WO2008093879A1 - Procédé de fabrication d'un composé aromatique conjugué - Google Patents

Procédé de fabrication d'un composé aromatique conjugué Download PDF

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WO2008093879A1
WO2008093879A1 PCT/JP2008/051897 JP2008051897W WO2008093879A1 WO 2008093879 A1 WO2008093879 A1 WO 2008093879A1 JP 2008051897 W JP2008051897 W JP 2008051897W WO 2008093879 A1 WO2008093879 A1 WO 2008093879A1
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group
carbon atoms
aromatic compound
formula
ring
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PCT/JP2008/051897
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Japanese (ja)
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Seiji Oda
Takashi Kamikawa
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Sumitomo Chemical Company, Limited
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/12—Polycyclic non-condensed hydrocarbons
    • C07C15/14—Polycyclic non-condensed hydrocarbons all phenyl groups being directly linked
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • 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
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides

Definitions

  • the present invention relates to a method for producing a conjugated aromatic compound.
  • Macomole cu les 1992, 25, 1214-1223 discloses a homocoupling reaction of an aromatic dioctalogene compound in the presence of a zerovalent nickel compound.
  • JP 2005-538154 discloses a force pulling reaction of an aromatic dihalogen compound using a catalytic amount of a zero-valent nickel complex with 2,2,1biviridine and 1,5-cyclocactogen as ligands. Has been.
  • RR 2 , R 3 , R 4 , R 5 and R 6 are the same or different from each other, hydrogen atom, fluorine atom, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms.
  • An aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms represents a cyano group.
  • I 1 , R 2 , R 3 , R 4 , R 5 and R 6 are not hydrogen atoms at the same time.
  • a process for producing a conjugated aromatic compound which comprises reacting in the presence of a phenanthroline compound represented by the formula:
  • the aromatic rings of the aromatic compound (A) and aromatic compound (B) are the same or different, and the benzene ring, biphenyl ring, naphthalene ring, fluorene ring, anthracene ring, phenanthrene ring, thiophene ring , A pyrrole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring or a quinoxaline ring, and may be substituted with at least one group not participating in the reaction. Production method;
  • R ⁇ RR 3, R 4, R 5 and R 6 are identical or different each represent a hydrogen atom, an alkyl group or Ariru group having 6 to 10 carbon atoms having 1 to 6 carbon atoms, the. Out At least one of which is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, ⁇ 1> or ⁇ 2>.
  • ⁇ 5> The method for producing a conjugated aromatic compound according to any one of ⁇ 1> to ⁇ 4>, wherein R 2 and R 5 are the same aryl group having 6 to 10 carbon atoms;
  • R 1 and R 6 and R 2 and R 5 are the same alkyl group having 1 to 6 carbon atoms ⁇ 1> - conjugated aromatic compound according to any one of ⁇ 4>;
  • a r 1 represents an n-valent aromatic group, and the aromatic ring constituting the aromatic group is a benzene ring, a phenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, a thiophene ring.
  • X 1 is Represents a leaving group, and n represents 1 or 2. When n is 2, X 1 may be the same or different.
  • a 2 represents an amino group substituted with one or two hydrocarbon groups having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.
  • the hydrocarbon group and the alkoxy group; The group is selected from the group consisting of a fluorine atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and a cyano group. It may be substituted with at least one group.
  • R 7 is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 2 carbon atoms.
  • ⁇ 20 represents an acyl group or cyano group, the alkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, or the 6 to 2 carbon atoms.
  • the aryloxy group of 0 and the acyl group having 2 to 20 carbon atoms include a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and a carbon number of 6 to 2 It may be substituted with at least one substituent selected from the group consisting of 0 aryloxy group.
  • R 7 is plural, R 7 may be the same group or different groups. Moreover, two adjacent R 7s may be bonded to form a ring.
  • X 2 represents a chlorine atom, a bromine atom or an iodine atom.
  • m represents 1 or 2
  • k represents 4 1 m.
  • a 3 represents an amino group substituted with one or two hydrocarbon groups having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.
  • the hydrocarbon group and The alkoxy group includes a fluorine atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and a cyan group. It may be substituted with at least one group selected from the group consisting of
  • R 8 is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or 2 carbon atoms.
  • An aryloxy group having 6 to 20 carbon atoms and a acyl group having 2 to 20 carbon atoms include a fluorine atom, a cyano group, and a carbon atom having 1 to 20 carbon atoms. It may be substituted with at least one substituent selected from the group consisting of a ruxoxy group, an aryl group having 6 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms.
  • R 8 is plural, R 8 may be the same group or different groups. Also, two adjacent R 8 may be bonded to form a ring.
  • X 3 represents a chlorine atom, a bromine atom or an iodine atom.
  • j represents an integer of 0 to 3.
  • a r 2 , A r 3 , A r 4 and A r 5 are the same or different and represent a divalent aromatic group.
  • the divalent aromatic group may be substituted with at least one substituent selected from the group consisting of the following (a2) to (e2).
  • (a 2) at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms
  • a substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms
  • An alkyl group having 1 to 20 carbon atoms which may be substituted with
  • (b2) at least one selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms An alkoxy group having 1 to 20 carbon atoms which may be substituted with one substituent;
  • (c 2) C 6-20 which may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1-20 carbon atoms and an aryloxy group having 6-10 carbon atoms Of the Aryl group;
  • (d2) carbon number that may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms 6-20 aryloxy groups; and
  • (e 2) at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms
  • a substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms
  • An acyl group having 2 to 20 carbon atoms which may be substituted with
  • Y 1 and Y 2 are the same or different, a single bond, - CO-, - S_ ⁇ 2 - one C (CH 3) 2 one, one C (CF 3) 2- or a fluorene one 9, 9 one Jiiru Represents a group.
  • Z 1 and Z 2 are the same or different and represent —O— or —S—.
  • X 4 represents a chlorine atom, a bromine atom or an iodine atom.
  • Aromatic compound represented by formula (3) described in 14> As the aromatic compound (A), the aromatic compound represented by the formula (3) described in 14> is used, and the aromatic compound (B) is structurally different from the aromatic compound (A).
  • Aromatic compound represented by formula (2), ⁇ 14> Aromatic compound represented by formula (3), ⁇ 15>
  • Aromatic compound represented by formula (4), ⁇ 15> A method for producing a conjugated aromatic compound according to any one of ⁇ 1> to ⁇ 11> and ⁇ 16>, wherein the aromatic compound represented by formula (5) according to 17 or above is used;
  • Aromatic compounds shown or formula (5) according to ⁇ 17> The method for producing a conjugated aromatic compound according to any one of ⁇ 1> to ⁇ 1 1> and ⁇ 1 6>, wherein the aromatic compound represented by the formula:
  • the leaving group is a chlorine atom, bromine atom, iodine atom, trifluoromethylsulfonyloxy group, alkylsulfonyloxy group having 1 to 6 carbon atoms, or arylsulfonyloxy group having 6 to 10 carbon atoms ⁇
  • ⁇ 21> The method for producing a conjugated aromatic compound according to any one of ⁇ 1> to ⁇ 20>, wherein the divalent nickel compound is nickel halide;
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are the same or different from each other, hydrogen atom, fluorine atom, alkyl group having 1 to 20 carbon atoms, carbon number 1 to 20 Represents an alkoxy group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, or a cyano group, provided that R 1 R 2 , RR 4 , R 5 and R 6 are not hydrogen atoms at the same time.
  • the aromatic compound (A) and the aromatic compound (B) are compounds having at least one aromatic ring and one or two leaving groups bonded to the aromatic ring.
  • Aromatic rings include aromatic hydrocarbon rings such as benzene ring, biphenyl ring, naphthalene ring, fluorene ring, anthracene ring, phenanthrene ring, thiophene ring, pyrrole ring, pyridin ring, pyrimidine ring, quinoline ring And aromatic heterocycles such as isoquinoline ring and quinoxaline ring.
  • the aromatic ring may be substituted with at least one group that does not participate in the reaction, and specific examples of the group that does not participate in the reaction include the following (al) to (g 1). '
  • (a1) Selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms
  • An alkyl group having 1 to 20 carbon atoms which may be substituted with at least one substituent selected from above;
  • (c1) carbon number 6 which may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms ⁇ 20 aryl groups;
  • (d1) carbon number 6 which may be substituted with at least one substituent selected from the group consisting of fluorine atom, cyano group, alkoxy group having 1 to 20 carbon atoms and aryloxy group having 6 to 20 carbon atoms ⁇ 20 aryloxy groups;
  • (el) at least one selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms
  • An acyl group having 2 to 20 carbon atoms which may be substituted with a substituent
  • (f 1) At least one selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms.
  • An acyloxy group having 2 to 20 carbon atoms which may be substituted with one substituent;
  • (g 1) Selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms At least one An arylsulfonyl group having 6 to 20 carbon atoms which may be substituted with two substituents;
  • a 1 represents an amino group substituted with one or two hydrocarbon groups having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.
  • the hydrocarbon group and the alkoxy group Is at least selected from the group consisting of a fluorine atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms and a cyan group. It may be substituted with one group.
  • alkoxy group having 1 to 20 carbon atoms in (al) to (hi) examples include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert- Butoxy, n-pentyloxy, 2, 2-dimethylpropoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n —Undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-tal decadecyloxy group , N-nonadecyloxy group, n-i
  • a phenyl group As the aryl group having 6 to 20 carbon atoms in the above (a 1) to (! 11), a phenyl group, a 4-methylphenyl group, a 2-methylphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 3-phenanthryl group, Examples include 2-anthryl group.
  • Examples of the aryloxy group having 6 to 20 carbon atoms in (al) to (hi) include a phenoxy group, a 4-methylphenoxy group, a 2-methylphenoxy group, a 1-naphthyloxy group, Examples thereof include those composed of the above-mentioned aryl group having 6 to 20 carbon atoms such as 2-naphthyloxy group, 3-phenanthryloxy group, 2-anthryloxy group, and oxygen atom.
  • alkyl group having 1 to 20 carbon atoms in (al) examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a see-butyl group, a tert-butyl group, an n- Pentyl group, 2,2-dimethylpropyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, 2-methylpentyl group, n-octyl group, 2-ethylhexyl group N-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, a
  • Examples of the acyl group having 2 to 20 carbon atoms in (el) and (hi) include an acetyl group, a propionyl group, a petityl group, an isoptylyl group, a benzoyl group, a 1-naphthoyl group, and a 2-naphthoyl group. There are 20 aliphatic or aromatic acyl groups.
  • Examples of the acyloxy group having 2 to 20 carbon atoms in ( ⁇ 1) include acetyloxy group, propionyloxy group, petityloxy group, isoptyryloxy group, benzoyloxy group, 1-naphthooxy group, 2-naphthooxy group, and the like. And those composed of an acyl group of 2 to 20 and an oxygen atom.
  • Examples of the arylsulfonyl group having 6 to 20 carbon atoms in the above (g l) include a phenylsulfonyl group and a p-toluenesulfonyl group.
  • Examples of the hydrocarbon group having 1 to 20 carbon atoms in (hi) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n —Pentyl group, 2,2-dimethylpropyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-year-octyl group, n-nonyl group, ⁇ -decyl group, ⁇ -undecyl group, ⁇ -dodecyl group, ⁇ -tridecyl group, ⁇ -tetradecyl group, ⁇ -pentadecyl group, ⁇ -hexadecyl group, ⁇ -heptadecyl group, ⁇ -octadecyl group, ⁇ -nonadecy
  • Examples of the amino group substituted with one or two hydrocarbon groups having 1 to 20 carbon atoms include methylamino group, dimethylamino group, ethylamino group, jetylamino group, n-propylamino group, di-n-propylamino group, Isopropylamino group, Diisopropylamino group, n-Butylamino group, Di-n-Butylamino group, sec-Butylamino group, Di-sec-Ptylamino group, tert-Ptylamino group, G-tert-Butylamino group, n-Pentylamino group, 2, 2-dimethylpropylamino, n-hexylamino, cyclohexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, n-undecylamino,
  • (a1) includes, for example, an unsubstituted alkyl group having 1 to 20 carbon atoms and a trifluoromethyl group.
  • (b 1) is preferably an unsubstituted alkoxy group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms such as a methoxymethoxy group.
  • (c 1) is preferably an unsubstituted aryl group having 6 to 20 carbon atoms.
  • an unsubstituted aryloxy group having 6 to 20 carbon atoms is preferable.
  • (el) includes an unsubstituted acyl group having 2 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms such as a phenoxybenzoyl group. preferable.
  • (f 1) includes, for example, an acyl having 2 to 20 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms such as an unsubstituted asiloxy group having 2 to 20 carbon atoms or a phenoxybenzoyloxy group.
  • An oxy group is preferred.
  • (1) is preferably an unsubstituted arylarylsulfonyl group having 6 to 20 carbon atoms.
  • (hi) is preferably an isopropoxy group, 2, 2-dimethylpropoxy group, cyclohexyloxy group, jetylamino group or ⁇ ; n-dodecylamino group, and A 1 is an isopropoxy group, 2 A group which is a 2-dimethylpropoxy group or a cyclohexyloxy group is more preferable.
  • an alkylsulfonyloxy group having 1 to 6 carbon atoms such as a chlorine atom, a bromine atom, an iodine atom, a trifluoromethylsulfonyloxy group, a methanesulfonyloxy group, and an ethylsulfonyloxy group
  • alkylsulfonyloxy group having 6 to 10 carbon atoms such as phenylsulfonyloxy group, p-methylphenylsulfonyloxy group, etc., preferably chlorine atom, bromine atom, iodine atom, chlorine atom
  • a bromine atom is more preferable.
  • aromatic compounds include the formula (2):
  • aromatic compound (2) (Hereinafter, abbreviated as “aromatic compound (2)”).
  • a r 1 represents an n-valent aromatic group, and the aromatic ring constituting the aromatic group is a benzene ring, biphenyl ring, naphthalene ring, fluorene ring, anthracene ring, phenanthrene ring A thiophene ring, a pyrrole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring or a quinoxaline ring, and an aromatic ring which may be substituted with at least one group not participating in the reaction.
  • X 1 represents a leaving group, and n represents 1 or 2. When n is 2, X 1 may be the same or different.
  • Examples of the group not involved in the reaction include the same groups as described above.
  • Examples of the leaving group include the same as those described above, and a chlorine atom, a bromine atom, and an iodine atom are preferable, and a chlorine atom and a bromine atom are more preferable.
  • aromatic compounds include the formula (3):
  • aromatic compound (3) (Hereinafter abbreviated as “aromatic compound (3)”).
  • examples of A 2 include the same groups as those described above for A 1 , preferably a unsubstituted alkoxy group having 3 to 20 carbon atoms, and includes an isopropyl group, an isobutoxy group, and 2,2-dimethylpropoxy. And a cyclohexyloxy group are more preferred.
  • R 7 alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, and 2 to 20 carbon atoms.
  • Examples of the acyl group are the same as those described above.
  • R 7 is preferably a hydrogen atom, an unsubstituted alkyl group having 1 to 20 carbon atoms, or an unsubstituted alkoxy group having 1 to 20 carbon atoms.
  • X 2 is preferably a chlorine atom or a bromine atom, and m is preferably 1.
  • aromatic compound (3) examples include 2,5-dichloro-pentabenzenesulfonic acid isopyl pill, 2,5-dichlorocyclobenzene sulfonic acid isobutyl, 2,5-dichlorobenzenesulphonic acid (2,2-dimethyl).
  • 2,5-Jodobenzenesulfonate isopropyl, 2,5-Jodobenzenesulfonate isobutyl, 2,5-Jodobenzenesulfonate (2,2-dimethylpropyl), 2,5-Jodobenzenesulfonate Xylyl, 2,5-Jodium benzenesulfonic acid n-octyl, 2,5-jodobenzenesulfonic acid n-pendedecyl, 2,5-jodobenzenesulfonic acid n-icosyl, N, N-jetyl 2,5-jodobenzenesulfonamide, N, N- Diisopropyl-1,2,5--Jodobenzenesulfonamide, N— (2,2-Dimethylpropyl) —2,5-—Jodobenzenesulfonamide, N—n—Dodecyl-2,5-—J
  • aromatic compounds include the formula (4):
  • aromatic compound (4) (Hereinafter abbreviated as “aromatic compound (4)”).
  • examples of A 3 include the same as A 2 above, and a unsubstituted alkoxy group having 3 to 20 carbon atoms is preferable, and an isopropyl group, an isobutoxy group, 2, 2-dimethylpropoxy A group and a hexyloxy group are more preferred.
  • R 8 is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and an acyl group having 2 to 20 carbon atoms.
  • R 8 is preferably a hydrogen atom, an unsubstituted alkyl group having 1 to 20 carbon atoms, or an unsubstituted alkoxy group having 1 to 20 carbon atoms.
  • X 3 is preferably a chlorine atom or a bromine atom, and j is preferably 0.
  • Aromatic compounds (4) include: 4,4, -dichloropiphenyl-2,2'-dimethyl disulfonate, 4,4'-dichloropiphenyl-2-ru 2,2'-jetyl disulfonate, 4,4'-dichlorobiphenyl Diluene 2, 2 'Di (n-propyl) disulfate, 4, 4' — Dichlorobiphenyl di 2,2 'Diisopropyl monodisulfonate, 4, 4' — Dichloropihue Diru 2,2 'Didisulfonic acid di ( n-butyl), 4,4'-dichlorobiphenyl-2,2'diisobutyl disulfate, 4,4'-dichlorobiphenyl 2,2, di-disulfonate (2,2-dimethylpropyl), 4, 4, 2-dichlorobiphenyl 1, 2, 2 '— Dicyclohexyl disulfone, 4, 4' — Dichlorobiphen
  • aromatic compound (2) a commercially available one may be used, or one produced according to a known method may be used.
  • Aromatic compound (3) is represented by formula (1 0) in the presence of a tertiary amine compound or pyridine compound:
  • Compound (10) includes 2,5-dichlorobenzenesulfonic acid chloride, 3, 5— Examples include dichlorobenzenesulfonic acid chloride, 2,5-dibromobenzenesulfonic acid chloride, 3,5-dibromobenzenesulfonic acid chloride, and the like. As such a compound (10), those commercially available are usually used.
  • Compound (11) includes isopropanol, isobutanol, 2,2-dimethylpropanol, cyclohexanol, n-octanol, n-pentadecanol, n-icosanol, jetylamine, diisopropylamine, 2, 2-dimethyl. Examples include propylamine, n-dodecylamine, n-icosylamine and the like. As the compound (11), a commercially available compound is usually used.
  • the amount of the compound (11) used is usually 0.2 mol or more per 1 mol of the group represented by —so 2 c 1 in the compound (10) ′, and there is no particular upper limit, and the compound (11) When is a liquid at the reaction temperature, a large excess amount may be used also as a reaction solvent.
  • Tertiary amine compounds include trimethylamine, triethylamine, tri (n-propyl) amine, tri (n-butyl) amine, disopropylethylamine, tri (n-octyl) amine, tri ( n-decyl) amine, triphenylamine, N, N-dimethylaniline, N, N, ⁇ ′, ⁇ ′-tetramethylethylenediamine, ⁇ -methylpyrrolidine and the like.
  • a commercially available tertiary amine compound is usually used.
  • the amount of the tertiary amin compound used is usually 1 mol or more per 1 mol of the group represented by —S0 2 C 1 in the compound (10), and there is no particular upper limit.
  • the amount of practical tertiary Amin compound, relative to 1 mole of the group represented in one S_ ⁇ 2 C 1 in compound (10) from 1 to 30 mol, preferably 1 to 20 moles, more preferably 1 to 10 moles.
  • pyridine compounds examples include pyridine and 4-dimethylaminopyridine.
  • a commercially available pyridine compound is usually used.
  • the amount of the pyridine compound used is usually 1 mol or more per 1 mol of the group represented by —S0 2 C 1 in the compound (10), There is no particular upper limit, and when the pyridine compound is liquid at the reaction temperature, a large excess amount may be used also as the reaction solvent.
  • the reaction of compound (10) and compound (11) is usually carried out by mixing compound (10), compound (11) and a tertiary amine compound or pyridine compound in the presence of a solvent.
  • the mixing order is not particularly limited.
  • Solvents include aromatic hydrocarbon solvents such as toluene and xylene; ether solvents such as jetyl ether, tetrahydrofuran and 1,4-dioxane; dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylformamide Aprotic polar solvents such as N, N-dimethylacetamide, hexamethylphosphoric triamide; halogenated hydrocarbon solvents such as dichloromethane, chloroform, dichloroethane, chloroform, dichlorobenzene, etc. It is done.
  • aromatic hydrocarbon solvents such as toluene and xylene
  • ether solvents such as jetyl ether, tetrahydrofuran and 1,4-dioxane
  • dimethyl sulfoxide N-methyl-2-pyrrolidone
  • Aprotic polar solvents such as N, N-dimethylacetamide
  • the compound (11), the tertiary amine compound or the pyridine compound when the compound (11), the tertiary amine compound or the pyridine compound is liquid at the reaction temperature, these may be used as the reaction solvent. These solvents may be used alone or in combination of two or more. The amount of solvent used is not particularly limited.
  • the reaction temperature between compound (10) and compound (11) is usually from 30 to 150 ° C, preferably from -10 to 70 ° C.
  • the reaction time is usually 0.5 to 24 hours.
  • the reaction mixture is mixed with water or an aqueous acid solution, and if necessary, an aromatic hydrocarbon solvent such as toluene or xylene; an aliphatic hydrocarbon solvent such as hexane or heptane; dichloromethane, dichloroethane A halogenated hydrocarbon solvent such as black form; an organic solvent insoluble in water such as an ester solvent such as ethyl acetate, and extraction treatment to obtain an organic layer containing the aromatic compound (3) Can do.
  • the aromatic layer (3) can be taken out by washing the organic layer with water, an aqueous alkali solution or the like, if necessary, and then concentrating.
  • the aromatic compound (4) is a compound (10) in the method for producing the aromatic compound (3). Instead of Equation (12):
  • the compounds (12) include 4, 4'-dichlorobiphenyl-2,2, monodisulfonic acid dichloride, 4,4 'monodibromopiphenyl-2,2'monodisulfonic acid dichloride, 3,3' monodimethyl-4 , 4, 1, Dichlorobiphenyl 1, 2, 2, — Disulfonic acid dichloride, 5, 5 '— Dimethyl-4, 4' — Dichlorobiphenyl— 2, 2 'Monodisulfonic acid dichloride, 6, 6' — Dimethyl 4 , 4 '— Dichlorobiphenyl 1, 2, 2' — Disulfonic acid dichloride, 3, 3 'Dimethyl 4, 4,' — Dichlorobiphenyl 1, 2, 2 '— Disulfonic dichloride, 5, 5' — Dimethoxy 4 , 4 '-Dichloropiphenyl 2-Lu, 2' Mono-disulfonic acid dichloride, 6, 6, -Dimethoxy- 4,4 '-Dichloropi
  • a commercially available compound may be used.
  • Bu l l. S 0 c. Ch i m. F r., 4, 49 (1 931), 1047-1049, etc. Those produced according to the known methods described in 1) may be used.
  • Examples of the compound (13) include those similar to the compound (11), and those commercially available are usually used. '
  • aromatic compounds include the formula (5):
  • aromatic compound (5) (Hereinafter abbreviated as “aromatic compound (5)”).
  • h is preferably an integer of 10 or more.
  • divalent monocyclic aromatic groups and divalent condensed aromatic groups are preferred, such as 1,4-monophenylene group, naphthalene-1, More preferred are 4-diyl group, naphthalene-1,5-diyl group, naphthalene-2,6-diyl group and naphthalene-2,7-diyl group.
  • Such a divalent aromatic group may be substituted with at least one substituent selected from the group consisting of the following (a 2) to (e 2).
  • (a 2) at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms
  • a substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms
  • An alkyl group having 1 to 20 carbon atoms which may be substituted with
  • (b 2) at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms An alkoxy group having 1 to 20 carbon atoms which may be substituted with
  • (c2) carbon number optionally substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 10 carbon atoms
  • substituents selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 10 carbon atoms.
  • (d2) carbon atoms that may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms
  • a substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms
  • (e 2) at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms
  • a substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms
  • An acyl group having 2 to 20 carbon atoms which may be substituted with
  • aryl group examples include the aryl group having 6 to 20 carbon atoms, the alkyl group having 1 to 20 carbon atoms, and the acyl group having 2 to 20 carbon atoms are the same as those described above.
  • Examples of (a 2) include the same as the above (al).
  • (B 2) is the same as (b 2) above.
  • Examples of (c 2) include the same as the above (cl).
  • Examples of (d2) include the same as (dl).
  • Examples of (e 2) include the same as (el).
  • X 4 is preferably a chlorine atom or a bromine atom.
  • aromatic compound (5) examples include compounds shown below, compounds in which the chlorine atoms at both ends of the compounds shown below are replaced by bromine atoms, and the like.
  • h represents the same meaning as described above.
  • aromatic compound (5) one produced according to a known method such as Japanese Patent No. 2,745,727 may be used, or a commercially available one may be used.
  • commercially available products include SUMIKAEXEL PES manufactured by Sumitomo Chemical Co., Ltd.
  • aromatic compound (5) those having a polystyrene equivalent weight average molecular weight of 2,000 or more are preferably used, and those having a weight average molecular weight of 3,000 or more are more preferred.
  • the invention of the present application comprises reacting an aromatic compound (A) with an aromatic compound (A) having the same structure or an aromatic compound (B) structurally different from the aromatic compound (A). It is.
  • aromatic compound (2) As aromatic compound (A),
  • aromatic compound (3) is used as aromatic compound (A).
  • Examples of the aromatic compound (A) include a case where the aromatic compound (4) is used.
  • aromatic compound (A) When aromatic compound (A) is used as aromatic compound (A), and aromatic compound (2) is structurally different from aromatic compound (A) as aromatic compound (B);
  • aromatic compound (2) When using aromatic compound (2) as aromatic compound (A) and using aromatic compound (3) structurally different from aromatic compound (A) as aromatic compound (B); When using aromatic compound (2) as aromatic compound (A) and using aromatic compound (4) structurally different from aromatic compound (A) as aromatic compound (B)
  • aromatic compound (A) is used as aromatic compound (A) and aromatic compound (5) is structurally different from aromatic compound (A) as aromatic compound (B)
  • aromatic compound (A) is used as aromatic compound (A)
  • aromatic compound (2) is used as aromatic compound (B), which is structurally different from aromatic compound (A)
  • aromatic compound (3) As aromatic compound (A), and using aromatic compound (3) structurally different from aromatic compound (A) as aromatic compound (B)
  • aromatic compound (A) is used as aromatic compound (A)
  • aromatic compound (4) is used as aromatic compound (B), which is structurally different from aromatic compound (A)
  • aromatic compound (A) is used as aromatic compound (A) and aromatic compound (5) is structurally different from aromatic compound (A) as aromatic compound (B)
  • aromatic compound (4) as aromatic compound (A) and using aromatic compound (2) structurally different from aromatic compound (A) as aromatic compound (B)
  • aromatic compound (4) is used as aromatic compound (A), and aromatic compound (3) structurally different from aromatic compound (A) is used as aromatic compound (B)
  • aromatic compound (4) is used as aromatic compound (A), and aromatic compound (4) structurally different from aromatic compound (A) is used as aromatic compound (B)
  • aromatic compound (A) is used as aromatic compound (A)
  • aromatic compound (5) is structurally different from aromatic compound (A) as aromatic compound (B); Can be mentioned.
  • divalent nickel compounds include nickel fluorides such as nickel fluoride, nickel chloride, nickel bromide and nickel iodide, nickel carboxylates such as nickel formate and nickel acetate, nickel sulfate, nickel carbonate, nickel nitrate, nickel Examples thereof include cetylacetonate, (dimethoxyethane) chloride nickel and the like, and nickel halide is preferable.
  • the amount of the divalent nickel compound used is a catalytic amount. If the amount used is too small, a conjugated aromatic compound having a small molecular weight is likely to be obtained. If the amount used is too large, post-treatment after the polymerization reaction will occur.
  • the amount of divalent nickel compound used is usually 0.001 to 0.8 mol, preferably 0.0 mol, per 1 mol of all aromatic compounds used. 1 to 0.4 mol.
  • the shape is not particularly limited, but usually powdered zinc is used.
  • the amount used is usually 1 mol or more with respect to 1 mol of all aromatic compounds to be used, and the upper limit is not particularly limited, but if it is too much, post-treatment after the polymerization reaction becomes complicated, Since it tends to be disadvantageous economically, it is practically 10 moles or less, preferably 5 moles or less.
  • R 1 R 2 , R 3 , R 4 , R 5 and R 6 are the same or different, respectively, in the formula of the phenantorin phosphorus compound (hereinafter abbreviated as phenantorin compound (1)), Hydrogen atom, fluorine atom, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, and acyl having 2 to 20 carbon atoms Represents a group or a cyan group, and R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are not simultaneously hydrogen atoms.
  • alkyl groups having 1 to 20 carbon atoms examples include alkoxy groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aryloxy groups having 6 to 20 carbon atoms, and acyl groups having 2 to 20 carbon atoms
  • alkoxy groups having 1 to 20 carbon atoms examples include alkoxy groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aryloxy groups having 6 to 20 carbon atoms, and acyl groups having 2 to 20 carbon atoms.
  • RK R 2 , R 3 , R 4 , R 5 and R 6 are the same or different and each is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, of which at least Preference is given to the phenanthroline compound (1) in which one is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms.
  • R ⁇ R 2 , R 3 , R 4 , R 5 and R 6 are the same or different and each represents a hydrogen atom, Preference is given to the phenantorin phosphorus compound (1), which is a methyl group or a phenyl group, at least one of which is a methyl group or a phenyl group.
  • R 1 and R 6 are the same group, R 2 and R 5 are the same aryl group having 6 to 10 carbon atoms,
  • Oral phosphorus compounds (1) are more preferred, R 1 and R 6 are the same group, R 2 and R 5 are phenyl groups, and R 3 and R 4 are the same groups. ), R 1 , R 2 , R 5 and R 6 are methyl groups, and R 3 and R 4 are the same group.
  • Phosphorus compound (1) and R 1 , R 2 , R 5 and R 6 are are the same group, R 3 and R 4 are methyl groups Fuenanto port phosphorus compound (1) is more preferable, R 1, R 3, R 4 and R e are hydrogen atom, R 2 and R 5 Phenantorporin compounds in which is a phenyl group 1), R 1 and R 2 and R 5 and R 6 is a methyl group, Fuenanto port phosphorus compounds R 3 and R 4 is a hydrogen atom (1) and R 1 and R 2 and R 5 and R A phenantorin phosphorus compound (1) in which 6 is a hydrogen atom and R 3 and R 4 are methyl groups is particularly preferred.
  • the phenanthroline compounds (1) include 5-methyl-1,10-phenanthroline, 4-methyl-1,1,10-phenantorin, 5,6-dimethyl-1,1,10-phenantorin, 4,7 1-dimethyl-1,10-phenantorin, 3,8-dimethyl-1,10-phenantorin, 4,7-diphenyl2,10-phenantorin, 3,8-di-t 61 "1; -butyl —1, 10—Phenant mouth phosphorus, 4, 7—Di-tert-butyl-1,10—Phenant mouth phosphorus, 3, 4, 7,8—Tetramethyl mono 1,10—Phenant mouth phosphorus, 2,9-dimethyl — 1, 10—Phenant mouth phosphorus, 2,9 1-dimethyl-4,7—Diphenyl bis 1,10—Phenant mouth phosphorus, 5, 6—Dimethoxy 1,10—Phenant mouth phosphorus, 4, 7—Dimethoxy 1,10 —Phenant mouth ring, 4, 7—D
  • phenantorporin compound (1) a commercially available one may be used. For example, a known method described in Journal of Heterocyclic Chemistry, 18, 641 (1981), etc. may be used. You may use what was manufactured similarly.
  • the amount of the phenantorin phosphorus compound (1) to be used is generally 0.2 to 2 mol, preferably 0.5 to 1.7 mol, per 1 mol of the divalent nickel compound.
  • a nickel complex in which a phenanthroline compound (1) is coordinated is prepared by previously bringing a phenantorin compound (1) into contact with a divalent nickel compound, and the prepared nickel complex is used as it is or after being isolated. Also good.
  • the nickel complex is usually prepared in a solvent described later, and it can be determined that the nickel complex has been prepared by changing the hue of the reaction mixture.
  • the solvent may be any solvent that can dissolve the aromatic compound to be used and the conjugated aromatic compound to be produced.
  • Specific examples of such solvents include aromatic hydrocarbon solvents such as toluene and xylene; ether solvents such as tetrahydrofuran and 1,4-dioxane; dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N , N-dimethylacetamide, aprotic polar solvents such as hexamethylphosphoric triamide; halogenated hydrocarbon solvents such as dichloromethane and dichloroethane. Such solvents may be used alone or in combination of two or more.
  • ether solvents and aprotic polar solvents are preferable, and tetrahydrofuran, dimethyl sulfoxide, N-methyl-1-pyrrolidone and N, N-dimethylacetamide are more preferable.
  • the amount of the solvent used is usually 1 to 200 parts by weight, preferably 5 to 100 parts by weight, based on 1 part by weight of all the aromatic compounds.
  • the reaction is usually carried out by mixing an aromatic compound, a divalent nickel compound, zinc and a phenanthrolin compound (1) under an atmosphere of an inert gas such as nitrogen gas.
  • the reaction temperature is usually 0 to 2500, preferably 30 to 100 ° C.
  • the reaction time is usually 0.5 to 48 hours.
  • halide salts may be used.
  • sodium halides such as sodium fluoride, sodium chloride, sodium odorant sodium and sodium iodide, potassium fluoride, potassium chloride.
  • Potassium halides such as potassium bromide and potassium iodide, tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium bromide, etc.
  • halogenated ammonium, sodium halide is preferred, and sodium iodide is more preferred.
  • the amount used is usually from 0.001 to 1 mol, preferably from 0.05 to 0.2 mol, based on 1 mol of all aromatic compounds used.
  • This reaction yields a conjugated aromatic compound, which has at least one aromatic ring and has a delocalized ⁇ -electron system in part or all of the molecule. Means a compound.
  • the reaction mixture is mixed with a solvent that does not dissolve or hardly dissolves the produced conjugated aromatic compound.
  • the compound can be precipitated and the precipitated conjugated aromatic compound can be removed by filtration from the reaction mixture.
  • an aqueous solution of an acid such as hydrochloric acid is added, and the precipitated conjugated aromatic compound is separated from the reaction mixture by filtration. Also good.
  • the molecular weight and structure of the obtained conjugated aromatic compound can be analyzed by ordinary analytical means such as gel permeation chromatography and NMR. A solution that does not dissolve the resulting conjugated aromatic compound.
  • the medium or the solvent difficult to dissolve include water, methanol, ethanol, and acetonitrile, and water and methanol are preferable.
  • the produced conjugated aromatic compound is not a polymer
  • the produced conjugated aromatic compound can be taken out by concentrating the reaction mixture.
  • the extracted conjugated aromatic compound may be further purified by ordinary purification means such as column chromatography, distillation, recrystallization and the like.
  • a conjugated aromatic compound having a repeating unit represented by is obtained.
  • Such conjugated aromatic compounds usually contain 2 to 10,000 repeating units represented by the formula (21), and the weight average molecular weight in terms of polystyrene is usually 500 to 3,000,000.
  • Specific examples of the repeating unit represented by the formula (21) include a repeating unit represented by the following formula (21 a) d).
  • a conjugated aromatic compound having a repeating unit represented by is obtained.
  • Such conjugated aromatic compounds usually contain 2 to: L 0,000 repeating units represented by the formula (22), and the weight average molecular weight in terms of polystyrene is usually 500 to 3,000,000. is there.
  • repeating unit represented by the formula (22) include the following formulas (22 a) to (22 e) The repeating unit indicated by
  • a conjugated aromatic compound having a repeating unit represented by is obtained.
  • Such conjugated aromatic compounds usually contain 2 to 10,000 repeating units represented by the formula (23), and the weight average molecular weight in terms of polystyrene is usually 1,000 to 6,000,000. is there.
  • repeating unit represented by the formula (23) include the repeating units represented by the following formulas (23a) to (23d).
  • the conjugated aromatic compound containing the segment shown by this is obtained.
  • the weight average molecular weight in terms of polystyrene of the conjugated aromatic compound is usually 3,000 to 3,000,000.
  • segment represented by the formula (24) include the segments represented by the following formulas (24 a) to (24 x).
  • h represents the same meaning as described above, and is preferably 10 or more.
  • the conjugated aromatic compound containing the repeating unit represented by the formula (21) and the segment represented by the formula (24) is any one of the repeating units represented by the above formulas (21 a) to (21 d).
  • Specific examples thereof include conjugated aromatic compounds represented by the following (I 1 1) to (I 1 16).
  • h represents the same meaning as described above, and p represents an integer of 2 or more.
  • the amount of the repeating unit represented by the formula (22) in the conjugated aromatic compound is preferably 5% by weight or more and 95% by weight or less, more preferably 30% by weight or more and 90% by weight or less, and the formula (24 4 ) Is preferably 5% by weight or more and 95% by weight or less, more preferably 10% by weight or more and 70% by weight or less.
  • the conjugated aromatic compound containing the repeating unit represented by the formula (22) and the segment represented by the formula (24) may be any one of the repeating units represented by the formulas (22 a) to (22 e). Examples thereof include conjugated aromatic compounds comprising one repeating unit and any one of the segments represented by the formulas (24a) to (24x). Specific examples include conjugated aromatic compounds represented by the following (I 1 -1) to (I 1-9).
  • h represents the same meaning as above, and p represents an integer of 2 or more.
  • the aromatic compound (A) is used as B
  • a conjugated aromatic compound containing a repeating unit represented by the formula (23) and a segment represented by the formula (24) is obtained.
  • the polystyrene-reduced weight average molecular weight of the conjugated aromatic compound is usually 3,000 to 3,000,000.
  • the amount of the repeating unit represented by the formula (23) in the conjugated aromatic compound is preferably 5% by weight or more and 95% by weight or less, more preferably 30% by weight or more and 90% by weight or less, and the formula (24 4 ) Is preferably 5% by weight or more and 95% by weight or less, more preferably 10% by weight or more and 70% by weight or less.
  • the conjugated aromatic compound containing the repeating unit represented by the formula (23) and the segment represented by the formula (24) may be any one of the repeating units represented by the above formulas (23 a) to (23 d). Examples thereof include a conjugated aromatic compound containing one repeating unit and any one of the segments represented by the formulas (24a) to (24x). Specific examples include conjugated aromatic compounds represented by the following (III I :!) to (III I 6).
  • h represents the same meaning as above, and p represents an integer of 2 or more.
  • the aromatic compound (A) In the case of reacting an aromatic compound (A) with a structurally different aromatic compound (B), using the aromatic compound (2) as the aromatic compound (A), the aromatic compound ( When the aromatic compound (3) is used as B), a conjugated aromatic compound containing the repeating unit represented by the formula (21) and the repeating unit represented by the formula (22) is obtained.
  • the polystyrene-reduced weight average molecular weight of the conjugated aromatic compound is usually 1,000 to 2,000,000.
  • the amount of the repeating unit represented by the formula (21) in the conjugated aromatic compound is preferably 1% by weight or more and 99% by weight or less, and the amount of the repeating unit represented by the formula (22) is 1% by weight or more, 99 weight% or less is preferable.
  • Examples of the common aromatic compound containing the repeating unit represented by the formula (21) and the repeating unit represented by the formula (22) include any of the repeating units represented by the formulas (21 a) to (21 d). Examples thereof include conjugated aromatic compounds containing one repeating unit and any one of the repeating units represented by the formulas (22a) to (22e). Specific examples include conjugated aromatic compounds represented by the following (IV-1) to (IV-4).
  • the aromatic compound (A) In the case of reacting an aromatic compound (A) with a structurally different aromatic compound (B), using the aromatic compound (2) as the aromatic compound (A), the aromatic compound ( When the aromatic compound (4) is used as B), a conjugated aromatic compound containing the repeating unit represented by the formula (21) and the repeating unit represented by the formula (23) is obtained.
  • the polystyrene-reduced weight average molecular weight of the conjugated aromatic compound is usually 000 to 2,000,000.
  • the amount of the repeating unit represented by the formula (21) in the conjugated aromatic compound is preferably 1% by weight or more and 99% by weight or less, and the amount of the repeating unit represented by the formula (23) is 1% by weight or more, 99 weight% or less is preferable.
  • Examples of the co-aromatic compound containing the repeating unit represented by the formula (21) and the repeating unit represented by the formula (23) include any of the repeating units represented by the formulas (21 a) to (21 d).
  • Examples thereof include conjugated aromatic compounds containing one repeating unit and any one of the repeating units represented by the formulas (23a) to (23d).
  • the content of each repeating unit in the conjugated aromatic compound containing two or more types of repeating units can be adjusted by appropriately adjusting the amount of the aromatic compound used.
  • the conjugated aromatic compound containing the repeating unit represented by the formula (22) or the formula (23) can be used as a raw material for synthesizing a polymer electrolyte for a solid polymer type fuel cell.
  • the weight average molecular weight of is 2,000 to 1,000,000, more preferably 3,000 to 800,000.
  • Example 1 3, 4, 7, 8—tetramethyl mono-1,10-phenanthrin 5
  • the reaction was conducted in the same manner as in Example 1 except that 36 mg of 2,2′-pipyridine was used instead of 4 mg, and a reaction mixture containing a conjugated aromatic compound consisting only of the repeating unit represented by the formula (i) I got a thing.
  • the Mw of the conjugated aromatic compound was 25,000 and Mn was 13,000. ⁇ Reference Example 2>
  • 2,2-Dimethylpropanol 25.2 g was dissolved in tetrahydrofuran 20 OmL. To this, 151.6 mL of n-butyl lithium in hexane (1.57M) was added dropwise at 0 ° C. Thereafter, the mixture was stirred at room temperature for 1 hour to prepare a solution containing lithium 2,2-dimethylpropoxide. Lithium 2,2-dimethylpropoxide prepared at 0 ° C in a solution obtained by dissolving 40 g of 4,4'-dichloropiphenyl-2,2 'monodisulfonic acid dichloride in 30 OmL of tetrahydrofuran A solution containing was added dropwise.
  • Example 2 the reaction was carried out in the same manner as in Example 2 except that 7 mg of 2,2′-pipyridine was used instead of 14 mg of 4,7-diphenyl-1,10-phenantorin, and the above formula (ii) A reaction mixture containing a conjugated aromatic compound consisting only of repeating units represented by the formula (1) was obtained.
  • the Mw of the synergistic aromatic compound was 70,000, and Mn was 28,000.
  • a reaction mixture containing a conjugated aromatic compound consisting of the segment represented by The Mw of the conjugated aromatic compound was 276,000 and Mn was 91,000.
  • a reaction mixture containing a conjugated aromatic compound consisting of the segment represented by The Mw of the conjugated aromatic compound was 567,000, and Mn was 140,000.
  • the reaction mixture containing the conjugated aromatic compound which consists only of repeating units shown by was obtained.
  • the Mw of the conjugated aromatic compound was 154,000, and the Mn was 36,000.
  • Example 6 2,5-dichloro-1,4-decyloxybenzene (212 mg) was replaced with 5 mL of N, N-dimethylacetamide instead of 24 Omg The reaction was carried out in the same manner as in Example 6 except that 3 mL of N-methyl-2-pyrrolidone was used.
  • a reaction mixture containing a conjugated aromatic compound consisting only of repeating units represented by the formula (1) was obtained.
  • the Mw of the conjugated aromatic compound was 32,000, and the Mn was 15,000.
  • Example 6 3,4,7,8-tetramethyl mono-1,10-phenanthrine 6 Omg was replaced with 2,5-dichloromono-1,10-phenanthrine 84 mg instead of 84 mg 4,7-diphenyl mono 4, Monophenoxybenzophenone 24, 7-dichloro-9,9-didodecyl 9 H-fluorene 462 mg instead of 5 mg N, N-dimethylacetamide 5 mL N, N-dimethylacetate Use a mixed solvent of amide 3.5 mL and toluene 1.5 mL The reaction was carried out in the same manner as in Example 6 except that
  • the reaction mixture containing the conjugated aromatic compound which consists only of repeating units shown by was obtained.
  • the Mw of the conjugated aromatic compound was 343,000, and the Mn was 75,000.
  • Example 9 the same reaction was carried out except that 17 mg of 5,6-dimethyl-1,10-phenanthrine was used instead of 2,4,7,8-tetramethyl-1,10-phenanthrine 2 Omg. And a reaction mixture containing 4,4′-dimethylpiphenyl was obtained. The yield of 4,4'-dimethylbifuel was 57 mg. ⁇ Example 1 2>
  • Example 9 the same procedure except that 6 mg of 5,4-methyl-1,10-phenanthorin was used instead of 3,4,7,8-tetramethyl-1,10-phenantorin 2 Omg. The reaction was conducted to obtain a reaction mixture containing 4,4′-dimethylbiphenyl. The yield of 4,4'-dimethylbiphenyl was 49 mg.
  • Example 9 ′ the reaction was carried out in the same manner except that 3,4,7,8-tetramethyl-1,10-phenanthorin 2 Omg was replaced by 2,2′-biviridine 13 mg, and 4,4 ′ A reaction mixture containing dimethylbiphenyl was obtained. The yield of 4,4′-dimethylbiphenyl was 36 mg.
  • Example 9 instead of 89 mg of 4-chloro toluene 4 1 chloroadisol 1 0
  • a reaction was carried out in the same manner except that Omg was used to obtain a reaction mixture containing 4,4′-dimethoxypiphenyl.
  • the yield of 4,4'-dimethoxybiphenyl was 58 mg.
  • Example 1 5> The reaction was carried out in the same manner as in Example 9 except that 3-chloroanisole 10 Omg was used in place of 89 mg of 4-monochlorotoluene to obtain a reaction mixture containing 3,3′-dimethoxybiphenyl. The yield of 3,3′-dimethoxybiphenyl was 69 mg.
  • Example 16> 3-chloroanisole 10 Omg was used in place of 89 mg of 4-monochlorotoluene to obtain a reaction mixture containing 3,3′-dimethoxybiphenyl. The yield of 3,3′-dimethoxybiphenyl was 69 mg.
  • Example 9 instead of 3, 4, 7, 8-tetramethyl-1,10-phenantorin 2 Omg, 28 mg of 4,7-diphenyl-1,10-phenantorin was substituted with 28 mg of 4-cloantorin 89 mg The reaction was carried out in the same manner except that 10 mg of 3-chloroanisole was used in place of 1, to obtain a reaction mixture containing 3,3, -dimethoxypiphenyl. The yield of 3,3, -dimethyloxybiphenyl was 64 mg.
  • Example 9 instead of 3, 4, 7, 8-tetramethyl-1,10-phenantine phosphorus 2 Omg, 17 mg of 5,6-dimethyl-1,10-phenantorin, 4 mg of monochlorotoluene 89 mg A reaction mixture containing 3,3′-dimethoxybiphenyl was obtained in the same manner except that 100 mg of 3-chloroanisole was used instead. The yield of 3,3'-dimethyoxyphenyl was 66 mg.
  • the reaction was carried out in the same manner, except that 16 mg of 5-methyl-1,10-phenanthral was substituted for Omg, and 3-chloroazol 10 Omg was substituted for 89 mg of 4-chlorotoluene. A reaction mixture containing dimethoxybiphenyl was obtained. The yield of 3,3'-dimethylbiphenyl was 66 mg.
  • Example 19 In Example 9, the reaction was carried out in the same manner except that 108 mg of 4′-chloroacetophenone was used in place of 89 mg of 4-chlorotoluene, and a reaction mixture containing 4,4′-diacetylbiphenyl was obtained. Obtained. The yield of 4, 4'-diacetyl bifuel was 79 mg. ⁇ Example 20>
  • Example 9 instead of 3,4,7,8-tetramethyl-1,10-phenantorin 2 O.mg, 28 mg of 4,7-diphenyl-1,10-phenantorin, and 89 mg of 4-clotoltoluene The reaction was carried out in the same manner except that 108 mg of 4′-chloroacetophenone was used instead of 4 to obtain a reaction mixture containing 4,4′-diacetylbiphenyl. The yield of 4,4′-diacetylbiphenyl was 76 mg.
  • Example 9 3,4,7,8-tetramethyl_1,10-phenantorin 2 Omg instead of 5,6 1-dimethyl-1,10-phenantorin 17 mg was replaced with 4-clotoluene 89 mg The reaction was carried out in the same manner except that 108 mg of 4′-chloroacetophenone was used to obtain a reaction mixture containing 4,4,1-diacetylpiphenyl. The yield of 4,4'-diacetylbiphenyl was 74 mg.
  • the reaction was carried out in the same manner except that 4-methyl-1,10-phenanthrine 16 mg was used instead of Omg, and 4'-chloroacetophenone 108 mg was used instead of 4-chlorotoluene 89 mg.
  • a reaction mixture containing 1-diacetylpiphenyl was obtained.
  • the yield of 4,4'-diacetyl pphenyl was 76 m.
  • Example 23 In Example 9, the reaction was carried out in the same manner except that 9 lmg of 4-chloro-fluobenzene was used instead of 89 mg of 4-chloro-toluene, and a reaction containing 4,4′-difluorobiphenyl was performed. A reaction mixture was obtained. The yield of 4,4′-difluorobiphenyl was 6 lmg. ⁇ Example 24>
  • Example 9 instead of 3, 4, 7, 8-tetramethyl-1,10-phenanthrine 2 Omg, 28 mg of 4,7-diphenyl-1,10-phenanthrine was replaced with 89 mg of 4-chlorotoluene. Instead, the reaction was conducted in the same manner except that 9 lmg of 4-chlorofluorobenzene was used to obtain a reaction mixture containing 4,4′-difluoropiphenyl. The yield of 4,4'-difluorobiphenyl was 55 mg.
  • Example 9 3,4,7,8-tetramethyl-1,10-phenantorin 2 Omg instead of 5,6 monodimethyl-1,10-phenantorin 17 mg was replaced with 4-monochlorotoluene 89 mg The reaction was carried out in the same manner except that 91 mg of 4-chlorofluorobenzene was used, and a reaction mixture containing 4,4, -difluorobiphenyl was obtained. The yield of 4,4'-difluoropiphenyl was 57 mg.
  • Example 27 In Example 9, the reaction was carried out in the same manner except that 96 mg of 4-chlorobenzoic benzonitrile was used instead of 89 mg of 4-chlorotoluene, to obtain a reaction mixture containing 4,4′-dicyanobiphenyl. It was. The yield of 4,4′-dicyanobiphenyl was 57 mg.
  • Example 9 the reaction was carried out in the same manner except that 4-chloro-11- (methoxymethyl) benzene 11 Omg was used instead of 89 mg of 4-chlorotoluene, and 4,4′-bis (methoxymethyl) piphenyl was used. A reaction mixture containing was obtained. The yield of 4,4, -bis (methoxymethyl) biphenyl was 68 mg.
  • Example 9 in place of 3, 4, 7, 7, 8-tetramethyl-1,10-phenantorin 2 Omg, 17 mg of 5,6-dimethyl-1,10-phenantorin was replaced with 89 mg of 4-clotoluene toluene.
  • the reaction was carried out in the same manner except that 11 Omg of 4-chloro (methoxymethyl) benzene was used, and a reaction mixture containing 4,4′-monobis (methoxymethyl) biphenyl was obtained.
  • the yield of 4,4'-bis (methoxymethyl) biphenyl was 68 mg.
  • Example 9 3,4,7,8-tetramethyl-1,10-phenantorin 2 Omg instead of 5-methyl-1,10-phenantorin 16 mg, 4-chlorotoluene 89 mg instead of 4-chloro Mouth (methoxymethyl) benzene 11 Omg was used in the same manner to obtain a reaction mixture containing 4,4′-bis (methoxymethyl) piphenyl.
  • the yield of 4,4′-bis (methoxymethyl) bifuel was 65 mg.
  • Example 9 2-bromothiophene 1 1 instead of 89 mg of toluene 4 ⁇ The reaction was carried out in the same manner except that 4 mg was used, and a reaction mixture containing 2,2′-one-pithiophene was obtained. The yield of 2,2'-one-pichiophene was 45 mg.
  • Example 9 instead of 3, 4, 7, 8-tetramethyl-1,10-phenantine phosphorus 2 Omg, 5-methyl-1,10-phenantine phosphorus 16 mg was replaced with 4-chlorotoluene 8 9 mg.
  • the reaction was carried out in the same manner except that 2-bromothiophene 1 1 4 mg was used, and a reaction mixture containing 2,2′-one-pithiophene was obtained.
  • the yield of 2,2'-one-pichiophene was 42 mg.
  • Example 9 4, 7, 8—tetramethyl-1,10—phenantoracin 2 Omg instead of 2,2′-bibilysin 1 3 mg, The reaction was carried out in the same manner except that 4 mg of promothiophene 1 1 was used, and a reaction mixture containing 2,2′-pichiofen was obtained. The yield of 2, 2 '-pitiophene was 25 mg.
  • a conjugated aromatic compound can be produced more advantageously.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Pyridine Compounds (AREA)

Abstract

L'invention porte sur un procédé de fabrication d'un composé aromatique conjugué qui est caractérisé par le fait qu'un composé aromatique (A) dans lequel un ou deux groupes partants sont liés à un noyau aromatique est mis à réagir avec un composé aromatique (A) ayant la même structure ou avec un composé aromatique (B) ayant une structure différente de celle du composé aromatique (A) dans lequel un ou deux groupes partants sont liés à un noyau aromatique, en présence d'une quantité catalytique d'un composé divalent du nickel, de zinc et d'un composé de phénanthroline représenté par la formule suivante (1). (1) (Dans la formule, R1, R2, R3, R4, R5 et R6 peuvent être identiques ou différents et représentent un groupe aryle ayant 6-20 atomes de carbone ou similaires, et R1, R2, R3, R4, R5 et R6 ne représentent pas des atomes d'hydrogène en même temps).
PCT/JP2008/051897 2007-02-01 2008-01-30 Procédé de fabrication d'un composé aromatique conjugué WO2008093879A1 (fr)

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EP2390241B1 (fr) * 2009-01-23 2014-10-01 Sumitomo Chemical Company, Limited Procédé de fabrication d'un composé aromatique conjugué
JP6508700B2 (ja) * 2014-10-29 2019-05-08 国立大学法人茨城大学 縮合多環芳香族骨格を有するポリマー及びそれを用いた発光素子及び電極
JP7113480B2 (ja) * 2017-07-18 2022-08-05 小西化学工業株式会社 共重合体の製造方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08231454A (ja) * 1994-12-26 1996-09-10 Tosoh Akzo Corp ビフェニル化合物の製造方法
JPH09194525A (ja) * 1996-01-19 1997-07-29 Ube Ind Ltd オレフィン重合用触媒
JP2000344815A (ja) * 1999-06-01 2000-12-12 Toyota Central Res & Dev Lab Inc オレフィン重合触媒
JP2003238665A (ja) * 2002-02-21 2003-08-27 Sumitomo Chem Co Ltd ポリフェニレンスルホン酸類の製造方法
JP2005248143A (ja) * 2004-02-05 2005-09-15 Sumitomo Chemical Co Ltd 高分子化合物およびその製造方法
JP2007177197A (ja) * 2005-03-10 2007-07-12 Sumitomo Chemical Co Ltd ポリアリーレン系ブロック共重合体及びその用途
JP2007284653A (ja) * 2005-10-13 2007-11-01 Sumitomo Chemical Co Ltd ポリアリーレン及びその製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08231454A (ja) * 1994-12-26 1996-09-10 Tosoh Akzo Corp ビフェニル化合物の製造方法
JPH09194525A (ja) * 1996-01-19 1997-07-29 Ube Ind Ltd オレフィン重合用触媒
JP2000344815A (ja) * 1999-06-01 2000-12-12 Toyota Central Res & Dev Lab Inc オレフィン重合触媒
JP2003238665A (ja) * 2002-02-21 2003-08-27 Sumitomo Chem Co Ltd ポリフェニレンスルホン酸類の製造方法
JP2005248143A (ja) * 2004-02-05 2005-09-15 Sumitomo Chemical Co Ltd 高分子化合物およびその製造方法
JP2007177197A (ja) * 2005-03-10 2007-07-12 Sumitomo Chemical Co Ltd ポリアリーレン系ブロック共重合体及びその用途
JP2007284653A (ja) * 2005-10-13 2007-11-01 Sumitomo Chemical Co Ltd ポリアリーレン及びその製造方法

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