Method for producing polymer compound, compound, palladium complex, and composition

Abstract

To provide a method of manufacturing a high polymer compound having a reduced amount of remaining monomers after polymerization, a ligand compound for use in the manufacturing method, a palladium complex, and a composition containing the ligand compound and a palladium complex precursor.SOLUTION: A method for manufacturing a high polymer compound comprising a step of reacting an aromatic compound having a boric acid residue in the presence of a palladium complex containing a compound represented by formula (0) as a ligand, and ligand compounds used in the manufacturing method, palladium complexes, and compositions comprising the ligand compounds and palladium complex precursors. [In the formula, Ar1A and Ar1B independently represent a substituted / unsubstituted arylene group or a divalent heterocyclic group. Ar1C, Ar1D,Ar1E and Ar1F independently represent a substituted / unsubstituted aryl group or a monovalent heterocyclic group].SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing a polymer compound, a compound, a palladium complex, and a composition. [Background technology]

[0002] As a method for producing a polymer compound, for example, a production method by Suzuki polymerization reaction (polymerization reaction utilizing Suzuki coupling reaction) using a phosphine ligand and a palladium complex is known. As the phosphine ligand used in this reaction, for example, a monodentate phosphine ligand (Patent Document 1 and Patent Document 2) and a bidentate phosphine ligand in which two phosphorus atoms are linked by an alkylene group or a ferrocenediyl group (Non-Patent Document 1) are known. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2008-45110 A [Patent Document 2] JP 2008-95065 A [Non-Patent Document 1] Macromolecules 2009, 42, 5471 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the above-mentioned methods for producing polymer compounds have not been able to sufficiently reduce the amount of monomer remaining after polymerization. Therefore, an object of the present invention is to provide a method for producing a polymer compound in which the amount of monomer remaining after polymerization is reduced, and to provide a ligand compound for use in the production method, a palladium complex containing the ligand compound, and a composition containing a palladium complex precursor and the ligand compound. [Means for solving the problem]

[0005] The present invention provides the following [1] to

[12] . [1] A method for producing a polymer compound, comprising a step of reacting an aromatic compound having a boric acid residue in the presence of a palladium complex containing a compound represented by formula (0) as a ligand. TIFF0007636272000001.tif34130[where, Ar 1A and Ar 1B each independently represents an arylene group or a divalent heterocyclic group, and these groups may have a substituent. When a plurality of the substituents are present, they may be bonded to each other to form a ring together with the atom to which they are bonded. Ar 1C , Ar 1D , Ar 1E and Ar 1F each independently represents an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. When a plurality of such substituents are present, they may be bonded to each other to form a ring together with the atom to which they are bonded. [2] The method according to [1], wherein the compound represented by formula (0) is a compound represented by formula (1). TIFF0007636272000002.tif38130[where, Ar 1C , Ar 1D , Ar 1E and Ar 1F has the same meaning as above. Ring Ar A and ring Ar B each independently represents an aromatic hydrocarbon ring or a heterocyclic ring, and these rings may have a substituent. When a plurality of such substituents are present, they may be bonded to each other to form a ring together with the atom to which they are bonded. [3] The method according to [2], wherein the compound represented by formula (1) is a compound represented by formula (2) or formula (3). TIFF0007636272000003.tif47130[where, Ar 1C , Ar 1D, Ar 1E and Ar 1F has the same meaning as above. R 2A , R 2B , R 2C , R 2D , R 2E , R 2F , R 2G , R 2H , R 3A , R 3B , R 3C , R 3D , R 3E , R 3F , R 3G , R 3H , R 3I , R 3J , R 3K and R 3L R each independently represents a hydrogen atom, an electron-withdrawing group, an amino group, a substituted amino group, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group, an aryloxy group, or a monovalent heterocyclic group, and these groups may have a substituent. When a plurality of the substituents are present, they may be bonded to each other to form a ring together with the atom to which they are bonded. 2A and R 2B , R 2B and R 2C , R 2C and R 2D , R 2D and R 2E , R 2E and R 2F , R 2F and R 2G , R 2G and R 2H , R 3A and R 3B , R 3B and R 3C , R 3C and R 3D , R 3D and R 3E , R 3E and R 3F , R 3F and R 3G , R 3G and R 3H , R 3H and R 3I , R 3I and R 3J, R 3J and R 3K , and R 3K and R 3L may be bonded to each other to form a ring together with the carbon atom to which they are bonded. [4] The method according to [2], wherein the compound represented by formula (1) is a compound represented by formula (3-1). TIFF0007636272000004.tif73130[where, R 3A , R 3B , R 3C , R 3D , R 3E , R 3F , R 3G , R 3H , R 3I , R 3J , R 3K and R 3L has the same meaning as above. R 3M , R 3N , R 3O , R 3P , R 3Q , R 3R , R 3S , R 3T , R 3U , R 3V , R 3W , R 3X , R 3Y , R 3Z , R 3AA , R 3AB , R 3AC , R 3AD , R 3AE and R 3AF each independently represents a hydrogen atom, an electron-withdrawing group, an amino group, a substituted amino group, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group, an aryloxy group, or a monovalent heterocyclic group, and these groups may have a substituent. When a plurality of such substituents are present, they may be bonded to each other to form a ring together with the atom to which they are bonded.] [5] R 3M , R 3Q , R 3R , R 3V , R3W , R 3AA , R 3AB and the above R 3AF At least one of the groups is an alkoxy group, a cycloalkoxy group, or an aryloxy group, which may have a substituent. [6] The process according to any one of [1] to [5], wherein the aromatic compound having a boric acid residue is a compound represented by formula (B-1) or formula (B-2). TIFF0007636272000005.tif47138[In the formula, Ar B0 represents an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded to each other, and these groups may have a substituent. a B1 and a B2 each independently represents an integer of 0 or greater. Ar B1 and Ar B3 each independently represents an arylene group or a divalent heterocyclic group, and these groups may have a substituent. Ar B2 and Ar B4 each independently represents an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded to each other, and these groups may have a substituent. B2 and Ar B4 When multiple are present, they may be the same or different. R B1 , R B2 and R B3 R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. B2 and R B3 When multiple are present, they may be the same or different. Z B1 , Z B2 , Z B3 and Z B4are each independently -B(OR C2 )2(wherein, R C2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and these groups may have a substituent. C2 may be the same or different and may be linked to each other to form a ring structure together with the oxygen atom to which they are bonded.) or a group represented by -BFQ' (wherein Q' represents Li, Na, K, Rb, or Cs). [7] The step of reacting an aromatic compound having a boric acid residue includes: The aromatic compound having a boric acid residue; Halogen atoms and -OS(=O)2R C1 (In the formula, R C1 represents an alkyl group, a cycloalkyl group, or an aryl group, and these groups may have a substituent; The method according to any one of [1] to [6], wherein the reacting step is [8] The aromatic compound is a compound having a halogen atom and -OS(=O)R C1 (In the formula, R C1 has the same meaning as defined above.) [9] The method according to [7] or [8], wherein the aromatic compound is a compound represented by formula (C-1) or formula (C-2). TIFF0007636272000006.tif47138[In the formula, Ar Y1 represents an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded to each other, and these groups may have a substituent. a 1 and a 2 each independently represents an integer of 0 or greater. Ar X1 and ArX3 each independently represents an arylene group or a divalent heterocyclic group, and these groups may have a substituent. Ar X2 and Ar X4 each independently represents an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded to each other, and these groups may have a substituent. X2 and Ar X4 When multiple are present, they may be the same or different. R X1 , R X2 and R X3 R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. X2 and R X3 When multiple are present, they may be the same or different. Z C1 , Z C2 , Z C3 and Z C4 each independently represents a chlorine atom, a bromine atom, an iodine atom, or -OS(=O)R C1 It represents a group represented by the following formula:

[10] A compound represented by formula (4). TIFF0007636272000007.tif72130[where, R 4A , R 4B , R 4C , R 4D , R 4E , R 4F , R 4G , R 4H , R 4I , R 4J , R 4K , R 4L , R 4M , R 4N , R 4O , R 4P , R 4Q , R 4R , R 4S , R 4T , R 4U , R 4V , R4W , R 4X , R 4Y , R 4Z , R 4AA , R 4AB , R 4AC , R 4AD , R 4AE and R 4AF Each of R independently represents a hydrogen atom, an electron-withdrawing group, an amino group, a substituted amino group, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group, an aryloxy group, or a monovalent heterocyclic group, and these groups may have a substituent. When a plurality of the substituents are present, they may be bonded to each other to form a ring together with the atom to which they are bonded. However, R 4M , R 4Q , R 4R , R 4V , R 4W , R 4AA , R 4AB and R 4AF At least one of these is an alkoxy group, a cycloalkoxy group, or an aryloxy group, and these groups may have a substituent.]

[11] A palladium complex containing the compound according to

[10] as a ligand.

[12] A composition comprising the compound according to

[10] and a palladium complex precursor. Effect of the Invention

[0006] By carrying out Suzuki polymerization reaction using a palladium complex containing the compound of the present invention as a ligand, it is possible to produce a polymer compound in which the amount of monomer remaining after the reaction is reduced. Furthermore, according to the production method of the present invention, the amount of monomer remaining after the reaction is reduced, and the weight average molecular weight is relatively low (for example, 7.0×10 4 Below, 4.0×10 4 Furthermore, the present invention also provides a compound (i.e., a ligand compound) that can be used in the Suzuki polymerization reaction, a palladium complex, and a composition that contains the ligand compound and a palladium complex precursor. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] Preferred embodiments of the present invention will now be described in detail.

[0008] <Explanation of common terms> Terms commonly used in this specification have the following meanings unless otherwise specified. Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, i-Pr represents an isopropyl group, and t-Bu represents a tert-butyl group. The hydrogen atom may be a deuterium atom or a protium atom. In the formula representing a metal complex, the solid line representing a bond to a central metal means an ionic bond, a covalent bond or a coordinate bond.

[0009] "Polymer compound (hereinafter also referred to as "polymer")" means a polymer having a molecular weight distribution and a weight average molecular weight of 2×10 3 ~2×10 8 The polymer refers to a polymer in which The polymer compound may be any one of a block copolymer, a random copolymer, an alternating copolymer, a graft copolymer, and the like, or may be in other forms. The end group of the polymer compound is preferably a stable group. The end group of the polymer compound is preferably a group conjugated with the main chain, and examples thereof include an aryl group or a monovalent heterocyclic group bonded to the main chain of the polymer compound via a carbon-carbon bond. A "low molecular weight compound" is a compound that does not have a molecular weight distribution and has a molecular weight of 1×10 4 The following compound is meant:

[0010] The term "structural unit" refers to a unit that exists in a polymer compound, one or more of which are present.

[0011] The "alkyl group" may be either linear or branched. The number of carbon atoms in a linear alkyl group, not including the number of carbon atoms in the substituent, is usually 1 to 50, preferably 1 to 30, and more preferably 1 to 20. The number of carbon atoms in a branched alkyl group, not including the number of carbon atoms in the substituent, is usually 3 to 50, preferably 3 to 30, and more preferably 4 to 20. The alkyl group may have a substituent, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isoamyl group, a 2-ethylbutyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a 3-propylheptyl group, a decyl group, a 3,7-dimethyloctyl group, a 2-ethyloctyl group, a 2-hexyldecyl group, a dodecyl group, and groups in which a hydrogen atom in these groups is substituted with a substituent (for example, a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a 3-phenylpropyl group, a 3-(4-methylphenyl)propyl group, a 3-(3,5-di-hexylphenyl)propyl group, and a 6-ethyloxyhexyl group). The number of carbon atoms in a "cycloalkyl group", not including the number of carbon atoms in the substituent, is usually 3 to 50, preferably 3 to 30, and more preferably 4 to 20. The cycloalkyl group may have a substituent, and examples thereof include a cyclohexyl group, a cyclohexylmethyl group, a cyclohexylethyl group, and groups in which a hydrogen atom in these groups is substituted with a substituent.

[0012] The term "aryl group" refers to an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon. The number of carbon atoms in an aryl group is usually 6 to 60, preferably 6 to 20, and more preferably 6 to 10, not including the number of carbon atoms in the substituent. The aryl group may have a substituent, and examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a 1-pyrenyl group, a 2-pyrenyl group, a 4-pyrenyl group, a 2-fluorenyl group, a 3-fluorenyl group, a 4-fluorenyl group, a 2-phenylphenyl group, a 3-phenylphenyl group, a 4-phenylphenyl group, and groups in which a hydrogen atom in these groups is substituted with a substituent.

[0013] The "alkoxy group" may be either linear or branched. The number of carbon atoms in a linear alkoxy group is usually 1 to 40, and preferably 1 to 10, not including the number of carbon atoms in the substituent. The number of carbon atoms in a branched alkoxy group is usually 3 to 40, and preferably 4 to 10, not including the number of carbon atoms in the substituent. The alkoxy group may have a substituent, and examples thereof include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, an isobutyloxy group, a tert-butyloxy group, a pentyloxy group, a hexyloxy 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, and groups in which hydrogen atoms in these groups are substituted with a substituent. The number of carbon atoms of the "cycloalkoxy group", not including the number of carbon atoms of the substituent, is usually 3 to 40, and preferably 4 to 10. The cycloalkoxy group may have a substituent, and examples thereof include a cyclohexyloxy group. The number of carbon atoms in the "aryloxy group", not including the number of carbon atoms of the substituent, is usually 6 to 60, and preferably 6 to 48. The aryloxy group may have a substituent, and examples thereof include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 1-anthracenyloxy group, a 9-anthracenyloxy group, a 1-pyrenyloxy group, and groups in which a hydrogen atom in these groups is substituted with a substituent.

[0014] The term "p-valent heterocyclic group" (p is an integer of 1 or more) refers to an atomic group remaining after removing p hydrogen atoms from among the hydrogen atoms directly bonded to the carbon atoms or heteroatoms constituting the ring of a heterocyclic compound. Among p-valent heterocyclic groups, a "p-valent aromatic heterocyclic group" which is an atomic group remaining after removing p hydrogen atoms from among the hydrogen atoms directly bonded to the carbon atoms or heteroatoms constituting the ring of an aromatic heterocyclic compound is preferred. The term "aromatic heterocyclic compound" refers to compounds in which the heterocycle itself exhibits aromaticity, such as oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, and dibenzophosphole, as well as compounds in which an aromatic ring is condensed with a heterocycle, even if the heterocycle itself does not exhibit aromaticity, such as phenoxazine, phenothiazine, dibenzoborole, dibenzosilole, and benzopyran.

[0015] The number of carbon atoms of the monovalent heterocyclic group, not including the number of carbon atoms of the substituent, is usually 2 to 60, and preferably 4 to 20. The monovalent heterocyclic group may have a substituent, and examples thereof include a thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a piperidinyl group, a quinolinyl group, an isoquinolinyl group, a pyrimidinyl group, a triazinyl group, and groups in which a hydrogen atom in these groups is substituted with a substituent.

[0016] The term "halogen atom" refers to a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

[0017] The "amino group" may have a substituent, and is preferably a substituted amino group. The substituent of the amino group is preferably an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group. Examples of the substituted amino group include a dialkylamino group, a dicycloalkylamino group, and a diarylamino group. Examples of the amino group and substituted amino group include a dimethylamino group, a diethylamino group, a diphenylamino group, a bis(4-methylphenyl)amino group, a bis(4-tert-butylphenyl)amino group, a bis(3,5-di-tert-butylphenyl)amino group, and groups in which the hydrogen atoms in these groups are substituted with substituents.

[0018] The "alkenyl group" may be either linear or branched. The number of carbon atoms in a linear alkenyl group, not including the number of carbon atoms in the substituent, is usually 2 to 30, and preferably 3 to 20. The number of carbon atoms in a branched alkenyl group, not including the number of carbon atoms in the substituent, is usually 3 to 30, and preferably 4 to 20. The number of carbon atoms in a "cycloalkenyl group" is usually 3 to 30, and preferably 4 to 20, not including the number of carbon atoms of substituents. The alkenyl group and cycloalkenyl group may have a substituent. Examples of the alkenyl group and cycloalkenyl group include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 2-butenyl group, a 3-butenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-hexenyl group, a 5-hexenyl group, a 7-octenyl group, and groups in which a hydrogen atom in these groups is substituted with a substituent.

[0019] The "alkynyl group" may be either linear or branched. The number of carbon atoms of the alkynyl group, not including the carbon atoms of the substituent, is usually 2 to 20, preferably 3 to 20. The number of carbon atoms of the branched alkynyl group, not including the carbon atoms of the substituent, is usually 4 to 30, preferably 4 to 20. The number of carbon atoms in the "cycloalkynyl group" is usually 4 to 30, and preferably 4 to 20, not including the carbon atoms of the substituents. The alkynyl group and cycloalkynyl group may have a substituent. Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 3-pentynyl group, a 4-pentynyl group, a 1-hexynyl group, a 5-hexynyl group, and groups in which a hydrogen atom in these groups is substituted with a substituent.

[0020] The term "arylene group" refers to an atomic group remaining after removing two hydrogen atoms directly bonded to carbon atoms constituting a ring from an aromatic hydrocarbon. The number of carbon atoms in the arylene group is usually 6 to 60, preferably 6 to 30, and more preferably 6 to 18, not including the number of carbon atoms of the substituent. The arylene group may have a substituent, and examples thereof include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a dihydrophenanthrenediyl group, a naphthacenediyl group, a fluorenediyl group, a pyrenediyl group, a perylenediyl group, a chrysenediyl group, and groups in which hydrogen atoms in these groups are substituted with a substituent. The arylene group is preferably a group represented by formula (A-1) to formula (A-20). The arylene group includes a group in which a plurality of these groups are bonded.

[0021] TIFF0007636272000008.tif32143

[0022] TIFF0007636272000009.tif31146

[0023] TIFF0007636272000010.tif40148

[0024] TIFF0007636272000011.tif43155 [wherein R and R a each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group. a may be the same or different, R a may be bonded to each other to form a ring together with the atoms to which they are bonded.

[0025] The divalent heterocyclic group has usually 2 to 60 carbon atoms, preferably 3 to 20 carbon atoms, and more preferably 4 to 15 carbon atoms, not including the number of carbon atoms of the substituent. The divalent heterocyclic group may have a substituent, and examples thereof include divalent groups obtained by removing two hydrogen atoms from the hydrogen atoms directly bonded to the carbon atoms or heteroatoms constituting the ring of pyridine, diazabenzene, triazine, azanaphthalene, diazanaphthalene, carbazole, dibenzofuran, dibenzothiophene, dibenzosilole, phenoxazine, phenothiazine, acridine, dihydroacridine, furan, thiophene, azole, diazole, and triazole, and groups in which the hydrogen atoms in the groups are substituted with substituents. The divalent heterocyclic group is preferably a group represented by formula (AA-1) to formula (AA-34). The divalent heterocyclic group includes a group in which a plurality of these groups are bonded.

[0026] TIFF0007636272000012.tif34155

[0027] TIFF0007636272000013.tif34156

[0028] TIFF0007636272000014.tif28153

[0029] TIFF0007636272000015.tif31155

[0030] TIFF0007636272000016.tif29158

[0031] TIFF0007636272000017.tif25158

[0032] TIFF0007636272000018.tif27158 [wherein R and R a has the same meaning as above.]

[0033] The number of carbon atoms in the "silyl group", not including the carbon atoms of the substituent, is usually 3 to 30, and preferably 3 to 20. The silyl group may have a substituent. Examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a triisopropylsilyl group, a dimethylisopropylsilyl group, a diethylisopropylsilyl group, a tert-butyldimethylsilyl group, a n-pentyldimethylsilyl group, a n-hexyldimethylsilyl group, a n-heptyldimethylsilyl group, a n-octyldimethylsilyl group, a 2-ethylhexyldimethylsilyl group, a n-nonyldimethylsilyl group, a n-decyldimethylsilyl group, a 3,7-dimethyloctyldimethylsilyl group, a n-dodecyldimethylsilyl group, a phenylalkylsilyl group, an alkoxyphenylalkylsilyl group, an alkylphenylalkylsilyl group, a naphthylalkylsilyl group, a phenylallyldimethylsilyl group, a triphenylsilyl group, a trixylylsilyl group, a tribenzylsilyl group, a diphenylmethylsilyl group, a tert-butyldiphenylsilyl group, a dimethylphenylsilyl group, and groups in which a hydrogen atom in these groups is substituted with a substituent.

[0034] The "crosslinking group" refers to a group capable of generating a new bond by being subjected to heating, ultraviolet light irradiation, near-ultraviolet light irradiation, visible light irradiation, infrared light irradiation, radical reaction, or the like, and is preferably a crosslinking group represented by formulae (XL-1) to (XL-19).

[0035] TIFF0007636272000019.tif74170

[0036] Examples of the "substituent" include an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, a hydroxyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an amino group, a substituted amino group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, and a silyl group. The substituent may be a bridging group or an electron-withdrawing group. When there are a plurality of substituents, they may be the same or different. When there are a plurality of substituents, they may be bonded to each other to form a ring together with the atom to which they are bonded, but it is preferable that they do not form a ring.

[0037] Examples of the "electron-withdrawing group" include an alkyl group having a fluorine atom as a substituent, a halogen atom, a cyano group, a nitro group, an acyl group, a carboxyl group, and an alkoxycarbonyl group. Preferably, it is a halogen atom, a cyano group, a nitro group, an acyl group, or an alkoxycarbonyl group, more preferably a halogen atom, and even more preferably a chlorine atom or a fluorine atom, and these groups may have a substituent. The alkyl group having a fluorine atom as a substituent is preferably a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group or a perfluorooctyl group. The halogen atom in the electron-withdrawing group is preferably a chlorine atom or a fluorine atom. The number of carbon atoms in the "acyl group", not including the carbon atoms of the substituent, is usually 2 to 30, and preferably 2 to 10. The acyl group may have a substituent. Examples of the acyl group include aliphatic acyl groups such as an acetyl group, a propionyl group, a butyryl group, and an isobutyryl group; aromatic acyl groups such as a benzoyl group and a naphthoyl group; and groups in which the hydrogen atom in these groups is substituted with a substituent. The number of carbon atoms of the "alkoxycarbonyl group", not including the carbon atoms of the substituent, is usually 2 to 30, and preferably 2 to 10. The alkoxycarbonyl group may have a substituent. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, an n-pentyloxycarbonyl group, an n-hexyloxycarbonyl group, an n-heptyloxycarbonyl group, an n-octyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, an aryl ... Examples of the alkyl group include a difluorocarbonyl group, an n-nonyloxycarbonyl group, an n-decyloxycarbonyl group, a 3,7-dimethyloctyloxycarbonyl group, an n-dodecyloxycarbonyl group, a trifluoromethoxycarbonyl group, a pentafluoroethoxycarbonyl group, a perfluorobutoxycarbonyl group, a perfluorohexyloxycarbonyl group, a perfluorooctyloxycarbonyl group, and groups in which the hydrogen atoms in these groups are substituted with substituents.

[0038] The term "boric acid residue" refers to a group having a boron atom and bonded to a carbon atom via the boron atom. Examples of the boric acid residue include a boronic acid group, a boronic acid ester group, a trifluoroborate group, a trihydroxyborate group, a triolborate group, a borane group, and groups in which the hydrogen atom in these groups is substituted with a substituent.

[0039] The term "palladium complex precursor" refers to a palladium element or a palladium compound (e.g., a palladium complex and a palladium salt, hereinafter the same applies unless otherwise specified) that is reacted with a new ligand to synthesize a new palladium complex containing the ligand. Examples of the palladium complex precursor include a palladium compound and a palladium element that do not contain a compound represented by formula (0) as a ligand, and are used to synthesize a palladium complex that contains a compound represented by formula (0) as a ligand.

[0040] <Compound represented by formula (0)> The compound represented by formula (0) can be suitably used in a method for producing a polymer compound (hereinafter also referred to as the "production method of the present embodiment"), which includes a step of reacting an aromatic compound having a boric acid residue. In the production method of the present embodiment, the compound represented by formula (0) can be suitably used, for example, as a ligand of a palladium complex described later. In the production method of the present embodiment, the compound represented by formula (0) can be suitably used, for example, as a composition containing the compound represented by formula (0) and a palladium complex precursor described later. In the production method of this embodiment, the compound represented by formula (0) may be used alone or in combination with two or more kinds. In the production method of this embodiment, the compound represented by formula (0) is preferably used in combination with three or less kinds, more preferably used in combination with one or two kinds, and even more preferably used in combination with one kind.

[0041] Ar 1A and Ar 1B is preferably an arylene group which may have a substituent. Ar 1A and Ar 1B The arylene group in the formula (I) is preferably a group in which two hydrogen atoms have been removed from an aromatic hydrocarbon ring containing a 5- or 6-membered ring, among the hydrogen atoms directly bonded to carbon atoms constituting the ring, more preferably a group in which two hydrogen atoms have been removed from an aromatic hydrocarbon ring containing a 6-membered ring, among the hydrogen atoms directly bonded to carbon atoms constituting the ring, still more preferably a phenylene group, a naphthalenediyl group, an anthracenediyl group, or a phenanthrenediyl group, particularly preferably a phenylene group or a naphthalenediyl group, and particularly preferably a naphthalenediyl group, and these groups may have a substituent. Ar 1A and Ar 1BThe divalent heterocyclic group in the formula (I) is preferably a divalent group obtained by removing two hydrogen atoms from a heterocyclic compound containing a 5- or 6-membered ring, among the hydrogen atoms directly bonded to the carbon atoms or hetero atoms constituting the ring, and more preferably a divalent group obtained by removing two hydrogen atoms from pyridine, diazabenzene, azanaphthalene, diazanaphthalene, benzodioxane, or benzodioxole, among the hydrogen atoms directly bonded to the carbon atoms or hetero atoms constituting the ring, and these groups may have a substituent. Ar 1A and Ar 1B Examples of the group include groups represented by formulas (1-A) to (1-Q) described below, preferably groups represented by formulas (1-A) to (1-O) described below, and more preferably groups represented by formulas (1-A) to (1-C) described below. Ar 1A and Ar 1B are preferably identical. Ar 1A and Ar 1B The substituent that may be possessed by the aryl group is preferably an electron-withdrawing group, an amino group, a substituted amino group, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a hydroxyl group, or a silyl group, more preferably an electron-withdrawing group, an amino group, a substituted amino group, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group, an aryloxy group, or a monovalent heterocyclic group, still more preferably a fluorine atom, a chlorine atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, or a monovalent heterocyclic group, particularly preferably a fluorine atom, a chlorine atom, an alkyl group, an alkoxy group, or an aryl group, and these groups may further have a substituent. Ar 1A and Ar 1B Examples and preferred ranges of the aryl group and monovalent heterocyclic group in the substituent that may be possessed by Ar 1C ~Ar 1F The examples and preferred ranges of the aryl group and monovalent heterocyclic group in are the same as those in the above. Ar 1Aand Ar 1B Examples of the alkyl group include a benzene-1,2-diyl group, a 3-methylbenzene-1,2-diyl group, a 3-methoxybenzene-1,2-diyl group, a 3-trifluoromethylbenzene-1,2-diyl group, a 3-cyanobenzene-1,2-diyl group, a naphthalene-1,2-diyl group, a naphthalene-2,3-diyl group, a 3-methylnaphthalene-1,2-diyl group, a 6-cyanonaphthalene-1,2-diyl group, a 6-trifluoromethylnaphthalene-1,2-diyl group, and groups in which the hydrogen atoms in these groups are replaced with substituents.

[0042] Ar 1C ~Ar 1F is preferably an aryl group which may have a substituent. Ar 1C ~Ar 1F The aryl group in the formula (I) is preferably a group in which one hydrogen atom has been removed from a hydrogen atom directly bonded to a carbon atom constituting the ring of an aromatic hydrocarbon ring containing a 5- or 6-membered ring (preferably a 6-membered ring), more preferably a phenyl group, a naphthyl group, an anthracenyl group or a phenanthrenyl group, still more preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group, and these groups may further have a substituent. Ar 1C ~Ar 1F The monovalent heterocyclic group in the formula (I) is preferably a group obtained by removing one hydrogen atom from a heterocyclic compound containing a 5- or 6-membered ring (preferably a 6-membered ring) that is directly bonded to a carbon atom or hetero atom that constitutes the ring, more preferably a group obtained by removing one hydrogen atom from a pyridine, diazabenzene, azanaphthalene, or diazanaphthalene that is directly bonded to a carbon atom or hetero atom that constitutes the ring, and even more preferably a group obtained by removing one hydrogen atom from a pyridine or diazabenzene that is directly bonded to a carbon atom or hetero atom that constitutes the ring, and these groups may further have a substituent. Ar 1C ~Ar 1F At least two of the Ar1C ~Ar 1F It is more preferred that all of are identical. Ar 1C ~Ar 1F The substituent that may be present is preferably an electron-withdrawing group, an amino group, a substituted amino group, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a hydroxyl group, or a silyl group, more preferably an electron-withdrawing group, an amino group, a substituted amino group, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group, an aryloxy group, or a monovalent heterocyclic group, still more preferably a fluorine atom, a chlorine atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group, or an aryloxy group, particularly preferably an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group, or an aryloxy group, and particularly preferably an alkyl group or an alkoxy group, and these groups may further have a substituent. Ar 1C ~Ar 1F Examples and preferred ranges of the aryl group and monovalent heterocyclic group in the substituent that may be possessed by Ar 1C ~Ar 1F The examples and preferred ranges of the aryl group and monovalent heterocyclic group in are the same as those in the above. Ar 1C ~Ar 1F At least one of the above preferably has a substituent, more preferably has an electron-withdrawing group, an amino group, a substituted amino group, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a hydroxyl group, or a silyl group, further preferably has an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group, or an aryloxy group, particularly preferably has an alkoxy group, a cycloalkoxy group, or an aryloxy group, and particularly preferably has an alkoxy group, and these groups may further have a substituent. Ar 1C ~Ar 1FExamples of the aryl group include a phenyl group, a 2-methylphenyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a 2-methoxyphenyl group, a 4-methoxyphenyl group, a 4-trifluoromethylphenyl group, a 3,5-bis(trifluoromethyl)phenyl group, a 2-fluorophenyl group, a 4-fluorophenyl group, a 2,3,4,5,6-pentafluorophenyl group, and groups in which the hydrogen atoms in these groups are substituted with substituents.

[0043] <Compound represented by formula (1)> The compound represented by formula (0) is preferably a compound represented by formula (1).

[0044] Ring Ar A and ring Ar B The aromatic hydrocarbon ring in is preferably an aromatic hydrocarbon ring containing a 5-membered or 6-membered ring, more preferably an aromatic hydrocarbon ring containing a 6-membered ring, still more preferably a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring, particularly preferably a benzene ring or a naphthalene ring, and particularly preferably a naphthalene ring, and these rings may have a substituent. Ring Ar A and ring Ar B The heterocycle in is preferably a heterocycle containing a 5- or 6-membered ring, and more preferably a pyridine ring, a diazabenzene ring, an azanaphthalene ring, a diazanaphthalene ring, a benzodioxane ring, or a benzodioxole ring, and these rings may have a substituent. Ring Ar A and ring Ar B is preferably an aromatic hydrocarbon ring containing a 5-membered or 6-membered ring, or a heterocycle containing a 5-membered or 6-membered ring, more preferably an aromatic hydrocarbon ring containing a 5-membered or 6-membered ring, and even more preferably an aromatic hydrocarbon ring containing a 6-membered ring, and these rings may have a substituent. Ring Ar A and ring Ar B are preferably identical. Ring Ar A and ring Ar Bis preferably a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyridine ring, a quinoline ring, a 1,3-benzodioxole ring, or a 1,4-benzodioxane ring, more preferably a benzene ring or a naphthalene ring, and even more preferably a naphthalene ring, and these rings may have a substituent. Ring Ar A and ring Ar B Examples of the substituents that may be substituted by Ar 1A and Ar 1B The examples and preferred ranges of the substituents which may be possessed by the group are the same as those of the substituents which may be possessed by the group.

[0045] Ring Ar A and ring Ar B Examples of the alkyl group include groups represented by formulas (1-A) to (1-Q), preferably groups represented by formulas (1-A) to (1-O) described below, and more preferably groups represented by formulas (1-A) to (1-C).

[0046] TIFF0007636272000020.tif39170

[0047] TIFF0007636272000021.tif44170

[0048] TIFF0007636272000022.tif50170

[0049] TIFF0007636272000023.tif40170[where, R d and R e each independently represents a hydrogen atom, an electron-withdrawing group, an amino group, a substituted amino group, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a hydroxyl group, or a silyl group, and these groups may have a substituent. d may be the same or different, and may be bonded to each other to form a ring together with the atom to which each is bonded. emay be the same or different, and may be bonded to each other to form a ring together with the atom to which they are bonded.

[0050] R d and R e is preferably a hydrogen atom, an electron-withdrawing group, an amino group, a substituted amino group, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a hydroxyl group, or a silyl group, more preferably a hydrogen atom, an electron-withdrawing group, an amino group, a substituted amino group, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group, an aryloxy group, or a monovalent heterocyclic group, still more preferably a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, or a monovalent heterocyclic group, particularly preferably a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, or a monovalent heterocyclic group, and these groups may further have a substituent. R d and R e Examples and preferred ranges of the aryl group and monovalent heterocyclic group in 1C ~Ar 1F The examples and preferred ranges of the aryl group and monovalent heterocyclic group in are the same as those in the above.

[0051] <Compound represented by formula (2) or formula (3)> The compound represented by formula (1) is preferably a compound represented by formula (2) or a compound represented by formula (3), and more preferably a compound represented by formula (3).

[0052] R 2A ~R 2H and R 3A ~R 3Lis preferably a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group, an aryloxy group, or a monovalent heterocyclic group, more preferably a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group, an alkoxy group, or an aryl group, even more preferably a hydrogen atom or an aryl group, and particularly preferably a hydrogen atom, and these groups may have a substituent. R 2A ~R 2H and R 3A ~R 3L Examples and preferred ranges of the aryl group and monovalent heterocyclic group in 1C ~Ar 1F The examples and preferred ranges of the aryl group and monovalent heterocyclic group in are the same as those in the above.

[0053] R 2A ~R 2H may be partially or entirely different, or may be entirely the same. 2A and R 2B , R 2B and R 2C , R 2C and R 2D , R 2D and R 2E , R 2E and R 2F , R 2F and R 2G , and R 2G and R 2H are preferably not bonded to each other to form a ring with the carbon atom to which they are each bonded. R 3A ~R 3L may be partially or entirely different, or may be entirely the same. R 3A and R 3B , R 3B and R 3C , R 3C and R 3D , R 3D and R 3E , R 3E and R 3F , R 3F and R 3G , R 3Gand R 3H , R 3H and R 3I , R 3I and R 3J , R 3J and R 3K , and R 3K and R 3L are preferably not bonded to each other to form a ring with the carbon atom to which they are each bonded.

[0054] <Compound represented by formula (3-1)> The compound represented by formula (3) is more preferably a compound represented by formula (3-1).

[0055] R 3M ~R 3Z and R 3AA ~R 3AF is preferably a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group, or an aryloxy group, more preferably a hydrogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group, or an aryloxy group, and further preferably a hydrogen atom, an alkyl group, or an alkoxy group, and these groups may have a substituent. 3M ~R 3Z and R 3AA ~R 3AF Examples and preferred ranges of the aryl group and monovalent heterocyclic group in 1C ~Ar 1F The examples and preferred ranges of the aryl group and monovalent heterocyclic group in are the same as those in the above. R 3M , R 3Q , R 3R , R 3V , R 3W , R 3AA , R 3AB and R 3AF Among these, at least one (preferably at least two, more preferably at least four) is preferably an alkoxy group, a cycloalkoxy group, or an aryloxy group, more preferably an alkoxy group, and these groups may have a substituent. R 3M , R 3R , R 3W and R 3AB Among these, it is preferable that at least one (preferably at least two) is an alkoxy group, a cycloalkoxy group, or an aryloxy group, and R 3M , R 3R , R 3W and R 3AB is preferably an alkoxy group, a cycloalkoxy group, or an aryloxy group, and R 3M , R 3R , R 3W and R 3AB More preferably, all of the groups are alkoxy groups, and these groups may have a substituent.

[0056] <Compound represented by formula (4)> The compound represented by formula (3-1) is preferably a compound represented by formula (4).

[0057] R 4A ~R 4L may be partially or entirely different, or may be entirely the same. R 4M ~R 4Z and R 4AA ~R 4AF may be partially or entirely different, or may be entirely the same.

[0058] R 4A ~R 4L Examples and preferred ranges of R 3A ~R 3L The examples and preferred ranges are the same as those of the above. R 4M ~R 4Z and R 4AA ~R 4AF Examples and preferred ranges of R 3M ~R 3Z and R 3AA ~R 3AF The examples and preferred ranges are the same as those of the above. R 4M , R 4Q , R 4R , R4V , R 4W , R 4AA , R 4AB and R 4AF Among these, at least two (preferably at least four) are preferably alkoxy groups, cycloalkoxy groups, or aryloxy groups, and more preferably alkoxy groups, and these groups may have a substituent. 4M , R 4R , R 4W and R 4AB Among these, it is preferable that at least one (preferably at least two) is an alkoxy group, a cycloalkoxy group, or an aryloxy group, and R 4M , R 4R , R 4W and R 4AB More preferably, all of R are alkoxy groups, cycloalkoxy groups, or aryloxy groups. 4M , R 4R , R 4W and R 4AB More preferably, all of the groups are alkoxy groups, and these groups may have a substituent.

[0059] Examples of the compound represented by formula (0) include compounds represented by the following formula:

[0060] TIFF0007636272000024.tif83152

[0061] TIFF0007636272000025.tif84152

[0062] TIFF0007636272000026.tif86151

[0063] TIFF0007636272000027.tif89152

[0064] TIFF0007636272000028.tif110150

[0065] TIFF0007636272000029.tif102150

[0066] TIFF0007636272000030.tif104145

[0067] (Palladium complex containing a compound represented by formula (0) as a ligand) A palladium complex containing a compound represented by formula (0) as a ligand can be synthesized, for example, by reacting a compound represented by formula (0) with a palladium complex precursor described later.

[0068] (Composition containing a compound represented by formula (0) and a palladium complex precursor) In the production method of this embodiment, for example, a composition containing the compound represented by formula (0) and a palladium complex precursor can be prepared by mixing the compound represented by formula (0) and a palladium complex precursor. The composition may be a mixture of a solid (particularly powder) of the compound represented by formula (0) and a solid (particularly powder) of the palladium complex precursor.

[0069] In the production method of this embodiment, the compound represented by formula (0) and the palladium complex precursor may be used separately, or a palladium complex containing the compound represented by formula (0) as a ligand may be synthesized and then used, or a composition containing the compound represented by formula (0) and the palladium complex precursor may be prepared and then used.

[0070] In the production method of this embodiment, the palladium complex containing the compound represented by formula (0) as a ligand is preferably a zero-valent or divalent palladium complex, and more preferably a divalent palladium complex. In the production method of the present embodiment, the palladium complex precursor in the composition containing the compound represented by Formula (0) and a palladium complex precursor is preferably a zero-valent or divalent palladium complex precursor, and more preferably a divalent palladium complex precursor. In the production method of this embodiment, palladium in the divalent palladium complex and the divalent palladium complex precursor usually has a counter anion and / or a substituent. Examples of the counter anion of palladium in the divalent palladium complex and the divalent palladium complex precursor include a fluoride ion, a chloride ion, a bromide ion, an iodide ion, a cyanide ion, a trifluoromethanesulfonate ion (CF3SO3 - ), methanesulfonate ion (CH3SO3 - ), tetrafluoroborate ion (BF4 - ), acetate ion and acetylacetonate ion, preferably chloride ion, bromide ion, methanesulfonate ion or acetate ion, more preferably chloride ion or methanesulfonate ion. Examples of the substituent carried by palladium in the divalent palladium complex and the divalent palladium complex precursor include an alkyl group, an alkenyl group and an aryl group, and these groups may further have a substituent. Examples of the substituent possessed by palladium in the divalent palladium complex and the divalent palladium complex precursor include a methyl group, an ethyl group, a propyl group, an isopropyl group, an allyl group, a crotyl group, a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2-biphenyl group, a 3-biphenyl group, a 4-biphenyl group, a 2-fluoro-4-biphenyl group, a 2'-fluoro-2-biphenyl group, a 2'-amino-2-biphenyl group, a 2'-(methylamino-κN)-2-biphenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 4-trifluoromethylphenyl group.

[0071] <Palladium complex> The palladium complex used in the production method of this embodiment is a palladium complex containing a compound represented by formula (0) as a ligand (hereinafter, sometimes abbreviated as "the palladium complex of this embodiment"). This palladium complex is used as a catalyst for polymerization reaction using Suzuki coupling reaction. In the production method of this embodiment, the palladium complex of this embodiment may be used alone or in combination with two or more kinds. In the production method of this embodiment, the palladium complex of this embodiment is preferably used in combination with three or less kinds, more preferably used in combination with one or two kinds, and even more preferably used in combination with one kind.

[0072] The palladium complex precursor is preferably a palladium compound that does not contain a compound represented by formula (0) as a ligand. The palladium complex precursor is preferably a zero-valent or divalent palladium compound. Examples of the palladium complex precursor include tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3), bis(tri-tert-butylphosphine)palladium(0), bis(tricyclohexylphosphine)palladium(0), tetrakis(triphenylphosphine)palladium(0), diacetate bis(triphenylphosphine)palladium(II), dichlorobis(benzonitrile)palladium(II) (Pd(BnCN)2Cl2), dichlorobis(acetonitrile), and the like. )palladium(II) (Pd(MeCN)2Cl2), trans-dichlorobis(tricyclohexylphosphine)palladium(II), dichloro(1,5-cyclooctadiene)palladium(II), di-μ-chlorobis(2'-(2-(amino-κN)ethyl)phenyl-κC)dipalladium(II), di-μ-chlorobis(2'-(amino-κN)(1,1'-biphenyl)-2-yl-κC)dipalladium(II), bis(μ-methanesulfonato-κO:κO)(2'-(amino-κN) (1,1'-biphenyl)-2-yl-κC)dipalladium(II), bis(μ-methanesulfonato-κO:κO)(2'-(methylamino-κN)(1,1'-biphenyl)-2-yl-κC)dipalladium(II), trans-dichlorobis(triphenylphosphine)palladium(II), palladium(II) acetate, palladium(II) acetylacetonate, palladium(II) bromide, palladium(II) chloride, palladium(II) cyanide, palladium(II) iodide and and tetrakis(acetonitrile)palladium(II) tetrafluoroborate; tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3), dichlorobis(benzonitrile)palladium(II) (Pd(BnCN)2Cl2), dichlorobis(acetonitrile)palladium(II) (Pd(MeCN)2Cl2), dichloro(1,5-cyclooctadiene)palladium(II), bis(μ-methanesulfonato-κO:κO) (2'-(methylamino-κN)(1,1'-biphenyl)-2-yl-κC)dipalladium(II), palladium(II) acetate, palladium(II) acetylacetonate, palladium(II) bromide, palladium(II) chloride, palladium(II) cyanide, palladium(II) iodide or tetrakis(acetonitrile)palladium(II) tetrafluoroborate are preferred, tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba )3), dichlorobis(acetonitrile)palladium(II) (Pd(MeCN)2Cl2), bis(μ-methanesulfonato-κO:κO)(2'-(methylamino-κN)(1,1'-biphenyl)-2-yl-κC)dipalladium(II), palladium(II) acetate, palladium(II) acetylacetonate, palladium(II) bromide, palladium(II) chloride or palladium(II) iodide are more preferred.

[0073] The palladium complex of the present embodiment can be prepared, for example, by reacting a palladium complex precursor with a compound represented by formula (0). In the production method of the present embodiment, the palladium complex of the present embodiment prepared in advance in this manner can be used, and the palladium complex of the present embodiment prepared in advance may be used after isolation or may be used as it is without isolation. In the production method of this embodiment, the palladium complex of this embodiment generated in the reaction system may also be used. In the production method of this embodiment, the palladium complex precursor and the compound represented by formula (0) may be mixed separately in the reaction system to generate the palladium complex of this embodiment in the reaction system, and this may be used. In the production method of this embodiment, a composition containing the palladium complex precursor and the compound represented by formula (0) may be mixed in the reaction system to generate the palladium complex of this embodiment in the reaction system, and this may be used. In this specification, the phrase "in the presence of a palladium complex containing a compound represented by formula (0) as a ligand" is used to mean both the presence of a palladium complex prepared in advance and the presence of a palladium complex prepared in situ, as described above.

[0074] In the manufacturing method of this embodiment, when the compound represented by formula (0) and the palladium complex precursor are used (including the case of using a composition containing both), the amount of the palladium complex precursor used is usually 0.000001 mol% to 100 mol%, preferably 0.00001 mol% to 10 mol%, more preferably 0.0001 to 1 mol%, and even more preferably 0.001 mol% to 0.1 mol%, based on the total number of moles of the aromatic compound having a boric acid residue. The amount of the compound represented by formula (0) used is usually 0.000001 mol% to 100 mol%, preferably 0.00001 mol% to 10 mol%, more preferably 0.0001 mol% to 1 mol%, and even more preferably 0.001 mol% to 0.1 mol%, based on the total number of moles of the aromatic compound having a boric acid residue. The ratio of the amount of the palladium complex precursor to the amount of the compound represented by formula (0) is not particularly limited. The molar ratio of the amount of the palladium complex precursor to the amount of the compound represented by formula (0) is usually 1:0.01 to 1:100, preferably 1:0.1 to 1:10, more preferably 1:1 to 1:4, still more preferably 1:1 to 1:2, and particularly preferably 1:1.

[0075] In the manufacturing method of the present embodiment, when the palladium complex of the present embodiment is used, the amount of the palladium complex of the present embodiment is not particularly limited as long as the reaction proceeds. The amount of the palladium complex of the present embodiment is usually 0.000001 mol% to 100 mol%, preferably 0.00001 mol% to 10 mol%, more preferably 0.0001 mol% to 1 mol%, and even more preferably 0.001 mol% to 0.1 mol%, based on the total mole number of the aromatic compound having boric acid residue.

[0076] <base> In the production method of this embodiment, it is preferable to use a base. In the production method of this embodiment, only one type of base may be used, or two or more types of bases may be used.

[0077] In the production method of the present embodiment, the base may be an organic base or an inorganic base, for example, sodium hydroxide, sodium carbonate, tripotassium phosphate, ammonium hydroxide, tetramethylammonium hydroxide, and tetrabutylammonium hydroxide, and tripotassium phosphate, tetramethylammonium hydroxide, or tetrabutylammonium hydroxide is preferred.

[0078] In the production method of the present embodiment, the amount of base used is not particularly limited as long as the reaction proceeds. The amount of base used is usually 0.001 molar equivalent to 10000 molar equivalent, preferably 0.1 molar equivalent to 1000 molar equivalent, more preferably 1 molar equivalent to 100 molar equivalent, further preferably 2 molar equivalent to 50 molar equivalent, and particularly preferably 4 molar equivalent to 20 molar equivalent, based on the total number of moles of aromatic compounds having boric acid residues.

[0079] <Phase transfer catalyst> In the production method of this embodiment, it is preferable to use a phase transfer catalyst. In the production method of this embodiment, only one type of phase transfer catalyst may be used, or two or more types of phase transfer catalysts may be used.

[0080] In the production method of the present embodiment, the phase transfer catalyst is not particularly limited, but examples thereof include ammonium salts, phosphonium salts, and crown ethers. Examples of the phase transfer catalyst include trioctylmethylammonium bromide, tetrabutylammonium bromide, tetraphenylphosphonium bromide, tetraethylphosphonium bromide, and 18-crown-6-ether.

[0081] In the present embodiment, the amount of phase transfer catalyst is not particularly limited as long as the reaction proceeds. The amount of phase transfer catalyst is usually 0.001 to 10000 molar equivalents, preferably 0.01 to 1000 molar equivalents, more preferably 0.1 to 100 molar equivalents, based on the total mole number of aromatic compounds having boric acid residue.

[0082] <Solvent> In the production method of the present embodiment, it is preferable to use a solvent. In the production method of the present embodiment, only one type of solvent may be used, or two or more types of solvents may be used. In the production method of this embodiment, the solvent may be an organic solvent or may be water. In the production method of this embodiment, it is preferable to use both an organic solvent and water as the solvent.

[0083] In the production method of the present embodiment, when an organic solvent is used as a solvent, the organic solvent is not particularly limited and may be a hydrophilic organic solvent or a hydrophobic organic solvent. Examples of the organic solvent include acetone, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, benzene, toluene, xylene, mesitylene, o-dichlorobenzene, and chloroform.

[0084] In the production method of the present embodiment, the amount of the solvent used is not particularly limited as long as the reaction proceeds. The amount of the solvent used is usually 1 part by mass to 1,000,000 parts by mass, preferably 10 parts by mass to 100,000 parts by mass, and more preferably 100 parts by mass to 10,000 parts by mass, when the total amount of the aromatic compounds having boric acid residues is 100 parts by mass.

[0085] In the production method of this embodiment, when both an organic solvent and water are used as the solvent, the ratio of the organic solvent to the water is not particularly limited as long as the reaction proceeds. In the production method of this embodiment, when both an organic solvent and water are used as the solvent, the volume ratio of the amount of the organic solvent to the amount of the water is usually 1:100 to 100:1, preferably 1:10 to 10:1, more preferably 1:3 to 3:1, and further preferably 1:2 to 2:1.

[0086] In the production method of this embodiment, the reaction temperature is not particularly limited as long as the reaction proceeds at the temperature. The reaction temperature is, for example, -100°C to 300°C, preferably -20°C to 200°C, more preferably 0°C to 150°C, and further preferably 20°C to 100°C.

[0087] In the production method of this embodiment, the reaction time is usually 0.1 to 1000 hours, preferably 0.2 to 100 hours, more preferably 0.5 to 50 hours, and further preferably 1 to 24 hours.

[0088] <Aromatic compounds having boric acid residues> In the production method of this embodiment, the number of boric acid residues contained in the aromatic compound having a boric acid residue is usually 1 to 10, preferably 2 to 5, more preferably 2 or 3, and even more preferably 2. When the aromatic compound having a boric acid residue has a plurality of boric acid residues, the boric acid residues may be the same or different, but are preferably the same. In the production method of this embodiment, two or more types of aromatic compounds having a boric acid residue may be used, or only one type may be used.

[0089] The aromatic compound having a boric acid residue is preferably a compound represented by formula (B-1) or a compound represented by formula (B-2).

[0090] Z B1 ~Z B4 may all be the same or some or all of them may be different, and preferably, they are all the same.

[0091] Z B1 ~Z B4 Examples of the group include groups represented by formulae (BE-1) to (BE-13).

[0092] TIFF0007636272000031.tif49158

[0093] In formulae (BE-11) to (BE-13), M represents a metal atom and is preferably a lithium atom, a sodium atom, or a potassium atom.

[0094] Said Z B1 ~Z B4 is preferably a group represented by formula (BE-1) to formula (BE-3), formula (BE-5), formula (BE-6), formula (BE-9), formula (BE-12) or formula (BE-13), and more preferably a group represented by formula (BE-1) to formula (BE-3), formula (BE-5) or formula (BE-6).

[0095] <Aromatic compounds having halogen-reactive groups> In the production method of this embodiment, in addition to the aromatic compound having a boric acid residue, a halogen atom and -OS(=O)R C1 (In the formula, R C1 represents an alkyl group, a cycloalkyl group, or an aryl group, and these groups may have a substituent. It is preferable to use an aromatic compound containing at least one reactive group (hereinafter, sometimes referred to as a "halogen reactive group") selected from the group consisting of groups represented by the following formulas. Among them, it is preferable to use an aromatic compound containing at least two types selected from the group consisting of the halogen reactive groups. Here, when "at least two types selected from the group consisting of halogen-reactive groups" refers to at least two types selected from halogen atoms (chlorine atom, bromine atom, iodine atom, etc.), it is -OS(=O)R C1 and a halogen atom and -OS(=O)R C1 When at least one kind is selected from each of the above, totaling at least two kinds, the term is used to mean including all of the above.

[0096] Two or more kinds of aromatic compounds having a halogen-reactive group may be used, or only one kind may be used.

[0097] The aromatic compound having two or more halogen-reactive groups is preferably a compound represented by formula (C-1) or formula (C-2).

[0098] Said Z C1 ~Z C4 is preferably a chlorine atom, a bromine atom or an iodine atom, and more preferably a bromine atom.

[0099] Said Z C1 ~Z C4 may be all the same or some or all of them may be different, and preferably are all the same.

[0100] <Compound represented by formula (B-2) or formula (C-2)> a 1 and a B1 is preferably 2 or less, and more preferably 1.

[0101] a 2 and a B2 is preferably 2 or less, and more preferably 0.

[0102] R B1 , R B2 , R B3 , R X1 , R X2 and R X3 is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group, and these groups may have a substituent.

[0103] Ar B1 , Ar B3 , Ar X1 and Ar X3 The arylene group represented by the formula (A-1) is more preferably a group represented by formula (A-9), and even more preferably a group represented by formula (A-1), and these groups may have a substituent.

[0104] Ar B1 , Ar B3 , Ar X1 and ArX3 The divalent heterocyclic group represented by the formula (AA-1), (AA-2) or (AA-7) to (AA-26) is more preferably a group represented by the formula (AA-1), (AA-2) or (AA-7) to (AA-26), and these groups may have a substituent.

[0105] Ar B1 , Ar B3 , Ar X1 and Ar X3 is preferably an arylene group which may have a substituent.

[0106] Ar B2 , Ar B4 , Ar X2 and Ar X4 The arylene group represented by the formula (A-1), (A-6), (A-7), (A-9) to (A-11) or (A-19) is more preferably a group represented by the formula (A-1), and these groups may have a substituent.

[0107] Ar B2 , Ar B4 , Ar X2 and Ar X4 A more preferred range of the divalent heterocyclic group represented by Ar B1 , Ar B3 , Ar X1 and Ar X3 The more preferred range is the same as that of the divalent heterocyclic group represented by the following formula:

[0108] Ar B2 , Ar B4 , Ar X2 and Ar X4 In the divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded, more preferred and even more preferred ranges of the arylene group and the divalent heterocyclic group are, respectively, B1 , Ar B3 , Ar X1 and Ar X3 The more preferred and further preferred ranges are the same as those of the arylene group and divalent heterocyclic group represented by the following formula:

[0109] Ar B2 , ArB4 , Ar X2 and Ar X4 Examples of the divalent group in which at least one arylene group represented by the formula (I) and at least one divalent heterocyclic group are directly bonded to each other include groups represented by the formula (I), which may have a substituent.

[0110] TIFF0007636272000032.tif38164[where, R XX represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent.

[0111] R XX is preferably an alkyl group, a cycloalkyl group or an aryl group, and these groups may have a substituent.

[0112] Ar B2 , Ar B4 , Ar X2 and Ar X4 is preferably an arylene group which may have a substituent.

[0113] Ar B1 ~Ar B4 , R B1 ~R B3 , Ar X1 ~Ar X4 and R X1 ~R X3 The substituent which the group represented by the formula (I) may have is preferably an alkyl group, a cycloalkyl group or an aryl group, and these groups may further have a substituent.

[0114] The compound represented by formula (B-2) or formula (C-2) is preferably a compound represented by formulas (X-1) to (X-7), more preferably a compound represented by formulas (X-3) to (X-7), and even more preferably a compound represented by formulas (X-3) to (X-6).

[0115] TIFF0007636272000033.tif42139

[0116] TIFF0007636272000034.tif39139

[0117] TIFF0007636272000035.tif42156

[0118] TIFF0007636272000036.tif43162[where, R X4 and R X5 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a halogen atom, a monovalent heterocyclic group, or a cyano group, and these groups may have a substituent. X4 may be the same or different. X5 may be the same or different, and adjacent R X5 may be bonded to each other to form a ring together with the carbon atoms to which they are attached. BC is Z B1 ~Z B4 or Z C1 ~Z C4 represents.]

[0119] Examples of the compound represented by formula (B-2) or formula (C-2) include compounds represented by formulas (X1-1) to (X1-30), and preferably compounds represented by formulas (X1-6) to (X1-14).

[0120] TIFF0007636272000037.tif35170

[0121] TIFF0007636272000038.tif36170

[0122] TIFF0007636272000039.tif38170

[0123] TIFF0007636272000040.tif36170

[0124] TIFF0007636272000041.tif36170

[0125] TIFF0007636272000042.tif47170

[0126] TIFF0007636272000043.tif53170

[0127] TIFF0007636272000044.tif43170

[0128] TIFF0007636272000045.tif45170

[0129] TIFF0007636272000046.tif47140

[0130] <Compound represented by formula (B-1) or formula (C-1)> Ar B0 Or Ar Y1 The arylene group represented by the formula (A-1), (A-6), (A-7), (A-9) to (A-11), (A-13) or (A-19) is more preferably a group represented by the formula (A-1), (A-7), (A-9) or (A-19), and these groups may have a substituent.

[0131] Ar B0 Or Ar Y1 is more preferably a group represented by formula (AA-4), formula (AA-10), formula (AA-13), formula (AA-15), formula (AA-18) or formula (AA-20), and even more preferably a group represented by formula (AA-4), formula (AA-10), formula (AA-18) or formula (AA-20), and these groups may have a substituent.

[0132] Ar B0 Or Ar Y1 In the divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded, more preferred ranges of the arylene group and the divalent heterocyclic group are respectively as defined above in Ar B0Or Ar Y1 The more preferred and further preferred ranges are the same as those of the arylene group and divalent heterocyclic group represented by the following formula:

[0133] Ar B0 Or Ar Y1 As the divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded, Ar B2 and Ar B4 Or Ar of formula (C-2) X2 and Ar X4 and at least one divalent heterocyclic group directly bonded to one or more arylene groups represented by the following formula:

[0134] Ar B0 Or Ar Y1 The substituent which the group represented by the following formula may have is preferably an alkyl group, a cycloalkyl group or an aryl group, and these groups may further have a substituent.

[0135] Examples of the compound represented by formula (B-1) or formula (C-1) include compounds represented by formulas (Y-1) to (Y-10).

[0136] TIFF0007636272000047.tif25140[where, R Y1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. Y1 may be the same or different, and adjacent R Y1 may be bonded to each other to form a ring together with the carbon atoms to which they are attached. BC has the same meaning as above.]

[0137] R Y1 is preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and these groups may have a substituent.

[0138] TIFF0007636272000048.tif28140[In the formula, R Y1 and Z BC has the same meaning as above. X Y1 is -C(R Y2 )2-, -C(R Y2 )=C(R Y2 )- or C(R Y2 )2-C(R Y2 )2- represents a group represented by R Y2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. Y2 may be the same or different, R Y2 may be bonded to each other to form a ring together with the carbon atoms to which they are bonded.

[0139] R Y2 is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an alkyl group, a cycloalkyl group or an aryl group, and these groups may have a substituent.

[0140] X Y1 In the above, -C(R Y2 )2-, where R Y2 The combination of R is preferably such that both are alkyl groups or cycloalkyl groups, both are aryl groups, both are monovalent heterocyclic groups, or one is an alkyl group or cycloalkyl group and the other is an aryl group or monovalent heterocyclic group, more preferably one is an alkyl group or cycloalkyl group and the other is an aryl group, and these groups may have a substituent. Y2 may be bonded to each other to form a ring together with the atoms to which they are bonded, R Y2 When forms a ring, -C(R Y2 The group represented by 2- is preferably a group represented by formulae (Y-A1) to (Y-A5), more preferably a group represented by formula (Y-A4), and these groups may have a substituent.

[0141] TIFF0007636272000049.tif23140

[0142] X Y1 In the above, -C(R Y2 )=C(R Y2 Two R in the group represented by Y2 The combination of the above is preferably such that both are alkyl groups or cycloalkyl groups, or one is an alkyl group or cycloalkyl group and the other is an aryl group, and these groups may have a substituent.

[0143] X Y1 In the above, -C(R Y2 )2-C(R Y2 )2-, where R Y2 is preferably an alkyl group or a cycloalkyl group which may have a substituent. Y2 may be bonded to each other to form a ring together with the atoms to which they are bonded, R Y2 When forms a ring, -C(R Y2 )2-C(R Y2 The group represented by (Y-)2- is preferably a group represented by formulae (Y-B1) to (Y-B5), more preferably a group represented by formula (Y-B3), and these groups may have a substituent.

[0144] TIFF0007636272000050.tif24140[where, R Y2 has the same meaning as above.]

[0145] TIFF0007636272000051.tif24140[where, R Y1 , X Y1 and Z BC has the same meaning as above.]

[0146] TIFF0007636272000052.tif38145

[0147] TIFF0007636272000053.tif45148[In the formula, R Y1 and Z BC has the same meaning as above. R Y3 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent.

[0148] R Y3 is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group, and these groups may have a substituent.

[0149] TIFF0007636272000054.tif31148[In the formula, R Y1 and Z BC has the same meaning as above. R Y4 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent.

[0150] R Y4 is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group, and these groups may have a substituent.

[0151] Examples of the compound represented by formula (B-1) or formula (C-1) include a compound represented by formula (Y-101)-(Y-171) consisting of an arylene group, a compound represented by formula (Y-201)-(Y-211) consisting of a divalent heterocyclic group, and a compound represented by formula (Y-301)-(Y-306) consisting of a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded. In formula (Y-101)-(Y-171), formula (Y-201)-(Y-211) and formula (Y-301)-(Y-306), Z BC has the same meaning as above.

[0152] TIFF0007636272000055.tif31170

[0153] TIFF0007636272000056.tif48170

[0154] TIFF0007636272000057.tif30164

[0155] TIFF0007636272000058.tif42165

[0156] TIFF0007636272000059.tif39165

[0157] TIFF0007636272000060.tif52170

[0158] TIFF0007636272000061.tif42170

[0159] TIFF0007636272000062.tif27170

[0160] TIFF0007636272000063.tif41170

[0161] TIFF0007636272000064.tif37170

[0162] TIFF0007636272000065.tif39165

[0163] TIFF0007636272000066.tif37165

[0164] TIFF0007636272000067.tif44164

[0165] TIFF0007636272000068.tif54168

[0166] TIFF0007636272000069.tif38170

[0167] TIFF0007636272000070.tif36170

[0168] TIFF0007636272000071.tif46170

[0169] TIFF0007636272000072.tif44170

[0170] TIFF0007636272000073.tif41170

[0171] TIFF0007636272000074.tif43170

[0172] In the manufacturing method of the present embodiment, the ratio between the molar number of boric acid residue contained in the aromatic compound having boric acid residue and the molar number of halogen-reactive group contained in the aromatic compound having halogen-reactive group is not particularly limited.In the manufacturing method of the present embodiment, when the molar number of boric acid residue contained in the aromatic compound having boric acid residue is 100 moles, the molar number of halogen-reactive group contained in the aromatic compound having halogen-reactive group is, for example, 50 to 200 moles, preferably 70 to 150 moles, more preferably 80 to 120 moles, even more preferably 90 to 110 moles, and particularly preferably 95 to 105 moles.

[0173] In the production method of the present embodiment, after the polymerization reaction, the boric acid residue terminal or the halogen-reactive group terminal of the obtained polymer compound may be blocked as necessary. For example, the boric acid residue terminal and / or the halogen-reactive group terminal may be blocked by adding a monofunctional compound having a boric acid residue or a monofunctional compound having a halogen-reactive group, such as phenylboronic acid or bromobenzene, followed by heating and stirring.

[0174] In the production method of the present embodiment, the obtained polymer compound can be extracted by diluting the polymer compound to an appropriate concentration with a good solvent, performing operations such as washing and purification as necessary, and then dropping the polymer compound solution into a poor solvent to precipitate the polymer compound, which can then be extracted by filtration. The structure, weight average molecular weight, etc. of the extracted polymer compound can be analyzed by ordinary analytical methods such as gel permeation chromatography and NMR.

[0175] <Reasons why the present invention is effective> Although the reason why the present invention exhibits its effects is not entirely clear, the following mechanism of action is assumed. For example, in conventional methods for producing polymer compounds using palladium complexes, the ligands used are monodentate phosphine ligands and some bidentate phosphine ligands such as 1,1′-bis(diphenylphosphino)ferrocene and 1,2-bis(diphenylphosphino)ethane. When these ligands are used, particularly unreacted aromatic monomers remain. The present inventors believed that the cause of this was ring-walking (a phenomenon in which a transition metal such as palladium moves along an aromatic ring while interacting with the π electrons of the aromatic ring). Specifically, when a palladium complex containing a conventional ligand is used, the polymer chain is less likely to dissociate from palladium after reductive elimination in a palladium-catalyzed reaction, so ring-walking is more likely to occur. On the other hand, when the palladium complex of the present embodiment is used, the polymer chain is more likely to dissociate from palladium, so ring-walking is less likely to occur, and as a result, it is believed that the step-growth polymerization property is increased and the amount of residual monomer after the reaction is sufficiently reduced.

[0176] <Other> The polymer compound produced by the production method of this embodiment can be suitably used as a material (e.g., a hole transport material and a light emitting material) for a coating-type light emitting device (e.g., an organic EL display, etc.) produced by inkjet printing or the like. EXAMPLES

[0177] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[0178] For the NMR of the obtained compound, a measurement sample of 5 mg to 10 mg was dissolved in about 0.5 mL of deuterated chloroform (CDCl3), and the measurement was performed using an NMR apparatus (manufactured by Bruker, DPX300).

[0179] The analysis of the obtained polymer compound was performed by gel permeation chromatography (hereinafter sometimes referred to as "GPC") by the following method, and the weight average molecular weight in terms of polystyrene was calculated. In addition, the residual monomer amount was calculated by the area percentage method using a GPC chart. Residual monomer amount (%) = [(area of monomer) / (total area of monomer and polymer)] × 100

[0180] <Analysis conditions of GPC> GPC measuring apparatus: HLC-8220GPC (manufactured by Tosoh Corporation) Column: PLgel 10μm MIXED-B (manufactured by Agilent Technologies) Column temperature: 40 °C Mobile phase: Tetrahydrofuran Flow rate: 1.5 mL / min Detection: UV detection (wavelength 228 nm)

[0181] <Synthesis of aromatic monomers> Synthesis of Compounds 1 and 3 to 12 Compound 1 was synthesized according to the method described in JP-A-2011-174061. Compound 3, Compound 5, Compound 10, and Compound 12 were synthesized according to the method described in JP-A-2012-144722. Compound 4 was synthesized according to the method described in International Publication No. 2012 / 008550. Compound 6 was synthesized according to the method described in JP-A-2010-189630. Compound 7 and Compound 11 were synthesized according to the method described in International Publication No. 2002 / 045184. Compound 8 was synthesized according to the method described in JP 2008-106241 A. Compound 9 was synthesized according to the method described in JP 2010-215886 A. TIFF0007636272000075.tif172151

[0182] <Commercially available palladium complexes> Dichloro(2,2'-bis(diphenylphosphino)1,1'-binaphthyl)palladium(II) was purchased as a reagent from Sigma-Aldrich, and dichlorobis(tri-o-tolylphosphine)palladium(II), dichloro(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloromethane adduct, and dichloro(1,2-bis(diphenylphosphino)ethane)palladium(II) were purchased as reagents from Tokyo Chemical Industry Co., Ltd. and used.

[0183] <Synthesis Example 1> 2,2'-dibromo-1,1'-binaphthyl (0.50 g) was added to a glass reaction vessel, and the inside of the reaction vessel was replaced with nitrogen. Dehydrated tetrahydrofuran (10 mL) was added to the reaction vessel, and the vessel was cooled to -78°C. 1.6M n-butyllithium / hexane solution (1.7 mL) was slowly added dropwise to the obtained solution, and the mixture was stirred for 2 hours. Bis(2-methoxyphenyl)chlorophosphine (0.85 g) was suspended in dehydrated toluene (5 mL), and the mixture was slowly added dropwise to the reaction liquid, and the mixture was stirred for 30 minutes. The reaction liquid was heated to room temperature (meaning 25°C, and the same applies in this specification) and stirred for 1 hour, and then heated to 60°C and stirred for 3 hours. After the reaction liquid was cooled to room temperature, water (10 mL) was added to stop the reaction, and an aqueous sodium hydrogen carbonate solution was added to neutralize the mixture. The mixture obtained was transferred to a separatory funnel, and the organic phase was washed with water, and the organic phase was transferred to an Erlenmeyer flask. The organic phase was dried over magnesium sulfate and then concentrated using a rotary evaporator. The resulting crude product was purified by silica gel column chromatography using heptane and ethyl acetate to obtain 2,2'-bis(di(2-methoxyphenyl)phosphino)-1,1'-binaphthyl (0.12 g) as a white solid.

[0184] Analysis of 2,2'-bis[di(2-methoxyphenyl)phosphino]-1,1'-binaphthyl TIFF0007636272000076.tif42130

[0185] 1 H-NMR (δppm, CDCl3 solvent): 8.0-7.7(m, 12H), 7.5-6.7(m, 10H), 6.6(m, 4H), 6.4(m, 2H), 3.4(s, 6H), 3.3(s, 6H) 31 P-NMR (δppm, CDCl3 solvent): -36.6 (br s) APPI-HRMS:Calcd for C 48 H 41 O4P2[M+H] + :743.2474, found:743.2352

[0186] <Synthesis Example 2> 2,2'-Bis(di(2-methoxyphenyl)phosphino)-1,1'-binaphthyl (98 mg) and dichlorobis(acetonitrile)palladium(II) (34 mg) were placed in a glass reaction vessel, and the inside of the reaction vessel was replaced with nitrogen. Dehydrated toluene (3 mL) was added to the reaction vessel, and the mixture was stirred at room temperature for 13 hours. The resulting solid was filtered and washed three times with toluene (6 mL). The obtained solid was dried under reduced pressure to obtain a yellow solid, dichloro(2,2'-bis(di(2-methoxyphenyl)phosphino)-1,1'-binaphthyl)palladium(II) (88 mg).

[0187] Analysis of dichloro(2,2'-bis(di(2-methoxyphenyl)phosphino)-1,1'-binaphthyl)palladium(II) (hereinafter sometimes referred to as "Complex 1") TIFF0007636272000077.tif50130

[0188] 1H-NMR (δppm, CDCl3 solvent): 8.4-8.3(m, 2H), 7.6-7.5(m, 10H), 7.2-7.1(m, 2H), 7.0-6.9(m, 2H), 6.9-6.8(m, 6H), 6.6(m, 2H), 6.4(m, 2H), 5.8(m, 2H)4.4(s, 6H), 3.2(s, 6H) 31 P-NMR (δppm, CDCl3 solvent): 19.5(s)

[0189] <Example 1> Toluene (45 mL), compound 1 (1.44 g), compound 2 (0.57 g), compound 3 (1.32 g), compound 4 (0.40 g), compound 5 (0.35 g), and complex 1 (1.5 mg) were added to a glass reaction vessel. The reaction vessel was degassed by passing nitrogen gas at room temperature through it, and then heated in an oil bath at 90°C. A 10% by mass aqueous solution of tetramethylammonium hydroxide (30 mL) and tetrabutylammonium bromide (0.10 g) were added to the heated reaction vessel, and refluxed at 90°C for 1 hour. The reaction solution was sampled at 30-minute intervals, and the reaction vessel was cooled to room temperature when the weight-average molecular weight measured by gel permeation chromatography under the following analysis conditions became constant. The weight-average molecular weight was 12×10 3 The residual monomer content was 6%. The reaction solution was poured into methanol (400 mL), and the resulting solid was filtered out and washed three times with methanol. The resulting solid was dried under reduced pressure to obtain a yellow powdery polymer (2.8 g).

[0190] <Example 2> The experiment was carried out in the same manner as in Example 1, except that Complex 1 in Example 1 was changed to dichloro(2,2'-bis(diphenylphosphino)1,1'-binaphthyl)palladium(II) (1.3 mg) (hereinafter sometimes referred to as "PdCl2(binap)"). The weight average molecular weight was 32 × 10 3 The amount of residual monomer was 2%. A yellow powdery polymer (2.7 g) was obtained.

[0191] <Example 3> Toluene (45 mL), compound 6 (1.41 g), compound 7 (1.15 g), compound 8 (0.17 g), compound 9 (0.14 g), and complex 1 (1.5 mg) were added to a glass reaction vessel. The reaction vessel was degassed by passing nitrogen gas at room temperature through it, and then heated in an oil bath at 90 ° C. Tetramethylammonium hydroxide 10 mass% aqueous solution (30 mL) and tetrabutylammonium bromide (0.10 g) were added to the heated reaction vessel, and refluxed at 90 ° C. for 1 hour. The reaction solution was sampled at 30-minute intervals, and the reaction vessel was cooled to room temperature when the weight-average molecular weight measured by gel permeation chromatography in the same manner as in Example 1 became constant. The weight-average molecular weight was 17 × 10 3 The residual monomer content was 1%. The reaction solution was poured into methanol (400 mL), and the solid formed was filtered out and washed three times with methanol. The solid obtained was dried under reduced pressure to obtain a milky white powdery polymer (1.6 g).

[0192] <Example 4> The experiment was carried out in the same manner as in Example 3, except that the complex 1 in Example 3 was changed to PdCl2(binap) (1.3 mg). The weight average molecular weight was 21 × 10 3 The amount of residual monomer was 1%. A milky white powdery polymer (1.7 g) was obtained.

[0193] <Example 5> Toluene (45 mL), compound 10 (2.18 g), compound 3 (1.30 g), compound 11 (0.34 g), compound 5 (0.14 g), compound 12 (0.37 g), and complex 1 (1.5 mg) were added to a glass reaction vessel. The reaction vessel was degassed by passing nitrogen gas at room temperature through it, and then heated in an oil bath at 90 ° C. Tetramethylammonium hydroxide 10 mass% aqueous solution (30 mL) and tetrabutylammonium bromide (0.10 g) were added to the heated reaction vessel, and refluxed at 90 ° C. for 1 hour. The reaction solution was sampled at 30-minute intervals, and the reaction vessel was cooled to room temperature when the weight-average molecular weight measured by gel permeation chromatography in the same manner as in Example 1 became constant. The weight-average molecular weight was 30 × 10 3The residual monomer content was 1%. The reaction solution was poured into methanol (400 mL), and the solid formed was filtered out and washed three times with methanol. The solid obtained was dried under reduced pressure to obtain a yellow-green powdery polymer (3.1 g).

[0194] <Example 6> The experiment was carried out in the same manner as in Example 5, except that the complex 1 in Example 5 was changed to PdCl2(binap) (1.3 mg). The weight average molecular weight was 29 × 10 3 The amount of residual monomer was 1%. A yellow-green powdery polymer (3.1 g) was obtained.

[0195] <Comparative Example 1> The experiment was carried out in the same manner as in Example 1, except that the amount of compound 1 in Example 1 was changed to 0.98 g and complex 1 was changed to dichlorobis(tri-o-tolylphosphine)palladium(II) (1.2 mg) (hereinafter sometimes referred to as "PdCl2(P(o-tol)3)2"). The weight average molecular weight was 12×10 3 The amount of residual monomer was 12%. A yellow powdery polymer (2.5 g) was obtained.

[0196] <Comparative Example 2> The experiment was carried out in the same manner as in Comparative Example 1, except that PdCl2(P(o-tol)3)2 (1.2 mg) in Comparative Example 1 was replaced with dichloro(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloromethane adduct (1.3 mg) (hereinafter sometimes referred to as "PdCl2(dppf)·CH2Cl2"). The weight average molecular weight was 12×10 3 The amount of residual monomer was 12%. A yellow powdery polymer (2.5 g) was obtained.

[0197] <Comparative Example 3> The experiment was carried out in the same manner as in Comparative Example 1, except that PdCl2(P(o-tol)3)2 (1.2 mg) in Comparative Example 1 was replaced with dichloro(1,2-bis(diphenylphosphino)ethane)palladium(II) (0.9 mg) (hereinafter sometimes referred to as "PdCl2(dppe)"). The weight average molecular weight was 13 × 10 3 The amount of residual monomer was 12%. A yellow powdery polymer (2.5 g) was obtained.

[0198] [Table 1]

[0199] From the above results, it was shown that the use of the production method of this embodiment makes it possible to greatly reduce the amount of remaining monomers when producing a polymer compound. It was also shown that the use of the compound represented by formula (4), the palladium complex having the compound represented by formula (4) as a ligand, and the composition containing the compound represented by formula (4) and a palladium complex precursor to perform Suzuki polymerization makes it possible to produce a polymer compound having a relatively small weight average molecular weight while reducing the amount of remaining monomers. [Industrial Applicability]

[0200] According to the manufacturing method of the present invention, it is possible to manufacture a polymer compound in which the amount of monomer remaining after the reaction is reduced. It is also possible to manufacture a polymer compound having a relatively small weight average molecular weight. The polymer compound is useful as a material for a coating type light emitting device.

Claims

[Claim 1] A method for producing a polymer compound, comprising a step of reacting an aromatic compound having a boronic acid residue represented by formula (B-1) or formula (B-2) with an aromatic compound represented by formula (C-1) or formula (C-2) in the presence of a palladium complex containing a compound represented by formula (4) as a ligand. [In the formula, R 4A , R 4B , R 4C , R 4D , R 4E , R 4F , R 4G , R 4H , R 4I , R 4J , R 4K , R 4L , R 4M , R 4N , R 4O , R 4P , R 4Q , R 4R , R 4S , R 4T, R4U, R4V, R4W, R4X, R4Y, R4Z, R4AA, R4AB, R4AC, R4AD, R4AE and R4AF each independently represents a hydrogen atom, an electron-withdrawing group, an amino group, a substituted amino group, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group, an aryloxy group, or a monovalent heterocyclic group, and these groups may have a substituent. When a plurality of the substituents are present, they may be bonded to each other to form a ring together with the atom to which they are bonded. However, at least one of R 4M , R 4Q , R 4R , R 4V , R 4W , R 4AA , R 4AB and R 4AF is an alkoxy group, a cycloalkoxy group or an aryloxy group, and these groups may have a substituent.] [In the formula, Ar B0 represents an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded to each other, and these groups may have a substituent. a B1 and a B2 each independently represent an integer of 0 or more. Ar B1 and Ar B3 each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent. Ar B2 and Ar B4 each independently represent an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded, and these groups may have a substituent. When a plurality of Ar B2 and Ar B4 are present, they may be the same or different. R B1 , R B2 and R B3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. When a plurality of R B2 and R B3 are present, they may be the same or different. Z B1 , Z B2 , Z B3 and Z B4 each independently represent a group represented by -B(OR C2 ) 2 (wherein R C2 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and these groups may have a substituent. A plurality of R C2 may be the same or different and may be linked to each other to form a ring structure together with the oxygen atom to which they are bonded), or a group represented by -BF 3 Q' (wherein Q' represents Li, Na, K, Rb or Cs). [In the formula, Ar Y1 represents an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded to each other, and these groups may have a substituent. a 1 and a 2 each independently represents an integer of 0 or more. Ar X1 and Ar X3 each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent. Ar and Ar each independently represent an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded, and these groups may have a substituent. When there are a plurality of Ar and Ar, they may be the same or different. R, R and R each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. When a plurality of R and R are present, they may be the same or different. Z C1 , Z C2 , Z C3 and Z C4 each independently represent a chlorine atom, a bromine atom, an iodine atom or a group represented by —O—S(═O) 2 R C1 .]

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