WO2022264724A1 - Procédé de production d'un polymère, et composé, complexe de palladium et composition - Google Patents

Procédé de production d'un polymère, et composé, complexe de palladium et composition Download PDF

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WO2022264724A1
WO2022264724A1 PCT/JP2022/020183 JP2022020183W WO2022264724A1 WO 2022264724 A1 WO2022264724 A1 WO 2022264724A1 JP 2022020183 W JP2022020183 W JP 2022020183W WO 2022264724 A1 WO2022264724 A1 WO 2022264724A1
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航平 飯塚
卓 神川
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住友化学株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule

Definitions

  • the present invention relates to a method for producing a polymer compound, a compound, a palladium complex, and a composition.
  • a production method by Suzuki polymerization reaction (polymerization reaction using Suzuki coupling reaction) using a phosphine ligand and a palladium complex is known.
  • Phosphine ligands used in this reaction include, for example, monodentate phosphine ligands (Patent Documents 1 and 2) and bidentate phosphines having two phosphorus atoms linked by an alkylene or ferrocenediyl group.
  • Ligands Non-Patent Document 1 are known.
  • an object of the present invention is to provide a method for producing a polymer compound in which the amount of monomers remaining after polymerization is reduced.
  • Another object of the present invention is to provide a ligand compound used in the production method, a palladium complex containing the ligand compound, and a composition containing a palladium complex precursor and the ligand compound. .
  • a method for producing a polymer compound comprising the 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.
  • Ar 1A and Ar 1B each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent. When there are multiple such substituents, they may be bonded together to form a ring together with the atoms to which they are bonded.
  • Ar 1C , Ar 1D , Ar 1E and Ar 1F each independently represent an aryl group or a monovalent heterocyclic group, and these groups may have a substituent.
  • R2A and R2B , R2B and R2C , R2C and R2D , R2D and R2E , R2E and R2F , R2F and R2G , R2G and R2H , R3A and R3B , R3B and R3C , R3C and R3D , R3D and R3E , R3E and R3F , R3F and R3G , R3G and R3H , R3H and R3I , R3I and R3J , R3J and R 3K and R 3K and R 3L may be combined to form a ring together with the carbon atoms to which they are combined.
  • R3M , R3N , R3O , R3P , R3Q , R3R , R3S , R3T , R3U , R3V , R3W , R3X , R3Y , R3Z , R3AA , R3AB , R3AC , R 3AD , R 3AE and R 3AF each independently represent 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.
  • 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, and these groups are substituted
  • 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.
  • 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.
  • R B2 and R B3 may be the same or different.
  • Z B1 , Z B2 , Z B3 and Z B4 each independently represent -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.
  • 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 atoms to which they are attached. or a group represented by -BF 3 Q' (in the formula, Q' represents Li, Na, K, Rb or Cs).
  • Ar X2 and Ar X4 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.
  • Ar X2 and Ar X4 may be the same or different.
  • R X1 , R X2 and R X3 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.
  • R X2 and R X3 When multiple R X2 and R X3 are present, they may be the same or different.
  • R4A , R4B, R4C , R4D , R4E , R4F , R4G , R4H , R4I , R4J , R4K , R4L , R4M , R4N , R4O , R 4P , R4Q , R4R , R4S , R4T , R4U , R4V , R4W , R4X , R4Y , R4Z , R4AA , R4AB , R4AC , R4AD , R4AE and R4AF are , 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.
  • these groups may have a substituent. When there are multiple such substituents, they may be bonded together to form a ring together with the atoms to which they are bonded. provided that 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 are It may have a substituent.
  • 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 are It may have a substituent.
  • a polymer compound in which the amount of monomers remaining after the reaction is reduced can be produced.
  • the amount of monomers remaining after the reaction is reduced, and a polymer compound having a relatively low weight-average molecular weight (for example, 7.0 ⁇ 10 4 or less, further 4.0 ⁇ 10 4 or less) is produced.
  • a compound (that is, a ligand compound) that can be used in the Suzuki polymerization reaction, a palladium complex, and a composition containing the ligand compound and a palladium complex precursor are also provided. offer.
  • Me is a methyl group
  • Et is an ethyl group
  • Bu is a butyl group
  • i-Pr is an isopropyl group
  • t-Bu is a tert-butyl group.
  • a hydrogen atom may be a deuterium atom or a protium atom.
  • solid lines representing bonds with the central metal mean ionic bonds, covalent bonds or coordinate bonds.
  • a “polymer compound (hereinafter also referred to as “polymer”)” means a polymer having a molecular weight distribution and a polystyrene-equivalent weight-average molecular weight of 2 ⁇ 10 3 to 2 ⁇ 10 8 .
  • the polymer compound may be a block copolymer, a random copolymer, an alternating copolymer, a graft copolymer, or other forms.
  • the terminal groups of the polymer compound are preferably stable groups.
  • the terminal group of the polymer compound is preferably a group conjugated to the main chain, for example, an aryl group or a monovalent heterocyclic group that binds to the main chain of the polymer compound via a carbon-carbon bond. is mentioned.
  • a "low-molecular weight compound” means a compound having no molecular weight distribution and a molecular weight of 1 ⁇ 10 4 or less.
  • Constant unit means a unit that exists at least one in a polymer compound.
  • alkyl group may be either linear or branched.
  • the number of carbon atoms in the linear alkyl group is generally 1-50, preferably 1-30, more preferably 1-20, not including the number of carbon atoms in the substituents.
  • the number of carbon atoms in the branched alkyl group is usually 3-50, preferably 3-30, more preferably 4-20, not including the number of carbon atoms in the substituents.
  • the alkyl group may have a substituent, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, 2-butyl group, isobutyl group, tert-butyl group, pentyl group, isoamyl group, 2-ethylbutyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, 3-propylheptyl group, decyl group, 3,7-dimethyloctyl group, 2-ethyloctyl group, 2-hexyldecyl group, dodecyl group , and groups in which hydrogen atoms in these groups are substituted with substituents (e.g., trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, 3-phen
  • the number of carbon atoms in the "cycloalkyl group” is usually 3-50, preferably 3-30, more preferably 4-20, not including the number of carbon atoms in the substituents.
  • the cycloalkyl group may have a substituent, and examples thereof include a cyclohexyl group, a cyclohexylmethyl group, a cyclohexylethyl group, and groups in which hydrogen atoms in these groups are substituted with substituents.
  • Aryl group means 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 the aryl group is usually 6-60, preferably 6-20, more preferably 6-10, not including the number of carbon atoms in the substituents.
  • the aryl group may have a substituent, for example, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 1-pyrenyl group, 2 -pyrenyl group, 4-pyrenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 2-phenylphenyl group, 3-phenylphenyl group, 4-phenylphenyl group, and hydrogen atoms in these groups is a group substituted with a substituent.
  • phenyl group 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group
  • 1-pyrenyl group 2 -pyrenyl group
  • 4-pyrenyl group 2-fluorenyl group, 3-fluoreny
  • alkoxy group may be either linear or branched.
  • the straight-chain alkoxy group usually has 1 to 40 carbon atoms, preferably 1 to 10 carbon atoms, not including the carbon atoms of the substituents.
  • the number of carbon atoms in the branched alkoxy group is usually 3-40, preferably 4-10, not including the number of carbon atoms in the substituents.
  • the alkoxy group may have a substituent group, for example, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, isobutyloxy group, tert-butyloxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, and groups in which hydrogen atoms in these groups are substituted with substituents is mentioned.
  • a substituent group for example, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, isobutyloxy group, tert-butyloxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group,
  • the number of carbon atoms in the "cycloalkoxy group” is usually 3-40, preferably 4-10, not including the number of carbon atoms in the substituents.
  • a cycloalkoxy group may have a substituent, such as a cyclohexyloxy group.
  • the number of carbon atoms in the "aryloxy group” is usually 6-60, preferably 6-48, not including the number of carbon atoms in the substituents.
  • the aryloxy group may have a substituent, for example, phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 1-anthracenyloxy group, 9-anthracenyloxy group, 1- A pyrenyloxy group and a group in which a hydrogen atom in these groups is substituted with a substituent are included.
  • a “p-valent heterocyclic group” (p represents an integer of 1 or more) refers to, from a heterocyclic compound, p hydrogen atoms directly bonded to the carbon atoms or heteroatoms constituting the ring. means the remaining atomic groups excluding the hydrogen atoms of Among p-valent heterocyclic groups, it is an atomic group remaining after removing p hydrogen atoms among the hydrogen atoms directly bonded to the carbon atoms or heteroatoms constituting the ring from the aromatic heterocyclic compound.
  • a “p-valent aromatic heterocyclic group” is preferred.
  • “Aromatic heterocyclic compounds” include heterocyclic compounds such as oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole and dibenzophosphole.
  • Compounds in which the ring itself exhibits aromaticity, and heterocycles such as phenoxazine, phenothiazine, dibenzoborol, dibenzosilole and benzopyran in which an aromatic ring is condensed even if the heterocycle itself does not exhibit aromaticity means a compound.
  • the number of carbon atoms in the monovalent heterocyclic group is usually 2-60, preferably 4-20, not including the number of carbon atoms in the substituents.
  • the monovalent heterocyclic group may have a substituent, for example, thienyl group, pyrrolyl group, furyl group, pyridyl group, piperidinyl group, quinolinyl group, isoquinolinyl group, pyrimidinyl group, triazinyl group, and these and a group in which a hydrogen atom in the group is substituted with a substituent.
  • Halogen atom means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • amino group may have a substituent, preferably a substituted amino group.
  • substituent of the amino group an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group is preferable.
  • Substituted amino groups include, for example, dialkylamino groups, dicycloalkylamino groups and diarylamino groups.
  • amino groups and substituted amino groups include dimethylamino group, diethylamino group, diphenylamino group, bis(4-methylphenyl)amino group, bis(4-tert-butylphenyl)amino group, bis(3,5- di-tert-butylphenyl)amino groups and groups in which hydrogen atoms in these groups are substituted with substituents.
  • alkenyl group may be either linear or branched.
  • the straight-chain alkenyl group usually has 2 to 30 carbon atoms, preferably 3 to 20 carbon atoms, not including the carbon atoms of the substituents.
  • the number of carbon atoms in the branched alkenyl group is usually 3-30, preferably 4-20, not including the number of carbon atoms in the substituents.
  • the number of carbon atoms in the "cycloalkenyl group” is usually 3-30, preferably 4-20, not including the number of carbon atoms in the substituents.
  • Alkenyl groups and cycloalkenyl groups may have a substituent, for example, vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, 3-butenyl group, 3-pentenyl group, 4- A pentenyl group, a 1-hexenyl group, a 5-hexenyl group, a 7-octenyl group, and groups in which hydrogen atoms in these groups are substituted with substituents are included.
  • alkynyl group may be either linear or branched.
  • the number of carbon atoms in the alkynyl group is usually 2-20, preferably 3-20, not including the carbon atoms of the substituents.
  • the number of carbon atoms in the branched alkynyl group is usually 4-30, preferably 4-20, not including the carbon atoms of the substituents.
  • the number of carbon atoms in the "cycloalkynyl group” is usually 4-30, preferably 4-20, not including the carbon atoms of the substituents.
  • Alkynyl groups and cycloalkynyl groups may have substituents, for example, ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 3-pentynyl group, 4- Pentynyl group, 1-hexynyl group, 5-hexynyl group, and groups in which hydrogen atoms in these groups are substituted with substituents.
  • arylene group means 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 6-60, preferably 6-30, more preferably 6-18, not including the number of carbon atoms in the substituents.
  • the arylene group may have a substituent, for example, a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthenediyl group, a dihydrophenanthenediyl group, a naphthenediyl group, a fluorenediyl group, a pyrenediyl group, a perylenediyl group, Examples include chrysenediyl groups and groups in which hydrogen atoms in these groups are substituted with substituents.
  • Arylene groups are preferably groups represented by formulas (A-1) to (A-20).
  • the arylene group includes groups in which multiple of these groups are bonded.
  • R and R a each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group.
  • a plurality of R and R a may be the same or different, and R a may be bonded to each other to form a ring together with the atoms to which they are bonded.
  • the number of carbon atoms in the divalent heterocyclic group is usually 2-60, preferably 3-20, more preferably 4-15, not including the number of carbon atoms in the substituents.
  • the divalent heterocyclic group may have a substituent, such as pyridine, diazabenzene, triazine, azanaphthalene, diazanaphthalene, carbazole, dibenzofuran, dibenzothiophene, dibenzosilole, phenoxazine, phenothiazine, acridine, A divalent group obtained by removing two hydrogen atoms from among the hydrogen atoms directly bonded to the carbon atoms or heteroatoms constituting the ring from dihydroacridine, furan, thiophene, azole, diazole and triazole, and said group A group in which a hydrogen atom in is substituted with a substituent.
  • the divalent heterocyclic group is preferably a group represented by formulas (AA
  • the number of carbon atoms in the "silyl group” is usually 3-30, preferably 3-20, not including the carbon atoms of the substituents.
  • a silyl group may have a substituent.
  • Silyl groups include, for example, trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, dimethylisopropylsilyl group, diethylisopropylsilyl group, tert-butyldimethylsilyl group and n-pentyldimethylsilyl group.
  • crosslinking group is a group capable of forming a new bond by subjecting it to heating, ultraviolet irradiation, near-ultraviolet irradiation, visible light irradiation, infrared irradiation, radical reaction, or the like, and is preferably a group represented by the formula ( XL-1) to a cross-linking group represented by formula (XL-19).
  • the "substituent” includes, for example, 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 cyclo Alkenyl groups, alkynyl groups, cycloalkynyl groups and silyl groups are included.
  • Substituents may be bridging groups or electron withdrawing groups.
  • when multiple substituents are present they may be the same or different.
  • they may bond with each other to form a ring together with the atoms to which they are bonded, but preferably do not form a ring.
  • the "electron-withdrawing group” includes, for example, 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 a halogen atom, It is a cyano group, a nitro group, an acyl group or an alkoxycarbonyl group, more preferably a halogen atom, still 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 preferably includes a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group and a perfluorooctyl group.
  • a 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” is usually 2-30, preferably 2-10, not including the carbon atoms of the substituents.
  • the acyl group may have a substituent.
  • acyl groups include aliphatic acyl groups such as acetyl, propionyl, butyryl and isobutyryl; aromatic acyl groups such as benzoyl and naphthoyl; and hydrogen atoms in these groups are substituents. Substituted groups are included.
  • the number of carbon atoms in the "alkoxycarbonyl group” is usually 2-30, preferably 2-10, not including the carbon atoms of the substituents.
  • the alkoxycarbonyl group may have a substituent.
  • alkoxycarbonyl groups include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxycarbonyl group, 3 , 7-dimethyloctyloxycarbonyl group, n-dodecyloxycarbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group,
  • a "boric acid residue” is a group that has a boron atom and bonds to a carbon atom via the boron atom.
  • the boric acid residue includes, for example, a boronic acid group, a boronate ester group, a trifluoroborate group, a trihydroxyborate group, a triolborate group, a borane group, and a hydrogen atom in these groups is substituted with a substituent. groups.
  • Palladium complex precursor means palladium simple substance and palladium compound (e.g., palladium complexes and palladium salts, hereinafter, unless otherwise specified, the same), by reacting with a new ligand , means palladium alone or a palladium compound used for synthesizing a new palladium complex containing the ligand.
  • a palladium complex precursor for example, a compound represented by the formula (0) used for synthesizing a palladium complex containing the compound represented by the formula (0) as a ligand does not contain the compound represented by the formula (0) as a ligand. Palladium compounds and elemental palladium are included.
  • the compound represented by the formula (0) can be used, for example, in a method for producing a polymer compound (hereinafter also referred to as "production method of the present embodiment"), which includes a step of reacting an aromatic compound having a boric acid residue. , can be preferably used.
  • production method of the present embodiment the compound represented by Formula (0) can be suitably used, for example, as a ligand of the palladium complex described below.
  • the compound represented by formula (0) is preferably used as a composition containing, for example, the compound represented by formula (0) and a palladium complex precursor described later. can be done.
  • only one compound represented by Formula (0) may be used, or two or more compounds may be used.
  • Ar 1A and Ar 1B are preferably optionally substituted arylene groups.
  • the arylene group for Ar 1A and Ar 1B is preferably an aromatic hydrocarbon ring containing a 5- or 6-membered ring, and two hydrogen atoms out of the hydrogen atoms directly bonded to the carbon atoms constituting the ring A group obtained by removing atoms, more preferably a group obtained by removing two hydrogen atoms from among the hydrogen atoms directly bonded to the carbon atoms constituting the ring from an aromatic hydrocarbon ring containing a 6-membered ring.
  • the divalent heterocyclic group for Ar 1A and Ar 1B is preferably a hydrogen atom directly bonded to a carbon atom or heteroatom constituting the ring from a heterocyclic compound containing a 5- or 6-membered ring.
  • Ar 1A and Ar 1B include, for example, groups represented by formulas (1-A) to (1-Q) described below, preferably groups represented by formulas (1-A) to (1-Q) described below. O), more preferably groups represented by the following formulas (1-A) to (1-C).
  • Ar 1A and Ar 1B are preferably the same.
  • Preferred substituents that Ar 1A and Ar 1B may have include 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, aryloxy group, monovalent heterocyclic group, hydroxyl group or silyl group, more preferably electron withdrawing group, amino group, substituted amino group, alkyl group, alkoxy group, cycloalkyl group, cycloalkoxy group, aryl an aryloxy group or a monovalent heterocyclic group, 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.
  • a cyclic 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.
  • aryl group and the monovalent heterocyclic group in the substituents that Ar 1A and Ar 1B may have are the aryl group and the monovalent heterocyclic group in Ar 1C to Ar 1F described below, respectively.
  • Ar 1A and Ar 1B are, for example, benzene-1,2-diyl group, 3-methylbenzene-1,2-diyl group, 3-methoxybenzene-1,2-diyl group, 3-trifluoromethylbenzene- 1,2-diyl group, 3-cyanobenzene-1,2-diyl group, naphthalene-1,2-diyl group, naphthalene-2,3-diyl group, 3-methylnaphthalene-1,2-diyl group, 6 -cyanonaphthalene-1,2-diyl group, 6-trifluoromethylnaphthalene-1,2-diyl group, and groups in which hydrogen atoms in these groups are substituted with substituents.
  • Ar 1C to Ar 1F are preferably aryl groups optionally having substituents.
  • the aryl group for Ar 1C to Ar 1F is preferably an aromatic hydrocarbon ring containing a 5-membered ring or a 6-membered ring (preferably a 6-membered ring), and a hydrogen directly bonded to a carbon atom constituting the ring.
  • a group from which one hydrogen atom has been removed 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, particularly preferably a phenyl group, and these groups may further have a substituent.
  • the monovalent heterocyclic group for Ar 1C to Ar 1F is preferably a heterocyclic compound containing a 5- or 6-membered ring (preferably a 6-membered ring) to carbon atoms or heteroatoms constituting the ring.
  • a group in which one hydrogen atom is removed from directly bonded hydrogen atoms and more preferably pyridine, diazabenzene, azanaphthalene or diazanaphthalene directly bonded to a ring-constituting carbon atom or heteroatom.
  • Ar 1C to Ar 1F are preferably the same, and more preferably all of Ar 1C to Ar 1F are the same.
  • Preferred substituents that Ar 1C to Ar 1F may have include 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, aryloxy group, monovalent heterocyclic group, hydroxyl group or silyl group, more preferably electron withdrawing group, amino group, substituted amino group, alkyl group, alkoxy group, cycloalkyl group, cycloalkoxy group, aryl group, aryloxy group or monovalent heterocyclic group, more preferably fluorine atom, chlorine atom, alkyl group, alkoxy group, cycloalkyl group, cycloalkoxy group, aryl group or aryloxy group, particularly preferably is an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group or an aryloxy group
  • Examples and preferred ranges of the aryl group and the monovalent heterocyclic group in the substituents that Ar 1C to Ar 1F may have are the examples of the aryl group and the monovalent heterocyclic group in Ar 1C to Ar 1F , respectively. and the same as the preferred range.
  • At least one of Ar 1C to Ar 1F preferably has a substituent, 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 alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group or an aryloxy group, An alkoxy group, a cycloalkoxy group or an aryloxy group is particularly preferred, and an alkoxy group is particularly preferred, and these groups may further have a substituent.
  • Ar 1C to Ar 1F include, for example, phenyl group, 2-methylphenyl group, 4-methylphenyl group, 3,5-dimethylphenyl group, 2-methoxyphenyl group, 4-methoxyphenyl group, 4-trifluoromethyl phenyl group, 3,5-bis(trifluoromethyl)phenyl group, 2-fluorophenyl group, 4-fluorophenyl group, 2,3,4,5,6-pentafluorophenyl group, and hydrogen in these groups Groups in which atoms are substituted with substituents are included.
  • the compound represented by formula (0) is preferably a compound represented by formula (1).
  • the aromatic hydrocarbon ring in ring Ar A and ring Ar B is preferably an aromatic hydrocarbon ring containing a 5- or 6-membered ring, more preferably an aromatic hydrocarbon ring containing a 6-membered ring. , more preferably a benzene ring, a naphthalene ring, anthracene ring or a phenanthrene ring, particularly preferably a benzene ring or a naphthalene ring, particularly preferably a naphthalene ring, these rings having a substituent may be
  • the heterocyclic ring in ring Ar A and ring Ar B is preferably a heterocyclic ring containing a 5- or 6-membered ring, more preferably pyridine ring, diazabenzene ring, azanaphthalene ring, diazanaphthalene ring, benzodioxane ring or benzodioxole ring, and these rings may have a
  • Ring Ar A and ring Ar B are preferably an aromatic hydrocarbon ring containing a 5- or 6-membered ring, or a heterocyclic ring containing a 5- or 6-membered ring, and a 5- or 6-membered ring is more preferably an aromatic hydrocarbon ring containing a, 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 the same.
  • Ring Ar A and ring Ar B are preferably benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, pyridine ring, quinoline ring, 1,3-benzodioxole ring or 1,4-benzodioxane ring, A benzene ring or a naphthalene ring is more preferred, and a naphthalene ring is even more preferred, and these rings may have a substituent. Examples and preferred ranges of substituents that ring Ar 1 A and ring Ar 2 B may have are the same as examples and preferred ranges of substituents that Ar 1A and Ar 1B may have.
  • Examples of ring Ar A and ring Ar B include groups represented by formulas (1-A) to (1-Q), preferably groups represented by formulas (1-A) to (1- O), more preferably groups represented by formulas (1-A) to (1-C).
  • R d and R e each independently represent 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, monovalent heterocyclic group, hydroxyl group or silyl group, and these groups may have a substituent.
  • a plurality of R d's may be the same or different, and may be bonded to each other to form a ring together with the atoms to which they are bonded.
  • a plurality of R e may be the same or different, and may be bonded to each other to form a ring together with the atoms to which they are bonded.
  • R d and R e are 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, hydroxyl group or silyl group, more preferably hydrogen atom, electron withdrawing group, amino group, substituted amino group, alkyl group, alkoxy group, cycloalkyl group, cycloalkoxy group, aryl group, aryloxy or a monovalent heterocyclic group, 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 ring a group, particularly preferably a hydrogen atom
  • the compound represented by formula (1) is preferably a compound represented by formula (2) or a compound represented by formula (3), more preferably a compound represented by formula (3) be.
  • R 2A to R 2H and R 3A to R 3L are 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; is preferably a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group, an alkoxy group or an aryl group, more preferably a hydrogen atom or an aryl group, particularly preferably a hydrogen atom, These groups may have a substituent.
  • Examples and preferred ranges of the aryl group and monovalent heterocyclic group in R 2A to R 2H and R 3A to R 3L are respectively examples and preferred ranges of the aryl group and monovalent heterocyclic group in Ar 1C to Ar 1F is the same as
  • R 2A to R 2H may be different, or all may be the same.
  • R 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 each bound to It is preferred not to form a ring with the carbon atoms to which they are attached.
  • Some or all of R 3A to R 3L may be different, or all may be the same.
  • R3A and R3B , R3B and R3C , R3C and R3D , R3D and R3E , R3E and R3F , R3F and R3G , R3G and R3H , R3H and R3I , R3I and R 3J , R 3J and R 3K , and R 3K and R 3L are preferably bonded to each other without forming a ring together with the carbon atoms to which they are bonded.
  • the compound represented by formula (3) is more preferably a compound represented by formula (3-1).
  • R 3M to R 3Z and R 3AA to R 3AF are 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, and a hydrogen 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 or an alkoxy group, and these groups are substituents. may have.
  • Examples and preferred ranges of the aryl group and monovalent heterocyclic group in R 3M to R 3Z and R 3AA to R 3AF are respectively examples and preferred ranges of the aryl group and monovalent heterocyclic group in Ar 1C to Ar 1F is the same as at least one (preferably at least two, more preferably at least four) of R 3M , R 3Q , R 3R , R 3V , R 3W , R 3AA , R 3AB and R 3AF is an alkoxy group; It is preferably a cycloalkoxy group or an aryloxy group, more preferably an alkoxy group, and these groups may have a substituent.
  • At least one (preferably at least two) of R 3M , R 3R , R 3W and R 3AB is preferably an alkoxy group, a cycloalkoxy group or an aryloxy group
  • R 3M , R 3R , R All of 3W and R3AB are preferably an alkoxy group, a cycloalkoxy group or an aryloxy group, and more preferably all of R3M , R3R , R3W and R3AB are an alkoxy group.
  • the group may have a substituent.
  • the compound represented by formula (3-1) is preferably the compound represented by formula (4).
  • R 4A to R 4L may be different, or all may be the same.
  • R 4M to R 4Z and R 4AA to R 4AF may be different, or all may be the same.
  • R 4A to R 4L are the same as examples and preferred ranges of R 3A to R 3L .
  • Examples and preferred ranges of R 4M to R 4Z and R 4AA to R 4AF are the same as examples and preferred ranges of R 3M to R 3Z and R 3AA to R 3AF .
  • at least two (preferably at least four) of R 4M , R 4Q , R 4R , R 4V , R 4W , R 4AA , R 4AB and R 4AF are alkoxy, cycloalkoxy or aryloxy groups; is preferred, and an alkoxy group is more preferred, and these groups may have a substituent.
  • At least one (preferably at least two) of R 4M , R 4R , R 4W and R 4AB is preferably an alkoxy group, a cycloalkoxy group or an aryloxy group
  • the group may have a substituent.
  • Examples of compounds represented by formula (0) include compounds represented by the following formula.
  • a palladium complex containing the compound represented by the formula (0) as a ligand is obtained by, for example, reacting the compound represented by the formula (0) with a palladium complex precursor to be described later. Palladium complexes containing the represented compounds as ligands can be synthesized.
  • composition containing compound represented by formula (0) and palladium complex precursor Composition containing compound represented by formula (0) and palladium complex precursor
  • a composition containing the compound represented by the formula (0) and the palladium complex precursor can be prepared.
  • 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.
  • the compound represented by formula (0) and the palladium complex precursor may be used separately, respectively, and the compound represented by formula (0) is used as a ligand.
  • the complex may be synthesized before use, or a composition containing the compound represented by formula (0) and a palladium complex precursor may be prepared before use.
  • the palladium complex containing the compound represented by formula (0) as a ligand is preferably a 0-valent or divalent palladium complex, more preferably a divalent palladium complex.
  • the palladium complex precursor in the composition containing the compound represented by formula (0) and the palladium complex precursor is preferably a 0valent or divalent palladium complex precursor, More preferably, it is a divalent palladium complex precursor.
  • palladium in the divalent palladium complex and the divalent palladium complex precursor usually has a counter anion and/or a substituent.
  • Counter anions of palladium in the divalent palladium complex and the divalent palladium complex precursor include, for example, fluoride ion, chloride ion, bromide ion, iodide ion, cyanide ion, trifluoromethanesulfonate ion (CF 3 SO 3 ⁇ ), methanesulfonate ion (CH 3 SO 3 ⁇ ), tetrafluoroborate ion (BF 4 ⁇ ), acetate ion and acetylacetonate ion, preferably chloride ion, bromide ion, methane It is a sulfonate ion or an acetate ion, more preferably a chloride ion or a methanesulfonate ion.
  • Substituents possessed by palladium in the divalent palladium complex and the divalent palladium complex precursor include, for example, alkyl groups, alkenyl groups and aryl groups, and these groups may further have substituents. good.
  • Substituents possessed by palladium in the divalent palladium complex and the divalent palladium complex precursor include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an allyl group, a crotyl group, a phenyl group, and a 2-methylphenyl group.
  • the palladium complex used in the production method of the present embodiment is a palladium complex containing the compound represented by formula (0) as a ligand (hereinafter, sometimes simply referred to as "the palladium complex of the present embodiment"). ).
  • This palladium complex is used as a catalyst for a polymerization reaction using the Suzuki coupling reaction.
  • only one type of palladium complex of the present embodiment may be used, or two or more types may be used.
  • the palladium complex precursor is preferably a palladium compound that does not contain the compound represented by formula (0) as a ligand.
  • the palladium complex precursor is preferably a 0-valent or divalent palladium compound.
  • Palladium complex precursors include, for example, tris(dibenzylideneacetone)dipalladium(0)(Pd 2 (dba) 3 ), bis(tri-tert-butylphosphine)palladium(0), bis(tricyclohexylphosphine) palladium(0), tetrakis(triphenylphosphine)palladium(0), diacetatebis(triphenylphosphine)palladium(II), dichlorobis(benzonitrile)palladium( II ) (Pd(BnCN) 2Cl2 ), dichlorobis( acetonitrile)palladium(II) (Pd(MeCN) 2 Cl 2 ), trans-dichlorobis(tricycl
  • dichlorobis(acetonitrile)palladium(II) (Pd(MeCN) 2 Cl 2 ), dichloro(1,5-cyclooctadiene)palladium(II), bis( ⁇ -methanesulfonate- ⁇ O: ⁇ O) (2′- (methylamino- ⁇ N)(1,1′-biphenyl)-2-yl- ⁇ C)dipalladium(II), palladium(II) acetate, palladium(II) acetylacetonate, palladium(II) bromide, palladium is preferred, tris(dibenzylideneacetone)dipalladium(0)(Pd 2 ( dba) 3 ), dichlorobis(acetonitrile)palladium(II) (Pd(MeCN) 2 Cl 2 ), bis( ⁇ -methanesulfonate- ⁇ O: ⁇ O)(2′-(methylamino- ⁇ N)(1,1
  • 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).
  • 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 isolated and then used, It may be used as it is without isolation.
  • the palladium complex of this embodiment produced in the reaction system can also be used.
  • the palladium complex precursor and the compound represented by the formula (0) are separately mixed in a reaction system to produce the palladium complex of the present embodiment in the reaction system. may be used.
  • the composition containing the palladium complex precursor and the compound represented by formula (0) is mixed in the reaction system, and the palladium complex of the present embodiment is produced in the reaction system. You can generate it and use it.
  • "in the presence of a palladium complex containing a compound represented by formula (0) as a ligand” means, as described above, in the presence of a palladium complex prepared in advance and in the reaction system is used in the sense of including any in the presence of a palladium complex prepared in.
  • the amount of the palladium complex precursor used is It is usually 0.000001 mol% to 100 mol%, preferably 0.00001 mol% to 10 mol%, more preferably, based on the total number of moles of the aromatic compound having an acid residue, It is 0.0001 to 1 mol %, more preferably 0.001 mol % to 0.1 mol %.
  • the amount of the compound represented by formula (0) to be used is generally 0.000001 mol% to 100 mol%, preferably 0, based on the total number of moles of the aromatic compound having a boric acid residue.
  • the ratio between the amount of the palladium complex precursor used and the amount of the compound represented by formula (0) used is not particularly limited.
  • the molar ratio between the amount of the palladium complex precursor used and the amount of the compound represented by formula (0) used is generally 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.
  • the amount of the palladium complex of the present embodiment used is not particularly limited as long as the amount allows the reaction to proceed.
  • the amount of the palladium complex used in the present embodiment is usually 0.000001 mol% to 100 mol%, preferably 0.00001 mol, relative to the total number of moles of the aromatic compound having a boric acid residue. % to 10 mol %, more preferably 0.0001 mol % to 1 mol %, still more preferably 0.001 mol % to 0.1 mol %.
  • a base is preferably used in the production method of the present embodiment. In the production method of the present embodiment, only one type of base may be used, or two or more types may be used.
  • the base may be an organic base or an inorganic base.
  • Bases include, for example, sodium hydroxide, sodium carbonate, tripotassium phosphate, ammonium hydroxide, tetramethylammonium hydroxide and tetrabutylammonium hydroxide, tripotassium phosphate, tetramethylammonium hydroxide or hydroxide Tetrabutylammonium is preferred.
  • the amount of base used is not particularly limited as long as the amount allows the reaction to proceed.
  • the amount of the base used is generally 0.001 molar equivalent to 10000 molar equivalents, preferably 0.1 molar equivalent to 1000 molar equivalents, relative to the total number of moles of the aromatic compound having a boric acid residue. , more preferably 1 molar equivalent to 100 molar equivalents, still more preferably 2 molar equivalents to 50 molar equivalents, and particularly preferably 4 molar equivalents to 20 molar equivalents.
  • phase transfer catalyst is preferably used in the production method of the present embodiment. In the production method of the present embodiment, only one phase transfer catalyst may be used, or two or more phase transfer catalysts may be used.
  • phase transfer catalyst is not particularly limited, but examples include ammonium salts, phosphonium salts and crown ethers.
  • Phase transfer catalysts include, for example, trioctylmethylammonium bromide, tetrabutylammonium bromide, tetraphenylphosphonium bromide, tetraethylphosphonium bromide and 18-crown-6-ether.
  • the amount of the phase transfer catalyst used is not particularly limited as long as the amount allows the reaction to proceed.
  • the amount of the phase transfer catalyst used is usually 0.001 molar equivalent to 10000 molar equivalents, preferably 0.01 molar equivalents to 1000 molar equivalents, relative to the total number of moles of the aromatic compound having a boric acid residue. molar equivalents, more preferably 0.1 molar equivalents to 100 molar equivalents.
  • solvent it is preferable to use a solvent in the production method of the present embodiment.
  • the solvent may be an organic solvent or water.
  • both an organic solvent and water are preferably used as the solvent.
  • the organic solvent when used as the solvent, is not particularly limited, and may be a hydrophilic organic solvent or a hydrophobic organic solvent.
  • Organic solvents include, for example, acetone, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, benzene, toluene, xylene, mesitylene, o-dichlorobenzene and chloroform.
  • the amount of solvent used is not particularly limited as long as the amount allows the reaction to proceed.
  • 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, when the total amount of the aromatic compound having a boric acid residue is 100 parts by mass. , more preferably 100 parts by mass to 10000 parts by mass.
  • the ratio of the organic solvent and water is not particularly limited as long as the ratio allows the reaction to proceed.
  • the volume ratio of the amount of the organic solvent used and the amount of water used is usually 1:100 to 100:1, preferably is 1:10 to 10:1, more preferably 1:3 to 3:1, still more preferably 1:2 to 2:1.
  • the reaction temperature is not particularly limited as long as it is a temperature at which the reaction proceeds.
  • 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. preferable.
  • the reaction time is usually 0.1 hour to 1000 hours, preferably 0.2 hours to 100 hours, more preferably 0.5 hours to 50 hours. , more preferably 1 hour to 24 hours.
  • the number of boric acid residues possessed by the aromatic compound having a boric acid residue is usually 1 to 10, preferably 2 to 5, more preferably. is 2 or 3, more preferably 2.
  • the aromatic compound having a boric acid residue has a plurality of boric acid residues, they may be the same or different, but are preferably the same.
  • two or more kinds of aromatic compounds having a boric acid residue may be used, or only one kind may be used.
  • 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).
  • Z B1 to Z B4 may be all the same or partially or wholly different, and preferably all are the same.
  • Z B1 to Z B4 include, for example, groups represented by formulas (BE-1) to (BE-13).
  • M represents a metal atom, preferably a lithium atom, sodium atom or potassium atom.
  • the Z B1 to Z B4 are formulas (BE-1) to (BE-3), formula (BE-5), formula (BE-6), formula (BE-9), formula (BE-12) or It is preferably a group represented by formula (BE-13), and a group represented by formulas (BE-1) to (BE-3), formula (BE-5) or formula (BE-6). It is more preferable to have
  • Two or more types of aromatic compounds having halogen-reactive groups may be used, or only one type may be used.
  • the aromatic compound having two or more halogen-reactive groups is preferably a compound represented by formula (C-1) or formula (C-2).
  • Z C1 to Z C4 are preferably a chlorine atom, a bromine atom or an iodine atom, more preferably a bromine atom.
  • Z C1 to Z C4 may be all the same or partially or wholly different, and preferably all are the same.
  • a 1 and a B1 are preferably 2 or less, more preferably 1.
  • a 2 and a B2 are preferably 2 or less, more preferably 0.
  • R B1 , R B2 , R B3 , R X1 , R X2 and R X3 are preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group.
  • the group may have a substituent.
  • Arylene groups represented by Ar B1 , Ar B3 , Ar X1 and Ar X3 are more preferably groups represented by formula (A-1) or formula (A-9), more preferably groups represented by formula (A- 1), and these groups may have a substituent.
  • the divalent heterocyclic groups represented by Ar B1 , Ar B3 , Ar X1 and Ar X3 are more preferably represented by formula (AA-1), formula (AA-2) or formulas (AA-7) to formulas (AA -26), and these groups may have a substituent.
  • Ar B1 , Ar B3 , Ar X1 and Ar X3 are preferably optionally substituted arylene groups.
  • Arylene groups represented by Ar B2 , Ar B4 , Ar X2 and Ar X4 are more preferably represented by formulas (A-1), (A-6), (A-7), and (A-9) to It is a group represented by formula (A-11) or formula (A-19), and these groups may have a substituent.
  • a more preferable range of the divalent heterocyclic groups represented by Ar B2 , Ar B4 , Ar X2 and Ar X4 is more preferable than the divalent heterocyclic groups represented by Ar B1 , Ar B3 , Ar X1 and Ar X3 . Same as the preferred range.
  • the arylene group and the divalent heterocyclic group in the divalent group in which at least one arylene group and at least one divalent heterocyclic group represented by Ar B2 , Ar B4 , Ar X2 and Ar X4 are directly bonded The more preferred range and more preferred range of the cyclic group are the same as the more preferred range and more preferred range of the arylene group and divalent heterocyclic group represented by Ar B1 , Ar B3 , Ar X1 and Ar X3 , respectively. .
  • 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.
  • R XX is preferably an alkyl group, a cycloalkyl group or an aryl group, and these groups may have a substituent.
  • Ar B2 , Ar B4 , Ar X2 and Ar X4 are preferably optionally substituted arylene groups.
  • Substituents that the groups represented by Ar B1 to Ar B4 , R B1 to R B3 , Ar X1 to Ar X4 and R X1 to R X3 may have are preferably an alkyl group, a cycloalkyl group or an aryl group. and these groups may further have a substituent.
  • the compounds represented by formula (B-2) or formula (C-2) are preferably compounds represented by formulas (X-1) to (X-7), more preferably compounds represented by formula (X- 3) to compounds represented by (X-7), more preferably compounds represented by formulas (X-3) to (X-6).
  • R X4 and R X5 are each independently 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 represents a group, and these groups may have a substituent.
  • Multiple R X4 may be the same or different.
  • a plurality of R 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 bonded.
  • Z BC represents Z B1 to Z B4 or Z C1 to Z C4 . ]
  • Examples of the compound represented by formula (B-2) or formula (C-2) include compounds represented by formulas (X1-1) to (X1-30), preferably formula (X1- 6) A compound represented by (X1-14).
  • the arylene group represented by Ar B0 or Ar Y1 is more preferably represented by formula (A-1), formula (A-6), formula (A-7), formula (A-9) to formula (A-11) , a group represented by formula (A-13) or formula (A-19), more preferably formula (A-1), formula (A-7), formula (A-9) or formula (A- 19), and these groups may have a substituent.
  • the divalent heterocyclic group represented by Ar B0 or Ar Y1 is more preferably represented by formula (AA-4), formula (AA-10), formula (AA-13), formula (AA-15), formula ( AA-18) or a group represented by formula (AA-20), more preferably formula (AA-4), formula (AA-10), formula (AA-18) or formula (AA-20) These groups may have a substituent.
  • the more preferable range is the same as the more preferable range and the more preferable range of the arylene group and the divalent heterocyclic group represented by Ar B0 or Ar Y1 described above, respectively.
  • Ar B2 and Ar B4 of formula (B-2) As the divalent group in which at least one arylene group and at least one divalent heterocyclic group represented by Ar B0 or Ar Y1 are directly bonded, Ar B2 and Ar B4 of formula (B-2) Or the same divalent group in which at least one arylene group represented by Ar X2 and Ar X4 in formula (C-2) and at least one divalent heterocyclic group are directly bonded. .
  • the substituent that the group represented by Ar B0 or Ar Y1 may have is preferably an alkyl group, a cycloalkyl group or an aryl group, and these groups may further have a substituent.
  • Examples of compounds represented by formula (B-1) or formula (C-1) include compounds represented by formulas (Y-1)-(Y-10).
  • 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 .
  • a plurality of R 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 bonded.
  • ZBC has the same meaning as above.
  • R Y1 is preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and these groups may have a substituent.
  • R Y1 and Z BC have the same meanings as above.
  • 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.
  • a plurality of R Y2 may be the same or different, and R Y2 may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. ]
  • 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 have substituents.
  • the combination of two R Y2 in the group represented by —C(R Y2 ) 2 — is preferably both alkyl groups or cycloalkyl groups, both aryl groups, and both monovalent heteroalkyl groups.
  • R Y2 may be bonded to each other to form a ring together with the atoms to which they are bonded, and when R Y2 forms a ring, the group represented by -C(R Y2 ) 2 - is preferably a group represented by formulas (Y-A1) to (Y-A5), more preferably a group represented by formula (Y-A4), these groups having a substituent may be
  • R Y2 in the group represented by —C(R Y2 ) 2 —C(R Y2 ) 2 — are preferably optionally substituted alkyl groups or cycloalkyl groups is.
  • a plurality of R Y2 may be bonded to each other to form a ring together with the atoms to which they are bonded, and when R Y2 forms a ring, -C(R Y2 ) 2 -C(R Y2 ) 2 -
  • the groups represented are preferably groups represented by formulas (Y-B1) to (Y-B5), more preferably groups represented by formula (Y-B3), and these groups are substituted You may have a group.
  • R Y1 , X Y1 and Z BC have the same meanings as above.
  • R Y1 and Z BC have the same meanings 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.
  • 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 have a substituent.
  • R Y1 and Z BC have the same meanings 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.
  • 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 have a substituent.
  • the compound represented by formula (B-1) or formula (C-1) includes, for example, a compound comprising an arylene group represented by formulas (Y-101)-(Y-171), a compound represented by formula (Y-201 )-(Y-211), at least one arylene group represented by the formula (Y-301)-(Y-306) and at least one bivalent and a compound composed of a divalent group to which the heterocyclic group of is directly bonded.
  • ZBC has the same meaning as above.
  • the number of moles of the boric acid residue contained in the aromatic compound having a boric acid residue and the number of moles of the halogen reactive group contained in the aromatic compound having a halogen reactive group is not particularly limited.
  • the halogen reaction contained in the aromatic compound having a halogen reactive group is, for example, 50 to 200 mol, preferably 70 to 150 mol, more preferably 80 to 120 mol, still more preferably 90 to 110 mol, particularly preferably is 95-105 molar.
  • the boric acid residue terminal or the halogen reactive group terminal of the resulting polymer compound may be capped, if necessary.
  • a method for blocking the terminal of boric acid residue and/or the terminal of reactive halogen group for example, a monofunctional compound having a boric acid residue or a monofunctional compound having a halogen reactive group, such as phenyl After adding the boronic acid or bromobenzene, heating and stirring may be performed.
  • the polymer compound is diluted with a good solvent to an appropriate concentration, and after performing operations such as washing and purification as necessary, By dropping the polymer compound solution into the solvent, the polymer compound can be precipitated and separated by filtration.
  • the structure, weight-average molecular weight, and the like of the polymer compound taken out can be analyzed by ordinary analytical techniques such as gel permeation chromatography and NMR.
  • the ligands used are monodentate phosphine ligands, 1,1′-bis(diphenylphosphino)ferrocene and 1,2- Some bidentate phosphine ligands, such as bis(diphenylphosphino)ethane, especially leave unreacted aromatic monomers when these ligands are used.
  • the present inventors considered the cause of this to be ring-walking (a phenomenon in which a transition metal such as palladium moves on an aromatic ring while interacting with ⁇ electrons of the aromatic ring).
  • ring-walking is likely to occur because polymer chains are less likely to dissociate from palladium after reductive elimination in the palladium-catalyzed reaction.
  • the palladium complex of the present embodiment is used, the polymer chain is easily dissociated from palladium, so ring-walking is less likely to occur, and as a result, the sequential polymerizability is increased, and the remaining after the reaction It is believed that the amount of monomer is sufficiently reduced.
  • the polymer compound produced by the production method of the present embodiment is suitably used as a material (for example, a hole transport material and a light-emitting material) for a coating-type light-emitting device (for example, an organic EL display, etc.) produced by inkjet printing or the like. can be used.
  • a material for example, a hole transport material and a light-emitting material
  • a coating-type light-emitting device for example, an organic EL display, etc.
  • NMR of the obtained compound was measured by dissolving 5 mg to 10 mg of a measurement sample in about 0.5 mL of deuterated chloroform (CDCl 3 ) and using an NMR apparatus (DPX300, manufactured by Bruker).
  • GPC analysis conditions GPC measurement device: HLC-8220GPC (manufactured by Tosoh Corporation) Column: PLgel 10 ⁇ m 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)
  • Dichloro(2,2′-bis(diphenylphosphino)1,1′-binaphthyl)palladium(II) was purchased as a reagent from Sigma-Aldrich, 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 Kasei. used.
  • the reaction solution was heated to room temperature (meaning 25° C., which is the same in this specification) and stirred for 1 hour, then heated to 60° C. and stirred for 3 hours.
  • water (10 mL) was added to terminate the reaction, and an aqueous sodium hydrogencarbonate solution was added for neutralization.
  • the resulting mixture was transferred to a separatory funnel, 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 on a rotary evaporator.
  • 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 were added to a glass reaction vessel. (1.5 mg) was added. Nitrogen gas at room temperature was passed through the reactor to deaerate it, and then the reactor was 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 the mixture was 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 and the residual monomer content was 6%.
  • the resulting reaction solution was poured into methanol (400 mL), and the solid produced was collected by filtration and washed with methanol three times. The resulting solid was dried under reduced pressure to obtain a yellow powdery polymer (2.8 g).
  • Example 2 Complex 1 in Example 1 was prepared with dichloro(2,2′-bis(diphenylphosphino)1,1′-binaphthyl)palladium(II) (1.3 mg) (hereinafter sometimes referred to as “PdCl 2 (binap)”). ) was performed in the same manner as in Example 1, except that The weight average molecular weight was 32 ⁇ 10 3 and the residual monomer content was 2%. A yellow powdery polymer (2.7 g) was obtained.
  • 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. . Nitrogen gas at room temperature was passed through the reactor to deaerate it, and then the reactor was 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 the mixture was refluxed at 90° C. for 1 hour.
  • the reaction solution was sampled at intervals of 30 minutes, and when the weight-average molecular weight measured by gel permeation chromatography in the same manner as in Example 1 became constant, the reaction vessel was cooled to room temperature. The weight average molecular weight was 17 ⁇ 10 3 and the residual monomer content was 1%.
  • the resulting reaction solution was poured into methanol (400 mL), and the solid produced was collected by filtration and washed with methanol three times. The resulting solid was dried under reduced pressure to obtain a milky white powdery polymer (1.6 g).
  • Example 4 An experiment was conducted in the same manner as in Example 3, except that complex 1 in Example 3 was changed to PdCl 2 (binap) (1.3 mg). The weight average molecular weight was 21 ⁇ 10 3 and the residual monomer content was 1%. A milky white powdery polymer (1.7 g) was obtained.
  • 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 were added to a glass reaction vessel. (1.5 mg) was added. Nitrogen gas at room temperature was passed through the reactor to deaerate it, and then the reactor was 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 the mixture was refluxed at 90° C. for 1 hour.
  • the reaction solution was sampled at intervals of 30 minutes, and when the weight-average molecular weight measured by gel permeation chromatography in the same manner as in Example 1 became constant, the reaction vessel was cooled to room temperature. The weight average molecular weight was 30 ⁇ 10 3 and the residual monomer content was 1%.
  • the resulting reaction solution was poured into methanol (400 mL), and the solid produced was collected by filtration and washed with methanol three times. The resulting solid was dried under reduced pressure to obtain a yellow-green powdery polymer (3.1 g).
  • Example 6 An experiment was conducted in the same manner as in Example 5, except that complex 1 in Example 5 was changed to PdCl 2 (binap) (1.3 mg). The weight average molecular weight was 29 ⁇ 10 3 and the residual monomer content was 1%. A yellow-green powdery polymer (3.1 g) was obtained.
  • Example 1 The amount of compound 1 in Example 1 was changed to 0.98 g, and complex 1 was replaced with dichlorobis(tri-o-tolylphosphine)palladium(II) (1.2 mg) (hereinafter referred to as "PdCl 2 (P(o-tol) 3 ) The experiment was carried out in the same manner as in Example 1, except that it was changed to " 2 "). The weight average molecular weight was 12 ⁇ 10 3 and the residual monomer content was 12%. A yellow powdery polymer (2.5 g) was obtained.
  • the production method of the present invention it is possible to produce a polymer compound with a reduced amount of monomers remaining after the reaction. Moreover, a polymer compound having a relatively small weight average molecular weight can also be produced.
  • the polymer compound is useful as a material for coating-type light-emitting devices.

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Abstract

L'invention concerne : un procédé de production d'un polymère dont la teneur en monomère restant après polymérisation est réduite ; et un composé ligand, un complexe de palladium, et une composition comprenant le composé ligand et un précurseur de complexe de palladium qui sont destinés à être utilisés dans le procédé de production.　Le procédé de production d'un polymère comprend une étape dans laquelle un composé aromatique ayant un résidu d'acide borique est mis à réagir en présence d'un complexe de palladium comprenant un composé représenté par la formule (0) en tant que ligand. Le composé ligand, le complexe de palladium, et la composition comprenant le composé ligand et un précurseur de complexe de palladium sont utilisés dans le procédé de production. Dans la formule, Ar1A et Ar1B représentent chacun un groupe arylène ou un groupe hétérocyclique divalent, ces groupes comprenant éventuellement des substituants, et Ar1C, Ar1D, Ar1E, et Ar1F représentent chacun un groupe aryle ou un groupe hétérocyclique monovalent, ces groupes ayant facultativement des substituants.]
PCT/JP2022/020183 2021-06-18 2022-05-13 Procédé de production d'un polymère, et composé, complexe de palladium et composition WO2022264724A1 (fr)

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Citations (3)

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JP2004513950A (ja) * 2000-11-17 2004-05-13 ザ　ペン　ステイト　リサーチ　ファンデーション オルト置換キラルホスフィンおよびホスフィナイトならびに非対称触媒反応でのその使用
JP2008045110A (ja) * 2006-07-18 2008-02-28 Hitachi Chem Co Ltd 共役ポリマーの製造方法、共役ポリマー、有機エレクトロニクス素子及び有機エレクトロルミネッセンス素子
JP2015144260A (ja) * 2013-12-26 2015-08-06 住友化学株式会社 発光素子およびそれに用いる高分子化合物

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JP2004513950A (ja) * 2000-11-17 2004-05-13 ザ　ペン　ステイト　リサーチ　ファンデーション オルト置換キラルホスフィンおよびホスフィナイトならびに非対称触媒反応でのその使用
JP2008045110A (ja) * 2006-07-18 2008-02-28 Hitachi Chem Co Ltd 共役ポリマーの製造方法、共役ポリマー、有機エレクトロニクス素子及び有機エレクトロルミネッセンス素子
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