolium chloride; and trialkylphosphonium tetrafluoroborate compounds such as t-Bu3P·HBF4 (tri-tert-butylphosphonium tetrafluoroborate).

[0028] In the method for producing a homocoupling reaction product of the present invention, the amount of a heteroatom-containing compound used is not particularly limited. For example, the amount is 10 mol or less, preferably 8 mol or less, more preferably 5 mol or less, and even more preferably 3 mol or less per mol of nickel catalyst. The use of a heteroatom-containing compound allows the homocoupling reaction to proceed with high selectivity.

[0029] <Reducing agent> In the method for producing a homocoupling reaction product of the present invention, a reducing agent can also be used. The reducing agent is not particularly limited as long as it is capable of reducing divalent nickel to zero-valent nickel. Examples include compounds containing one or more selected from the group consisting of zinc, boron, manganese, magnesium, aluminum, sodium, etc. Among these, one or more selected from the group consisting of zinc, boron, and manganese are preferred. These reducing agents can be used in any shape, and for example, granular forms (fine particles, powder, chips, etc.) of any size can be used.

[0030] In the method for producing a homocoupling reaction product of the present invention, examples of the reducing agent include one or more selected from the group consisting of zinc powder, boron powder, manganese powder, magnesium powder, aluminum powder, sodium, sodium hydride, aluminum hydride compounds (lithium aluminum hydride, diisobutylaluminum hydride, sodium bis(2-methoxyethoxy)aluminum hydride, etc.), boron hydride compounds (sodium borohydride, lithium triethylborohydride, nickel borohydride, zinc borohydride, etc.), silicon hydride compounds (triethylsilane, triisopropylsilane, etc.), tin hydride compounds (tributyltin hydride), and transition metal hydride compounds. Preferably, the reducing agent is one or more selected from the group consisting of zinc powder, boron powder, manganese powder, magnesium powder, aluminum powder, etc., and more preferably one or more selected from the group consisting of zinc powder, boron powder, and manganese powder.

[0031] In the method for producing a homocoupling reaction product of the present invention, the amount of a reducing agent used is not particularly limited. It is, for example, 100 mol or less, preferably 80 mol or less, more preferably 50 mol or less, and even more preferably 30 mol or less per mol of nickel catalyst. By using a reducing agent, the nickel catalyst in the reaction system is regenerated by the reducing agent, making it possible to reduce the amount of nickel catalyst used.

[0032] <Other ingredients> In the method for producing a homocoupling reaction product of the present invention, other components may be used in addition to the "organohalogen compound," "nickel catalyst," "solvent," "heteroatom-containing compound," and "reducing agent." Examples of other components that may be used include a homocoupling reaction promoter (e.g., water), a base, and an unsaturated hydrocarbon compound.

[0033] <Mechanochemical method> The mechanochemical method used in the method for producing a homocoupling reaction product of the present invention is a method in which mechanical energy is applied to reaction components such as a halogen compound (substrate) and a nickel catalyst to cause a reaction. Mechanical energy can be generated mechanically by means of grinding, shearing, impact, compression, etc. By applying such mechanical energy to the halogen compound, nickel catalyst, etc., these can be activated and reacted. The mechanochemical reaction method is an organic synthesis reaction method in which the components contained in the reaction system are directly contacted and mixed to cause a reaction, eliminating the need for organic solvents, and is highly reactive while having a low environmental impact. The reaction apparatus and reaction conditions in the mechanochemical method used in the method for producing a homocoupling reaction product of the present invention can be as follows.

[0034] (Reaction Apparatus) The reaction apparatus used in the method for producing a homocoupling reaction product of the present invention is not particularly limited as long as it is an apparatus that can apply mechanical energy to the components involved in the reaction and thereby carry out the homocoupling reaction. Such devices include, for example: Grinding machines such as ball mills, rod mills, jet mills, SAG mills, etc.; Rotary mills, grinders, and other grinding machines; Horizontal cylindrical, V-type, double cone type, square cube type, S-type and continuous V-type (horizontal axis rotation) container rotating type mixers; Horizontal cylindrical, V-shaped, double cone-shaped and ball mill-shaped (with baffle blades) container-rotating mixers; (Rotary vibration) container-rotating mixers such as rocking and cross-rotary types; Ribbon, paddle, single-shaft rotor and bag mill type (horizontal axis rotating) stationary vessel mixers; Ribbon, screw, planetary, turbine, high-speed flow, rotating disk and Mahler type (vertical axis rotating) stationary vessel type mixers; (vibrating) stationary vessel type mixing equipment such as vibrating mills and sieves; (Fluidization) fluid movement type mixers such as heterogeneous fluidized beds, swirling fluidized beds, types with risers and jot pump types; (gravity) fluid motion type mixing devices such as gravity type and static mixers; Twin-screw mixers, single-screw mixers, mixers, roll mills and other mixers; and the like.

[0035] In the method for producing a homocoupling reaction product of the present invention, preferably, one or more selected from the group consisting of a pulverizer such as a ball mill, a grinder, a mixer, a kneader, etc. are used, and particularly preferably, a mixer is used. Examples of the mixer include the powder mixers described in Table 5 and Figure 9 of Sakashita, "Powder Mixing Process Technology," Color Materials, 77(2), 75-85 (2004). Specifically, a ball mill, a twin-screw kneader, a planetary ball mill, a SPEX mixer mill, a twin-screw ball mill, etc. can be used.

[0036] The apparatus used for the reaction by the mechanochemical method may be equipped with one or more means selected from the group consisting of a measuring means, a decompression or pressure means, an atmosphere adjustment means (gas introduction or discharge means), a means for introducing various components, a means for discharging various components and reaction products, a purification means, an analysis means, a reaction monitoring means, and the like.

[0037] (Reaction vessel) In the method for producing a homocoupling reaction product of the present invention, the reaction vessel used in the reaction by the mechanochemical method is not particularly limited as long as it is a reaction vessel that can carry out the homocoupling reaction, taking into consideration the physical properties, reactivity, and amounts of the organohalogen compound, nickel catalyst, and other components present in the reaction system, as well as the reaction conditions for the mechanochemical method, etc. For example, when a device that performs mechanical mixing (e.g., a ball mill, etc.) is used, a ball mill jar or the like can be used as the reaction vessel.

[0038] In the method for producing a homocoupling reaction product of the present invention, the reaction vessel may be equipped with a means for stirring the components involved in the reaction in the reaction vessel. The means for stirring the components involved in the reaction in the reaction vessel is not particularly limited as long as it is a variety of stirring means that can be equipped in the reaction apparatus. Means using a device that performs mechanical mixing treatment, as described above (Reaction Apparatus), can be used. For example, a ball mill is preferably used as a device that performs mechanical mixing treatment.

[0039] (Mechanochemical reaction conditions) In the method for producing a homocoupling reaction product of the present invention, the reaction conditions for the reaction by the mechanochemical method are not particularly limited, as long as the reaction conditions allow for the homocoupling reaction to be carried out, taking into consideration the physical properties, reactivity, and amounts of the organic halogen compound, nickel catalyst, and other components present in the reaction system, as well as the reaction conditions for the mechanochemical method.

[0040] Although the details of the mechanochemical method, such as the principle, are unknown, it is thought to be as follows. Mechanical energy is applied to the components involved in the homocoupling reaction, which then absorbs the mechanical energy, activating the surfaces of the components involved in the reaction. This activates the components involved in the reaction, and a chemical reaction occurs between the energized surfaces, leading to a reaction between molecules. For example, when using a ball mill, the application of mechanical energy to the components involved in the reaction activates the surfaces of the components involved in the reaction (e.g., halogen compounds).

[0041] (added mechanical energy) In the method for producing a homocoupling reaction product of the present invention, the mechanical energy applied during the reaction by the mechanochemical method is not particularly limited as long as it is mechanical energy that can cause the homocoupling reaction. For example, when a mixer is used as the device used in the reaction by the mechanochemical method, the mixing speed is not particularly limited and can be appropriately determined taking into consideration the physical properties, reactivity, and amounts of the organic halogen compound, nickel catalyst, and other components present in the reaction system, as well as the reaction conditions for the mechanochemical method, etc. For example, when a ball mill is used, shaking can be performed at 5 Hz or higher, preferably 10 Hz or higher, and more preferably 20 Hz or higher.

[0042] (Reaction temperature) In the method for producing a homocoupling reaction product of the present invention, the reaction temperature (temperature inside the reaction vessel during mixing) is not particularly limited. The temperature can be set to a temperature at which the homocoupling reaction can be carried out, taking into consideration the physical properties, reactivity, and amounts of the organohalogen compound, nickel catalyst, and other components present in the reaction system, as well as the reaction conditions for the mechanochemical method. For example, the temperature is 20°C or higher, preferably 50°C or higher, and more preferably 60°C or higher, and is 500°C or lower, preferably 300°C or lower, and more preferably 250°C or lower. The method for controlling the reaction temperature is not particularly limited, and any temperature control method used in chemical reactions can be used. Examples include a method for controlling the temperature inside the reaction vessel using hot air, a method for controlling the temperature inside the reaction vessel by covering the reaction vessel with a heat medium at a predetermined temperature, and a method for controlling the temperature inside the reaction vessel by providing a heating element. Among these, the method for controlling the temperature inside the reaction vessel by applying hot air generated by a heat gun to the reaction vessel is preferred from the viewpoints of safety and ease of temperature control operation.

[0043] (pressure) In the method for producing a homocoupling reaction product of the present invention, the reaction pressure (pressure inside the reaction vessel during mixing) when reacting by the mechanochemical method is not particularly limited. A pressure that allows the homocoupling reaction to be carried out can be set, taking into consideration the physical properties, reactivity, and amounts of the organohalogen compound, nickel catalyst, and other components present in the reaction system, as well as the reaction conditions for the mechanochemical method. If necessary, the reaction pressure can be controlled using a pressure reducing device or a pressure increasing device, and the reaction can be carried out without pressurizing or depressurizing. Of these, carrying out the reaction without pressurizing or depressurizing (carrying out the reaction at atmospheric pressure) is preferred from the standpoint of reaction operation, reaction equipment, and the like.

[0044] (reaction atmosphere) In the method for producing a homocoupling reaction product of the present invention, the reaction atmosphere (the atmosphere in the reaction vessel during mixing) is not particularly limited. The reaction atmosphere can be selected in such a way that the homocoupling reaction can be carried out, taking into consideration the physical properties, reactivity, and amounts of the organohalogen compound, nickel catalyst, and other components present in the reaction system, as well as the reaction conditions for the mechanochemical method. For example, the reaction can be carried out in an air atmosphere without any particular atmospheric adjustment, or, if necessary, in an inert gas atmosphere such as nitrogen, helium, neon, or argon. For example, bis(1,5-cyclooctadiene)nickel(0) [Ni(cod)], a widely used nickel catalyst, is unstable in air and must be handled and used in an inert gas atmosphere. However, in the homocoupling method of the present invention, it can be used without adjusting the atmosphere in the reaction vessel.

[0045] (Reaction time) In the method for producing a homocoupling reaction product of the present invention, the reaction time (mixing time; time for performing treatment by mechanical means) is not particularly limited. It can be appropriately determined taking into consideration the physical properties, reactivity, and amounts of the organohalogen compound, nickel catalyst, and other components present in the reaction system, as well as the reaction conditions for the mechanochemical method. For example, the reaction time can be 1 minute or more, preferably 3 minutes or more, and more preferably 5 minutes or more. The upper limit of the reaction time is not particularly limited, but can be, for example, 10 hours or less, preferably 5 hours or less, and more preferably 3 hours or less.

[0046] (Order of adding reaction components, post-reaction treatment, etc.) In the method for producing a homocoupling reaction product of the present invention, when reacting by a mechanochemical method, the order in which the reaction components are charged into a reaction vessel is not particularly limited, and the means for charging them is also not particularly limited. In the method for producing a homo-coupling reaction product of the present invention, a multi-stage synthesis reaction can be performed in which a first-stage reaction is carried out by a mechanochemical method, the reaction product is isolated, and then reaction components including the first-stage reaction product are added again to the reaction vessel to carry out subsequent reactions. In the method for producing a homo-coupling reaction product of the present invention, after the first reaction is carried out by a mechanochemical method, the reaction components necessary for the next reaction are added to the reaction vessel in which the first reaction has been completed, without isolating the reaction product, etc., and the next and subsequent reactions are carried out, thereby enabling a one-pot sequential reaction. After completion of the reaction, the resulting homocoupling reaction product may be purified as necessary. The purification method is not particularly limited, and methods such as filtration, distillation, recrystallization, column chromatography, and washing with a solvent may be used.

[0047] [Reaction product of homocoupling reaction] In the method for producing a homocoupling reaction product of the present invention, the organic halogen compound is a compound of the formula (I); A 1 -X m (I) (In formula (I), A 1 , X and m are the same as those described above in [Method for producing homocoupling reaction product]. Examples of reaction products of the homocoupling reaction when a compound represented by the formula: is used include the following.

[0048] (1) When an organic halogen compound (monohalogen compound) where m = 1 is used, the formula (A); A 1 -A 1 (A) (In formula (A), A 1 may be the same or different.) Examples of the homocoupling reaction product include the following:

[0049] (2) When an organic halogen compound (dihalogen compound) where m = 2 is used, the formula (P1) is [ka] (In formula (P1), a plurality of A 1 may be the same or different, and n1 is an integer of 2 or greater.) and a linear or cyclic homocoupling reaction polymerization product having a repeating unit represented by the formula: product Examples include:

[0050] (3) When an organic halogen compound (trihalogen compound, tetrahalogen compound, etc.) where m≧3 is used, examples include a homocoupling reaction crosslinked polymerization product and an intramolecular homocoupling reaction product. For example, when m=3, the homocoupling reaction crosslinked polymerization product is represented by the formula (P2): [ka] (In formula (P2), a plurality of A 1 may be the same or different, and n2 is an integer of 2 or greater.) Examples of the polymer include a polymer having a unit represented by the following formula: For example, when m=4, the homocoupling reaction crosslinked polymerization product is represented by formula (P3): [ka] (In formula (P3), a plurality of A 1 may be the same or different, and n3 is an integer of 2 or greater.) Examples of the polymer include a polymer having a unit represented by the following formula:

[0051] The reaction product produced by the method for producing a homocoupling reaction product of the present invention may be a reaction product having a variety of structures other than the reaction products represented by the above formula (A) and formulas (P1) to (P3).

[0052] The reaction product obtained by the method for producing a homo-coupling reaction product of the present invention can be used as a component of functional materials such as pharmaceuticals, liquid crystal compounds, organic electroluminescent compounds, organic thin-film solar cells, polymer compounds, oligomers, coloring materials, energy ray absorbing materials, information recording materials, wavelength conversion materials, indicator materials, sensor materials, organic light-emitting diodes (OLEDs), and organic semiconductor materials. [Example]

[0053] The present invention will be described in detail below with reference to specific examples. These specific examples are merely one embodiment of the present invention, and the present invention is not limited to these examples in any way. "Equiv" means "equivalent."

[0054] In the examples and comparative examples, when reactions were carried out using a ball mill, each reagent was placed in a stainless steel ball mill jar, and a ball mill MM400 manufactured by Verder Scientific Co., Ltd. (formerly Retsch) was used. When the homocoupling reaction was carried out using a ball mill, the outside of the ball mill jar was heated to a predetermined temperature using a heat gun (manufactured by Takagi Corporation, HG-1450B). The relationship between the heat gun temperature setting and the temperature inside the ball mill jar (temperature of the reaction system) was confirmed using a thermographic image, and the results were as follows:

[0055] [Table 1]

[0056] [Mechanochemical Homocoupling Reaction of Monohalogen Compounds] [ka]

[0057] {Consideration of mechanochemical reaction conditions} Example 1 A 5 mL stainless steel ball mill jar containing a 10 mm diameter stainless steel ball was charged with 0.2 mmol of 1-Bromo-3,5-dimethoxybenzene (A-1) as a monohalogen compound and 1.0 equiv of 2,2'-Bipyridine (C-1; melting point 70-72 °C) as a heteroatom-containing compound under air. The ball mill jar was then placed in an argon-filled glove box, and 1.0 equiv of Bis(1,5-cyclooctadiene)nickel(0) as a nickel catalyst was added to the jar. The ball mill jar was then closed, removed from the glove box, and attached to a ball mill. The mixture was heated with a heat gun set to 160 °C (internal temperature of the ball mill jar: 80 °C) and shaken and stirred at a frequency of 30 Hz for 10 min to allow the reaction to proceed. The reaction product was then extracted, dried, and purified, and the homo-coupling reaction product (B-1) was obtained by mechanochemical reaction with an NMR yield of 56%.

[0058] <Examples 2 to 5> A homocoupling reaction product (B-1) was obtained by carrying out the homocoupling reaction in the same manner as in Example 1, except that the frequency and time conditions were as shown in Table 2. The NMR yield thereof is also shown in Table 2.

[0059] [Table 2]

[0060] {Consideration of heteroatom-containing compounds} Example 6 A 5 mL stainless steel ball mill jar containing a 10 mm diameter stainless steel ball was charged with 0.2 mmol of 1-Bromo-3,5-dimethoxybenzene (A-1) as a monohalogen compound and 1.0 equiv of 2,2'-Bipyridine (C-1; melting point 70-72 °C) as a heteroatom-containing compound under air. The ball mill jar was then placed in an argon-filled glove box, and 1.0 equiv of Bis(1,5-cyclooctadiene)nickel(0) as a nickel catalyst was added to the jar. The lid of the ball mill jar was closed, removed from the glove box, and attached to a ball mill. The mixture was heated with a heat gun set to 160 °C (internal temperature of the ball mill jar: 80 °C) and shaken and stirred at a frequency of 20 Hz for 30 minutes to allow the reaction to proceed. The reaction product was then extracted, dried, and purified, and the homo-coupling reaction product (B-1) was obtained by mechanochemical reaction with an NMR yield of 71%.

[0061] <Examples 7 to 13> Homocoupling reaction product (B-1) was obtained by carrying out the homocoupling reaction in the same manner as in Example 6, except that (C-2) to (C-8) listed in Table 3 were used as heteroatom-containing compounds. The NMR yields are also shown in Table 3.

[0062] [Table 3]

[0063] {Consideration of temperature and reaction scale} Example 14 A 5 mL stainless steel ball mill jar containing a 10 mm diameter stainless steel ball was charged with 0.20 mmol of 1-Bromo-3,5-dimethoxybenzene (A-1) as a monohalogen compound and 1.0 equiv (0.20 mmol) of 4,4'-Bis(di-t-butyl)-2,2'-bipyridine (C-2; melting point 161 °C) as a heteroatom-containing compound under air. The ball mill jar was then placed in an argon-filled glove box, and 1.0 equiv (0.20 mmol) of Bis(1,5-cyclooctadiene)nickel(0) as a nickel catalyst was added to the jar. The lid of the ball mill jar was closed, removed from the glove box, and attached to a ball mill. The mixture was heated with a heat gun set to 160 °C (internal temperature of the ball mill jar: 80 °C) and shaken and stirred at a frequency of 20 Hz for 30 min to carry out the reaction. The reaction product was then extracted, dried, and purified, and the homo-coupling reaction product (B-1) was obtained by mechanochemical reaction with an NMR yield of 86%.

[0064] <Examples 15 and 16> A homocoupling reaction product (B-1) was obtained by carrying out the homocoupling reaction in the same manner as in Example 14, except that the amount of monohalogen compound used and the set temperature of the heat gun (temperature inside the ball mill jar) were set as shown in Table 4. The NMR yield of the homocoupling reaction product (B-1) is also shown in Table 4.

[0065] Example 17 The homocoupling reaction was carried out in the same manner as in Example 14, except that the amount of nickel catalyst used was 1.2 equiv, the amount of heteroatom-containing compound used was 1.2 equiv, and the amount of monohalogen compound used and the set temperature of the heat gun (temperature inside the ball mill jar) were set as shown in Table 4, to obtain homocoupling reaction product (B-1). The NMR yield is also shown in Table 4.

[0066] [Table 4]

[0067] {Study of monohalogen compounds} Example 18 A 5 mL stainless steel ball mill jar containing a 10 mm diameter stainless steel ball was charged with 0.5 mmol of 1-Bromo-3,5-dimethoxybenzene (A-1) as a monohalogen compound and 1.2 equiv of 4,4'-Bis(di-t-butyl)-2,2'-bipyridine (C-2; melting point 161 °C) as a heteroatom-containing compound under air. The ball mill jar was then placed in an argon-filled glove box, and 1.2 equiv of Bis(1,5-cyclooctadiene)nickel(0) as a nickel catalyst was added to the jar. The ball mill jar was then closed, removed from the glove box, and attached to a ball mill. The mixture was heated with a heat gun set to 200 °C (internal temperature of the ball mill jar: 100 °C) and shaken and stirred at a frequency of 20 Hz for 30 min to carry out the reaction. The reaction product was then extracted, dried, and purified, and the homo-coupling reaction product (B-1) was obtained by mechanochemical reaction with an isolation yield of 91%.

[0068] <Examples 19 to 21> Homocoupling reactions were carried out in the same manner as in Example 18, except that the compounds shown in Table 5 were used as monohalogen compounds, to obtain the corresponding homocoupling reaction products shown in Table 5. The isolation yields are also shown in Table 5.

[0069] [Table 5]

[0070] <Example 22> A 1.5 mL stainless steel ball mill jar containing a 5 mm diameter stainless steel ball was charged with 0.2 mmol of 1-Bromo-3,5-dimethoxybenzene (A-1) as a monohalogen compound and 1.0 equiv of phenanthroline (C-4; melting point 117 °C) as a heteroatom-containing compound under air. The ball mill jar was then placed in an argon-filled glove box, and 1.0 equiv of bis(1,5-cyclooctadiene)nickel(0) as a nickel catalyst was added to the jar. The lid of the ball mill jar was closed, removed from the glove box, and attached to a ball mill. The mixture was heated with a heat gun set to 160 °C (internal temperature of the ball mill jar: 80 °C) and shaken and stirred at a frequency of 30 Hz for 10 min to carry out the reaction. The reaction product was then extracted, dried, and purified, and the homo-coupling reaction product (B-1) was obtained by mechanochemical reaction with an isolation yield of 99%.

[0071] <Examples 23 to 28> The homocoupling reaction was carried out in the same manner as in Example 22, except that the compound shown in Table 6 was used as the monohalogen compound, 2,2'-bipyridine (C-1: melting point 70-72°C) was used as the heteroatom-containing compound, and the shaking and stirring conditions were as shown in Table 6, to obtain the corresponding reaction products shown in Table 6. The isolation yields are also shown in Table 6.

[0072] [Table 6]

[0073] Example 29 A 5 mL stainless steel ball mill jar containing a 10 mm diameter stainless steel ball was charged with 0.5 mmol of N,N-diphenyl-4-bromoaniline (A-5) as a monohalogen compound and 1.2 equiv (0.6 mmol) of 4,4'-bis(di-t-butyl)-2,2'-bipyridine (C-2; melting point 161 °C) as a heteroatom-containing compound under air. The ball mill jar was then placed in an argon-filled glove box, and 1.2 equiv (0.6 mmol) of bis(1,5-cyclooctadiene)nickel(0) as a nickel catalyst was added to the jar. The ball mill jar was then closed, removed from the glove box, and attached to a ball mill. The mixture was heated with a heat gun set to 250 °C (internal temperature of the ball mill jar: 120 °C) and shaken and stirred at a frequency of 20 Hz for 30 minutes to allow the reaction to proceed. The reaction product was then extracted, dried, and purified, and the homo-coupling reaction product (B-5) was obtained by mechanochemical reaction with an isolation yield of 99%.

[0074] <Examples 30 to 41> Homocoupling reactions were carried out in the same manner as in Example 29, except that the compounds shown in Table 7 were used as monohalogen compounds, to obtain the corresponding reaction products shown in Table 7. The isolation yields are also shown in Table 7.

[0075] [Table 7]

[0076] {Study on the reactivity of halogen species} <Example 42> A 5 mL stainless steel ball mill jar containing a 10 mm diameter stainless steel ball was charged with 0.5 mmol of methyl 4-bromobenzoate (A-3) as a monohalogen compound, 1.2 equiv (0.6 mmol) of bis(1,5-cyclooctadiene)nickel(0) as a nickel catalyst, and 1.2 equiv (0.6 mmol) of 4,4'-bis(di-t-butyl)-2,2'-bipyridine (C-2; melting point 161 °C) as a heteroatom-containing compound under air. The ball mill jar was then closed, removed from the glove box, and attached to a ball mill. The mixture was heated with a heat gun set to 250 °C (internal temperature of the ball mill jar: 120 °C) and shaken and stirred at a frequency of 20 Hz for 30 minutes. The reaction product was then extracted, dried, and purified, and the homo-coupling reaction product (B-3) was obtained by mechanochemical reaction with an NMR yield of 83%.

[0077] <Examples 43 and 44> In Example 43, methyl 4-iodobenzoate (A-19) was used as the monohalogen compound, and in Example 44, methyl 4-chlorobenzoate (A-20) was used as the monohalogen compound. Homocoupling reactions were carried out in the same manner as in Example 42, except that homocoupling reaction product (B-3) was obtained. The NMR yields are also shown in Table 8.

[0078] [Table 8]

[0079] [Scale-up of homocoupling reactions] Example 45 A 10-mL stainless steel ball mill jar containing a 10-mm-diameter stainless steel ball was charged with 4.2 mmol of N,N-diphenyl-4-bromoaniline (A-5) as a monohalogen compound, 1.2 equiv of Bis(1,5-cyclooctadiene)nickel(0) as a nickel catalyst, and 1.2 equiv of 4,4'-Bis(di-t-butyl)-2,2'-bipyridine (C-2; melting point 161 °C) as a heteroatom-containing compound under air. The ball mill jar was then closed, removed from the glove box, and attached to a ball mill. The mixture was heated with a heat gun set to 250 °C (internal temperature of the ball mill jar: 120 °C) and shaken and stirred at 20 Hz for 30 minutes. The reaction product was then extracted, dried, and purified, and the homo-coupling reaction product (B-5) was obtained by mechanochemical reaction in an isolated yield of 99% (1.026 g).

[0080] [Monohalogen compounds, homocoupling reaction products and heteroatom-containing compounds] The monohalogen compounds (A-1) to (A-20), homocoupling reaction products (B-1) to (B-17), and heteroatom-containing compounds (C-1) to (C-8) used in Examples 1 to 45 are as follows: In these structural formulas, t-Bu represents a tertiary butyl group.

[0081] {Monohalogen compounds} [ka]

[0082] [ka]

[0083] {Homocoupling reaction product} [ka]

[0084] [ka]

[0085] {Heteroatom-containing compounds} [ka]

[0086] [Homocoupling reaction in the presence of a reducing agent] [ka]

[0087] <Example 46> A 1.5 mL stainless steel ball mill jar containing a 5 mm diameter stainless steel ball was charged with 0.5 mmol of 3-bromotoluene (A-21) as a monohalogen compound, 0.05 mmol of Bis(triphenylphosphine)nickel(II) dichloride as a nickel catalyst, 1.0 mmol of metallic zinc powder as a reducing agent, and 60 μL of tetrahydrofuran (THF; melting point -108 °C) as a solvent under air. The ball mill jar was then closed, removed from the glove box, and attached to a ball mill. The mixture was heated with a heat gun set to 250 °C (internal temperature of the ball mill jar: 120 °C) and shaken and stirred at 30 Hz for 60 minutes to react. The reaction product was then extracted, dried, and purified, and the homo-coupling reaction product (B-18) was obtained by mechanochemical reaction. The gas chromatographic yield was 44%.

[0088] [Homocoupling reaction of 1,2-dibromobenzene] [ka]

[0089] Example 47 A 5 mL stainless steel ball mill jar containing a 10 mm diameter stainless steel ball was charged with 0.5 mmol of 1,2-Dibromobenzene (A-22) as a halogen compound, 2.4 equiv of Bis(1,5-cyclooctadiene)nickel(0) as a nickel catalyst, and 2.4 equiv of 4,4'-Bis(di-t-butyl)-2,2'-bipyridine as a heteroatom-containing compound under air. The ball mill jar was then closed, removed from the glove box, and attached to a ball mill. The mixture was heated with a heat gun set to 200°C (internal temperature of the ball mill jar: 100°C) and shaken and stirred at 20 Hz for 30 minutes to react. The reaction product was then extracted, dried, and purified, and the homo-coupling reaction product (B-19) was obtained by mechanochemical reaction with an NMR yield of 26%.

[0090] [Application of Mechanochemical Homocoupling Reaction to Polymerization] {Homocoupling polymerization of 1,4-Dibromo-2,5-bis(decyloxy)benzene} [ka]

[0091] Example 48 A 1.5 mL stainless steel ball mill jar containing a 5 mm diameter stainless steel ball was charged with 56.6 mg (0.1 mmol) of 1,4-Dibromo-2,5-bis(decyloxy)benzene (A-51) as a halogen compound and 32.3 mg (0.2 mmol) of 2,2'-bipyridyl as a heteroatom-containing compound under air. The ball mill jar was then transferred to a glove box, and 55.1 mg (0.2 mmol) of Bis(1,5-cyclooctadiene)nickel(0) as a nickel catalyst was added. The ball mill jar was removed from the glove box, the lid was closed, and the jar was attached to a ball mill. The mixture was heated with a heat gun set to 160 °C (internal temperature of the ball mill jar: 80 °C) while being shaken and stirred at 30 Hz for 10 min. After the reaction was completed, the reaction product was extracted with dichloromethane and water, and the organic layer was dried over magnesium sulfate. After filtration, the dichloromethane was removed using an evaporator. The crude product was reprecipitated in a dichloromethane / methanol solvent to obtain 33.1 mg of a homocoupling polymerization reaction product. The homocoupling polymerization reaction product was a polymer having the repeating unit represented by (B-51). The conversion rate was over 95%, and the isolation yield was 87%. The number-average molecular weight (Mn), weight-average molecular weight (Mw), and polydispersity index (PDI) of the reaction product determined by size exclusion chromatography (SEC) were as follows: Mn=4.3 kg / mol Mw=5.5 kg / mol PDI=1.28

[0092] <Example 49> A 1.5 mL stainless steel ball mill jar containing a 5 mm diameter stainless steel ball was charged with 0.3 mmol of 1,4-Dibromo-2,5-bis(decyloxy)benzene (A-51) as a halogen compound and 0.72 mmol of 4,4'-Bis(di-t-butyl)-2,2'-bipyridine as a heteroatom-containing compound in an amount of 2.4 equiv (0.72 mmol) based on the halogen compound. The ball mill jar was then transferred to a glove box, and 2.4 equiv (0.72 mmol) of Bis(1,5-cyclooctadiene)nickel(0) as a nickel catalyst was added. The ball mill jar was removed from the glove box, the lid was closed, and the jar was attached to a ball mill. The reaction was carried out with a heat gun set to 200 °C (internal temperature of the ball mill jar: 100 °C) and shaken and stirred at 20 Hz for 30 min. After the reaction was complete, the reaction product was extracted with dichloromethane and water, and the organic layer was dried over magnesium sulfate. After filtration, the dichloromethane was removed using an evaporator. The crude product was reprecipitated in a dichloromethane / methanol solvent to obtain a homocoupling polymerization reaction product. The homocoupling polymerization reaction product was a polymer having the repeating unit (B-51), and the isolation yield was 70%. The number-average molecular weight (Mn), weight-average molecular weight (Mw), and polydispersity index (PDI) of the reaction product determined by size exclusion chromatography (SEC) were as follows, indicating that the 22-mer was primarily obtained. Mn=8.6 kg / mol Mw=11.4 kg / mol PDI=1.33

[0093] <Comparative Example 1> A reaction vessel was charged with 0.3 mmol of 1,4-Dibromo-2,5-bis(decyloxy)benzene (A-51) as a halogen compound, 2.4 equiv (0.72 mmol) of 4,4'-Bis(di-t-butyl)-2,2'-bipyridine as a heteroatom-containing compound relative to the halogen compound, 2.4 equiv (0.72 mmol) of Bis(1,5-cyclooctadiene)nickel(0) as a nickel catalyst relative to the halogen compound, and 3 mL of N,N-dimethylformamide (DMF) (0.1 M based on the halogen compound) as a solvent, and the reaction was carried out in the solution at 80°C for 24 hours. After the reaction was complete, the reaction product was extracted with dichloromethane and water, and the organic layer was dried over magnesium sulfate. After filtration, the dichloromethane was removed using an evaporator. The crude product was reprecipitated in a dichloromethane / methanol solvent to obtain a homocoupling polymerization reaction product. The homocoupling polymerization reaction product was a polymer having the repeating unit (B-51), and the isolation yield was 51%. The number-average molecular weight (Mn), weight-average molecular weight (Mw), and polydispersity index (PDI) of the reaction product determined by size exclusion chromatography (SEC) were as follows, indicating that the 6.4-mer was primarily obtained. Mn=2.5 kg / mol Mw=2.9 kg / mol PDI=1.17

[0094] {Homocoupling polymerization reaction of 2,7-Dibromo-9,9-bis(2-ethylhexyl)fluorene} [ka]

[0095] Example 50 A 1.5 mL stainless steel ball mill jar containing a 5 mm diameter stainless steel ball was charged with 0.3 mmol of 2,7-Dibromo-9,9-bis(2-ethylhexyl)fluorene (A-52) as a halogen compound and 0.72 mmol of 4,4'-Bis(di-t-butyl)-2,2'-bipyridine as a heteroatom-containing compound in an amount of 2.4 equiv (0.72 mmol) based on the halogen compound. The ball mill jar was then transferred to a glove box, and 2.4 equiv (0.72 mmol) of Bis(1,5-cyclooctadiene)nickel(0) as a nickel catalyst was added. The ball mill jar was removed from the glove box, the lid was closed, and the jar was attached to a ball mill. The reaction was carried out with a heat gun set to 250 °C (internal temperature of the ball mill jar: 120 °C) and shaken and stirred at 20 Hz for 30 minutes. After the reaction was completed, the reaction product was extracted with dichloromethane and water, and the organic layer was dried over magnesium sulfate. After filtration, the dichloromethane was removed using an evaporator. The crude product was reprecipitated in a dichloromethane / methanol solvent to obtain a homocoupling polymerization reaction product. The homocoupling polymerization reaction product was a polymer having the repeating unit represented by (B-52). The isolation yield was 85%. The number-average molecular weight (Mn), weight-average molecular weight (Mw), and polydispersity index (PDI) of the reaction product determined by size exclusion chromatography (SEC) were as follows, indicating that the 7.5-mer was the main product. Mn=2.9 kg / mol Mw=9.7 kg / mol PDI=3.25

[0096] <Comparative Example 2> A reaction vessel was charged with 2,7-Dibromo-9,9-bis(2-ethylhexyl)fluorene (A- 52) as a heteroatom-containing compound, 4,4'-Bis(di-t-butyl)-2,2'-bipyridine as 2.4 equiv (0.72 mmol) relative to the halogen compound, Bis(1,5-cyclooctadiene)nickel(0) as a nickel catalyst, and 3 mL (0.1 M based on the halogen compound) of N,N-dimethylformamide (DMF) as a solvent were added, and the reaction was carried out in a solution at 80°C for 24 hours. After the reaction was completed, the reaction product was extracted with dichloromethane and water, and the organic layer was dried over magnesium sulfate. After filtration, the dichloromethane was removed using an evaporator. The crude product was reprecipitated in a dichloromethane / methanol solvent to obtain a homocoupling polymerization reaction product. The homocoupling polymerization reaction product was (B- 52 The isolated yield was 35%. The number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity index (PDI) of the reaction product determined by size exclusion chromatography (SEC) were as follows, indicating that the product was mainly an octamer. Mn=3.1 kg / mol Mw=5.7 kg / mol PDI=1.83

[0097] {Homocoupling polymerization of tetrakis(4-bromophenyl)ethylene} [ka]

[0098] <Example 51> A 5 mL stainless steel ball mill jar containing a 10 mm diameter stainless steel ball was charged with 32.4 mg (0.05 mmol) of Tetrakis(4-bromophenyl)ethylene (A-53) as a halogen compound, 55.0 mg (0.2 mmol) of Bis(1,5-cyclooctadiene)nickel(0) as a nickel catalyst, and 31.2 mg (0.2 mmol) of 2,2'-Bipyridine as a heteroatom-containing compound under air. The ball mill jar was then capped and attached to a ball mill. The mixture was heated with a heat gun set to 160 °C (internal temperature of the ball mill jar: 80 °C) and shaken and stirred at 30 Hz for 10 minutes to react. The reaction product was then extracted, dried, and purified to obtain 14.4 mg of homo-coupling polymerization product. The homo-coupling polymerization product was a polymer with four bond units, as shown in (B-53). The isolation yield was 88%.

[0099] {Homocoupling polymerization reaction of 2,2',7,7'-Tetrabromo-9,9'-spirobifluorene} [ka]

[0100] <Example 52> A 5 mL stainless steel ball mill jar containing a 10 mm diameter stainless steel ball was charged with 63.0 mg (0.2 mmol) of 2,2',7,7'-Tetrabromo-9,9'-spirobifluorene (A-54) as a halogen compound, 165.1 mg (0.6 mmol) of Bis(1,5-cyclooctadiene)nickel(0) as a nickel catalyst, and 93.7 mg (0.6 mmol) of 2,2'-Bipyridine as a heteroatom-containing compound under air. The ball mill jar was then capped and attached to a ball mill. The mixture was heated with a heat gun set to 160 °C (internal temperature of the ball mill jar: 80 °C) and shaken and stirred at 30 Hz for 10 minutes to react. The reaction product was then extracted, dried, and purified to obtain 13.1 mg of homo-coupling polymerization product. The homo-coupling polymerization product was a polymer with four bond units, as shown in (B-54). The isolation yield was 87%.

[0101] {Homocoupling polymerization of 1,3,5-tribromobenzene} [ka]

[0102] <Example 53> A 5 mL stainless steel ball mill jar containing a 10 mm diameter stainless steel ball was charged with 31.6 mg (0.05 mmol) of 1,3,5-tribromobenzene (A-55) as a halogen compound, 55.0 mg (0.2 mmol) of bis(1,5-cyclooctadiene)nickel(0) as a nickel catalyst, and 31.3 mg (0.2 mmol) of 2,2'-bipyridine as a heteroatom-containing compound under air. The ball mill jar was then capped and attached to a ball mill. The jar was heated with a heat gun set to 160 °C (internal temperature of the ball mill jar: 80 °C) and shaken and stirred at 30 Hz for 10 minutes to allow the reaction to proceed. The reaction product was then extracted, dried, and purified to obtain 14.4 mg of homo-coupling polymerization product. The homo-coupling polymerization product was a polymer with units having three bonds, as shown in (B-55). The isolated yield was 92%.

[0103] {Homocoupling polymerization reaction of 1,2,4,5-tetrabromobenzene} [ka]

[0104] <Example 54> A 5 mL stainless steel ball mill jar containing a 10 mm diameter stainless steel ball was charged with 78.7 mg (0.2 mmol) of 1,2,4,5-tetrabromobenzene (A-56) as a halogen compound, 220.1 mg (0.8 mmol) of bis(1,5-cyclooctadiene)nickel(0) as a nickel catalyst, and 125.0 mg (0.8 mmol) of 2,2'-bipyridine as a heteroatom-containing compound under air. The ball mill jar was then capped and attached to a ball mill. The jar was heated with a heat gun set to 160 °C (internal temperature of the ball mill jar: 80 °C) while being shaken and stirred at 30 Hz for 10 minutes. The reaction product was then extracted, dried, and purified to obtain 14.6 mg of homo-coupling polymerization product. The homo-coupling polymerization product was a polymer with units having six bonds, represented by (B-56). The isolation yield was 99%.

[0105] [About the Examples] As shown in Examples 1 to 44, the method for producing a homo-coupling reaction product according to the present invention can be carried out under mild reaction conditions and with simple reaction procedures without using an organic solvent, and can produce a reaction product in high yield in a short period of time. As shown in Examples 42 to 44, the method for producing a homo-coupling reaction product according to the present invention is a method that can carry out the reaction under mild reaction conditions and with simple reaction procedures, regardless of whether the halogen species is Br, I, or Cl, and can produce a reaction product in high yield in a short period of time. As shown in Example 45, the method for producing a homocoupling reaction product according to the present invention is a method that allows the reaction to be carried out under mild reaction conditions and with simple reaction procedures, even when the reaction is carried out on a gram scale, and enables the reaction product to be obtained in high yield in a short period of time. As shown in Example 46, among the methods for producing homo-coupling reaction products according to the present invention, the method using a reducing agent can reduce the amount of nickel catalyst used under conditions in which no organic solvent is used substantially, and can carry out the reaction under mild reaction conditions with simple reaction procedures, thereby enabling the production of reaction products in high yield in a short period of time. As shown in Examples 1 to 45 and 47, the method for producing a homo-coupling reaction product according to the present invention is a method in which the reaction can be carried out under mild reaction conditions and with simple reaction procedures without using an organic solvent, and the reaction product can be obtained in high yield in a short time, and further it can be seen that a wide range of compounds can be used as raw materials.

[0106] As shown in Examples 48 to 50 and Comparative Examples 1 and 2, the method for producing a homo-coupling reaction product according to the present invention can perform the reaction under mild reaction conditions and with simple reaction procedures without using an organic solvent, and is a method that can produce a high-molecular-weight π-conjugated polymer as a reaction product in high yield in a short period of time. As shown in Examples 51 to 54, the method for producing a homo-coupling reaction product according to the present invention can perform the reaction under mild reaction conditions and with simple reaction procedures without using an organic solvent, and is a method that can produce a high-molecular-weight π-conjugated polymer as a reaction product in high yield in a short period of time. Furthermore, it is clear that the method can use a wide range of compounds as raw materials and is therefore applicable to a variety of polymerization forms. From this, it can be seen that the present invention is extremely useful industrially.

Claims

1. Formula (I): A １ -X ｍ (I) (In formula (I), A １ represents any one of an m-valent aromatic hydrocarbon group which may have a substituent, an m-valent aromatic heterocyclic group which may have a substituent, an m-valent heterocyclic group which may have a substituent, an m-valent aliphatic hydrocarbon group which may have a substituent, or an m-valent unsaturated aliphatic hydrocarbon group which may have a substituent. X represents any one of chlorine, bromine, and iodine, and when there are a plurality of X's, they may be the same or different. m is the number of X's and represents an integer of 1 or more. in the presence of a nickel catalyst which is at least one selected from the group consisting of a zero-valent nickel complex having Ni(0) and a zero-valent Ni salt, under condition (a) and / or condition (b): Condition (a): the amount of solvent used is 0.8 mL or less per 1 mmol of the organic halogen compound; Condition (b): A condition in which the reaction is carried out in the presence of a heteroatom-containing compound, the heteroatom-containing compound being at least one compound selected from the group consisting of bipyridine-based compounds, arylphosphine-based compounds, alkylphosphine-based compounds, Buchwald phosphine ligand-based compounds, bidentate phosphine-based compounds, N-heterocarbene-based compounds, and trialkylphosphonium tetrafluoroborate-based compounds; a homocoupling reaction of the organohalogen compound represented by formula (I) by a mechanochemical method.

2. In the formula (I), m is 1 or more and 4 or less, and the homocoupling reaction product is represented by formula (A), formula (P1), formula (P2), or formula (P3): Formula (A): A １ -A １ (A) (In formula (A), A １ may be the same or different.) a homocoupling reaction product represented by Formula (P1): 【Chemistry 1】 (In formula (P1), a plurality of A １ may be the same or different, and n1 is an integer of 2 or more. a linear homocoupling reaction polymerization product, a cyclic homocoupling reaction polymerization product, or an intramolecular homocoupling reaction product having a repeating unit represented by the formula: Formula (P2): 【Chemistry 2】 (In formula (P2), a plurality of A １ may be the same or different, and n2 is an integer of 2 or more. A polymer having a unit represented by Formula (P3): 【Transformation 3】 (In formula (P3), a plurality of A １ may be the same or different, and n3 is an integer of 2 or more. A polymer having a unit represented by The method for producing the homocoupling reaction product according to claim 1,

3. 3. The method for producing a homocoupling reaction product according to claim 1, wherein the melting point of the solvent is 30°C or lower and / or the melting point of the heteroatom-containing compound is 50°C or higher.

4. 3. The method for producing a homocoupling reaction product according to claim 1 or 2, wherein a reducing agent is further present during the mechanochemical reaction.

5. 3. The method for producing a homocoupling reaction product according to claim 1, wherein the reaction is carried out at a temperature of 60°C or higher by the mechanochemical method.

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