WO2012176820A1 - Composé hétérocyclique condensé et polymère de celui-ci - Google Patents

Composé hétérocyclique condensé et polymère de celui-ci Download PDF

Info

Publication number
WO2012176820A1
WO2012176820A1 PCT/JP2012/065780 JP2012065780W WO2012176820A1 WO 2012176820 A1 WO2012176820 A1 WO 2012176820A1 JP 2012065780 W JP2012065780 W JP 2012065780W WO 2012176820 A1 WO2012176820 A1 WO 2012176820A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
substituent
compound
ring
independently
Prior art date
Application number
PCT/JP2012/065780
Other languages
English (en)
Japanese (ja)
Inventor
菅　誠治
耕一 光藤
泰輔 鎌田
美樹 ▲つる▼田
純一 吉本
杉岡　尚
Original Assignee
国立大学法人 岡山大学
株式会社クラレ
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 国立大学法人 岡山大学, 株式会社クラレ filed Critical 国立大学法人 岡山大学
Publication of WO2012176820A1 publication Critical patent/WO2012176820A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
    • 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
    • C08G61/123—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 derived from five-membered heterocyclic compounds
    • C08G61/124—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 derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
    • 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
    • C08G61/123—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 derived from five-membered heterocyclic compounds
    • C08G61/126—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 derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0672—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/22—Molecular weight
    • C08G2261/226—Oligomers, i.e. up to 10 repeat units
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/51—Charge transport
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/74—Further polymerisation of the obtained polymers, e.g. living polymerisation to obtain block-copolymers
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/91—Photovoltaic applications
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/92—TFT applications
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/94—Applications in sensors, e.g. biosensors
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/95—Use in organic luminescent diodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes
    • H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a condensed heterocyclic compound and a polymer thereof.
  • semiconductor materials semiconductor materials
  • organic electronic members such as solid electrolytic transistors, organic thin film transistors, and individual identification (RFID) devices using radio waves
  • RFID individual identification
  • these doped polymers have electrical conductivity, and the electrical characteristics and optical characteristics can be appropriately controlled by adjusting the amount of dopant to coexist. Therefore, these doped polymers have been studied for use in various applications such as various electrodes, electrochromic materials, various sensors, primary batteries, secondary batteries, solid electrolytic capacitors, antistatic agents and the like.
  • the fused heterocyclic compound of Patent Document 1 has been studied as a semiconducting material that can be applied and printed because it has excellent semiconductor properties and high solubility in organic solvents. Further, in Patent Document 2 and Non-Patent Document 1, polymers having a structural unit derived from dithienopyrrole have been reported, and their use as a conductive material or a semiconductive material has been studied. Non-Patent Document 2 reports a fused heterocyclic compound containing a pyrrole ring. However, no compound has been reported in which both ends are composed of an aromatic heterocyclic ring and five or more rings are condensed.
  • An object of the present invention is to provide a condensed heterocyclic compound and a polymer thereof that can be suitably used as a conductive material or a semiconductive material.
  • R 1 and each R 2 independently represent a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a hetero that may have a substituent.
  • An aryl group or —CO—R (wherein R represents an alkyl group which may have a substituent, an aryl group which may have a substituent or a heteroaryl group which may have a substituent); .)
  • Ring A, Ring B and Ring C are each independently a 5-membered or 6-membered aromatic heterocyclic ring which may have a substituent, n is an integer of 1 to 4. ]
  • W 1 to W 4 each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, An aryl group that may have a substituent, a heteroaryl group that may have a substituent, an alkoxy group that may have a substituent, an alkylthio group that may have a substituent, and a substituent It may have an alkylamino group, a cyano group, a nitro group, an azido group, a hydroxy group, a sulfanyl group, an amino group, a carboxyl group or a salt thereof, a phosphono group or a salt thereof, a sulfo group or a salt thereof, or a substituent.
  • R 1 , R 2 and W 1 to W 4 are as defined in the above [2].
  • R 1 and each R 2 are each independently an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heteroaryl group that may have a substituent.
  • R 1 and each R 2 are each independently an alkyl group having 1 to 10 carbon atoms, a benzyl group, or a phenyl group which may have a substituent.
  • a composition comprising the compound according to any one of [1] to [6] and a dopant.
  • a polymer comprising a structural unit derived from the compound according to [4].
  • R 1 and each R 2 are each independently an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heteroaryl group that may have a substituent.
  • R 1 and each R 2 are each independently an alkyl group having 1 to 10 carbon atoms, a benzyl group, or an optionally substituted phenyl group.
  • a composition comprising the polymer according to any one of [9] to [11] and a dopant.
  • the composition described in [12], wherein the polymer described in any one of [9] to [11] is a cation and the dopant is an anion.
  • [14] An organic electronic member comprising the compound according to any one of [1] to [6] or the composition according to [7] or [8].
  • An organic electronic member comprising the polymer according to any one of [9] to [11] or the composition according to [12] or [13].
  • X 1 to X 4 are each independently a chlorine atom, a bromine atom or an iodine atom
  • W 1 to W 4 each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, An aryl group that may have a substituent, a heteroaryl group that may have a substituent, an alkoxy group that may have a substituent, an alkylthio group that may have a substituent, and a substituent It may have an alkylamino group, a cyano group, a nitro group, an azido group, a hydroxy group, a sulfanyl group, an amino group, a carboxyl group or a salt thereof, a phosphono group or a salt thereof, a sulfo group or a salt thereof, or a substituent.
  • Ak represents an alkyl group.
  • R 1 represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, or —CO—R ( In the above formula, R represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.
  • a compound of formula (6) R 2 —NH 2 (6)
  • R 2 represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, or —CO—R ( In the above formula, R represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.
  • R 1 , R 2 and W 1 to W 4 are as defined above.
  • R 1 and R 2 are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.
  • R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms, a benzyl group, or an optionally substituted phenyl group.
  • the fused heterocyclic compound and polymer thereof of the present invention are suitably used as a conductive material or a semiconductive material.
  • R 1 and each R 2 in Formula (1) may each independently have a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent.
  • a good heteroaryl group or —CO—R (wherein R represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent) Represents.).
  • the alkyl group may be linear or branched, and the carbon number thereof is preferably 1-20, more preferably 1-15, still more preferably 1-10. It is.
  • the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, and hexyl.
  • the alkyl group may have a substituent.
  • substituent of the alkyl group examples include a halogen atom, an alkoxy group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 5), an aryl group which may have a substituent, and the like. .
  • the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 10 carbon atoms.
  • Examples of the aryl group include aryl groups derived from a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, pyrene ring, perylene ring, tetracene ring, pentaphen ring, pentacene ring, rubicene ring and the like.
  • the aryl group may have a substituent.
  • substituent of the aryl group examples include a halogen atom, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 5), and 1 to 20 carbon atoms (preferably 1 to 10, more preferably Are alkoxy groups of 1 to 5).
  • a heteroaryl group is a group derived from an aromatic heterocycle containing 1 to 5 heteroatoms such as nitrogen, oxygen, sulfur, selenium, silicon, germanium in addition to carbon atoms.
  • the aromatic heterocyclic ring may be monocyclic or polycyclic (eg, bicyclic, tricyclic).
  • the number of atoms of the heteroaryl group is preferably 5 to 30, more preferably 5 to 10.
  • heteroaryl groups include thiophene ring, pyrrole ring, furan ring, selenophene ring, silole ring, gelmol ring, imidazole ring, pyrazole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, triazole ring, tetrazole ring , Pyridine ring, pyrazine ring, pyrimidine ring, indole ring, isoindole ring, indazole ring, phthalazine ring, quinoline ring, isoquinoline ring, quinoxaline ring, quinazoline ring, cinnoline ring, ⁇ -carboline ring, etc.
  • the heteroaryl group may have a substituent.
  • substituent of the heteroaryl group include a halogen atom, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 5), and 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms). Preferred examples include alkoxy groups 1 to 5).
  • R 1 and each R 2 are each independently preferably an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heteroaryl group that may have a substituent, More preferably an alkyl group which may have a substituent or an aryl group which may have a substituent, and even more preferably an alkyl group which may have a substituent or a substituent
  • a phenyl group more preferably an alkyl group having 1 to 10 carbon atoms, a benzyl group or an optionally substituted phenyl group, still more preferably an alkyl group having 1 to 10 carbon atoms, a benzyl group, or A phenyl group which may have at least one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms, particularly preferably an alkyl group having 1 to 10 carbon atoms; Group, a benzyl group or an alkyl group and
  • the number of the substituent is preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.
  • n is 2 or more, the plurality of R 2 may be the same as or different from each other, and are preferably the same. Further, it is preferable that all of R 1 and each R 2 is the same.
  • Ring A, ring B and ring C in the formula (1) are each independently a 5-membered or 6-membered aromatic heterocyclic ring which may have a substituent. Ring A, ring B and ring C are preferably the same.
  • the 5-membered or 6-membered aromatic heterocycle contains a heteroatom such as nitrogen, oxygen, sulfur, selenium, silicon, germanium in addition to the carbon atom.
  • the number of heteroatoms in the 5-membered or 6-membered aromatic heterocycle is preferably 1 to 3, more preferably 1.
  • Examples of the 5- or 6-membered aromatic heterocycle include, for example, a thiophene ring, a pyrrole ring, a furan ring, a selenophene ring, a silole ring, a gelmol ring, an imidazole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, and an isothiazole. And a ring, a pyridine ring, a pyrazine ring, and a pyrimidine ring.
  • the 5-membered or 6-membered aromatic heterocyclic ring may have a substituent.
  • Examples of the substituent of the 5-membered or 6-membered aromatic heterocyclic ring include a halogen atom, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 5), and 1 to 20 carbon atoms ( Preferred examples include alkoxy groups of 1 to 10, more preferably 1 to 5).
  • Ring A, Ring B and Ring C are each independently preferably a 5-membered aromatic heterocyclic ring which may have a substituent, more preferably a thiophene ring which may have a substituent, More preferably, it is a thiophene ring which may have a halogen atom, more preferably a thiophene ring which may have at least one selected from the group consisting of a chlorine atom, a bromine atom and an iodine atom. An unsubstituted thiophene ring is preferred.
  • N in the formula (1) is an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.
  • R 1 and each R 2 are each independently an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heteroaryl group that may have a substituent, Examples include compounds in which Ring A, Ring B and Ring C are each independently a 5-membered or 6-membered aromatic heterocyclic ring which may have a substituent.
  • R 1 and each R 2 are each independently an alkyl group which may have a substituent or an aryl group which may have a substituent, Examples thereof include compounds in which Ring A, Ring B and Ring C are each independently a 5-membered aromatic heterocyclic ring which may have a substituent.
  • R 1 and each R 2 are each independently an alkyl group which may have a substituent or a phenyl group which may have a substituent
  • examples include a compound in which Ring A, Ring B and Ring C are each independently a thiophene ring which may have a substituent.
  • R 1 and each R 2 are each independently an alkyl group having 1 to 10 carbon atoms, a benzyl group or an optionally substituted phenyl group, Examples thereof include compounds in which Ring A, Ring B and Ring C are each independently a thiophene ring which may have a halogen atom.
  • R 1 and each R 2 are each independently at least one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a benzyl group, or an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms.
  • R 1 and each R 2 are each independently at least one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a benzyl group, or an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms.
  • R 1 and each R 2 are the same.
  • W 1 to W 4 in formula (2) each independently have a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent.
  • alkynyl group which may have a substituent an aryl group which may have a substituent, a heteroaryl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent
  • the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom, a bromine atom or an iodine atom, more preferably a bromine atom.
  • the alkenyl group may be linear or branched, and the carbon number thereof is preferably 2 to 20, more preferably 2 to 10.
  • the alkenyl group include a vinyl group, 1-propenyl group, 1-butenyl group, 1-pentenyl group, 1-hexenyl group, 1-heptenyl group, 1-octenyl group and the like.
  • the alkenyl group may have a substituent.
  • the substituent of the alkenyl group include a halogen atom, an alkoxy group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 5), and the like.
  • the alkynyl group may be linear or branched, and the alkynyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms. Examples include ethynyl group, 1-propynyl group, 1-butynyl group, 1-pentynyl group, 1-hexynyl group, 1-heptynyl group, 1-octynyl group and the like.
  • the alkynyl group may have a substituent. Examples of the substituent of the alkynyl group include a halogen atom, an alkoxy group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 5), and the like.
  • the alkoxy group may be linear or branched, and the carbon number thereof is preferably 1-20, more preferably 1-10.
  • the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, an isopentyloxy group, a neopentyloxy group, tert-pentyloxy group, hexyloxy group, isohexyloxy group, 2-ethylhexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, tetradecyloxy group, pentadecyloxy group, Hexadecyloxy group, heptadecyloxy group, octade
  • the alkylthio group may be linear or branched, and the carbon number thereof is preferably 1-20, more preferably 1-10.
  • the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isobutylthio group, a sec-butylthio group, a tert-butylthio group, a pentylthio group, an isopentylthio group, a neopentylthio group, tert-pentylthio group, hexylthio group, isohexylthio group, 2-ethylhexylthio group, heptylthio group, octylthio group, nonylthio group, decylthio group, undecylthio group, tetradecylthio
  • the alkylthio group may have a substituent.
  • substituent for the alkylthio group include a halogen atom, an alkoxy group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 5), and the like.
  • the alkylamino group may be linear or branched, and the carbon number thereof is preferably 1 to 10, more preferably 1 to 5, and the alkyl group. Is 1 or 2, preferably 1.
  • the alkylamino group include a methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, A dimethylamino group, a diethylamino group, etc. are mentioned.
  • the alkylamino group may have a substituent. Examples of the substituent of the alkylamino group include a halogen atom, an alkoxy group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 5), and the like.
  • any of the carboxyl group, phosphono group and sulfo group may be in a salt form.
  • these salt forms include alkali metal salts, alkaline earth metal salts, quaternary ammonium salts, quaternary phosphonium salts, imidazolium salts, guanidinium salts, and the like.
  • the carbamoyl group which may have a substituent is represented by —CO—N (R ′) (R ′′) (wherein R ′ and R ′′ each independently represents a hydrogen atom) Or a substituent.)
  • the substituent of the carbamoyl group is, for example, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heteroaryl group that may have a substituent.
  • the phosphinoyl group which may have a substituent is represented by —PO (R ′) (R ′′) (wherein R ′ and R ′′ each independently represents a hydrogen atom or a substituent).
  • the substituent of the phosphinoyl group is, for example, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heteroaryl group that may have a substituent.
  • the phosphanyl group which may have a substituent is represented by —P (R ′) (R ′′) (wherein R ′ and R ′′ each independently represents a hydrogen atom or a substituent).
  • the substituent of the phosphanyl group is, for example, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heteroaryl group that may have a substituent.
  • Ak represents an alkyl group.
  • Ak may be linear or branched, and the carbon number thereof is preferably 1 to 10, more preferably 1 to 5.
  • Examples of Ak include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, and hexyl groups. , Isohexyl group, 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group and the like.
  • W 1 to W 4 are preferably each independently a hydrogen atom, a halogen atom or an alkyl group which may have a substituent.
  • W 1 to W 4 are each independently more preferably a hydrogen atom or a halogen atom, still more preferably a hydrogen atom or a bromine atom, and still more preferably a hydrogen atom. It is preferable that W 1 to W 4 are all the same.
  • At least two of W 1 to W 4 are each independently required to be a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom. At least two of W 1 to W 4 are each independently preferably a hydrogen atom or a bromine atom, more preferably a hydrogen atom.
  • the “at least two of W 1 to W 4 ” is preferably W 1 and W 2 .
  • N in the formula (2) is an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 1 or 2.
  • the compound (2) in which n is 1 is the compound (3).
  • the explanation of R 1 , R 2 and W 1 to W 4 in the formula (3) is the same as described above.
  • R 1 and each R 2 are each independently an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heteroaryl group that may have a substituent
  • W 1 to W 4 are each independently a hydrogen atom, a halogen atom or an alkyl group which may have a substituent
  • Examples thereof include compounds in which at least two of W 1 to W 4 are each independently a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom.
  • R 1 and each R 2 are each independently an alkyl group which may have a substituent or an aryl group which may have a substituent
  • W 1 to W 4 are each independently a hydrogen atom or a halogen atom
  • Examples include compounds in which at least two of W 1 to W 4 are each independently a hydrogen atom or a bromine atom.
  • R 1 and each R 2 are each independently an alkyl group which may have a substituent or a phenyl group which may have a substituent, Examples thereof include compounds in which W 1 to W 4 are hydrogen atoms.
  • R 1 and each R 2 are each independently an alkyl group having 1 to 10 carbon atoms, a benzyl group or an optionally substituted phenyl group, Examples thereof include compounds in which W 1 to W 4 are hydrogen atoms.
  • R 1 and each R 2 are each independently at least one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a benzyl group, or an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms.
  • R 1 and each R 2 are the same.
  • a dopant may be added to the compound of the present invention.
  • the compound of the present invention is preferably a cation and the dopant is preferably an anion.
  • the addition amount of the dopant can be arbitrarily adjusted depending on the dopant to be used, but is preferably 1 to 1000 parts by weight, more preferably 1 to 200 parts by weight with respect to 100 parts by weight of the compound.
  • the method of doping the compound and the description of the dopant used therefor are the same as those of the polymer described later.
  • reaction A a method for producing the fused heterocyclic compound of the present invention (that is, compound (1) to compound (3))
  • a manufacturing method is first demonstrated from the manufacturing method of a compound (3).
  • Compound (3) can be produced by reacting compound (4), compound (5) and compound (6) as shown in the following formula (hereinafter abbreviated as “reaction A”). It is preferable that a compound (5) and a compound (6) are the same compounds.
  • W 1 to W 4 in the formula (4) and R 1 and R 2 in the formulas (5) and (6) are as defined above.
  • X 1 to X 4 are each independently a chlorine atom, bromine atom or iodine atom, preferably a bromine atom.
  • saturated aliphatic hydrocarbons or alicyclic hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, and cyclohexane; benzene, toluene, ethylbenzene, propyl Aromatic hydrocarbons such as benzene, xylene, ethyl toluene, chlorobenzene, o-dichlorobenzene; dimethyl ether, ethyl methyl ether, diethyl ether, dipropyl ether, butyl methyl ether, tert-butyl methyl ether, dibutyl ether, tetrahydrofuran, 1, And ethers such as 4-dioxane; aprotic polar solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrol
  • Reaction A is performed in the presence of a catalyst and a base.
  • the catalyst used in the reaction A include metal catalysts such as a palladium catalyst and a nickel catalyst.
  • the amount of the catalyst is preferably 0.001 to 1 mol with respect to 1 mol of the compound (4).
  • the base used in the reaction A include n-butyllithium, tert-butyllithium, methyllithium and the like.
  • the amount of the base is preferably 0.8 to 1.2 mol with respect to 1 mol of the compound (4).
  • the crude product is preferably purified by a known method (for example, extraction, chromatography).
  • reaction B The compound (4) used in the reaction A is produced by reacting the compound (7), the compound (8) and the compound (9) as shown in the following formula (hereinafter abbreviated as “reaction B”). be able to.
  • X 1 to X 4 and W 1 to W 4 are as defined above.
  • X 5 to X 8 in the formulas (7) to (9) are each independently a chlorine atom, a bromine atom or an iodine atom, preferably a bromine atom.
  • the methods and conditions of Kumada-Tamao coupling and Negishi coupling are preferred, and the methods and conditions of Negishi coupling are more preferred.
  • Both Kumada-Tamao coupling and Negishi coupling are well known in the field of synthetic organic chemistry. For example, the Kumada-Tamao coupling is described in Pure and Applied Chemistry, 1980, Vol. 52, p. 669, Negishi Coupling is described in Accounts of Chemical Research, 1982, Vol. 15, p. 340.
  • saturated aliphatic hydrocarbons or alicyclic hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, and cyclohexane; benzene, toluene, ethylbenzene, propyl Aromatic hydrocarbons such as benzene, xylene, ethyl toluene, chlorobenzene, o-dichlorobenzene; dimethyl ether, ethyl methyl ether, diethyl ether, dipropyl ether, butyl methyl ether, tert-butyl methyl ether, dibutyl ether, tetrahydrofuran, 1, And ethers such as 4-dioxane; aprotic polar solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrroli
  • Examples of the catalyst used in the reaction B include metal catalysts such as a palladium catalyst and a nickel catalyst.
  • the temperature of reaction B is not particularly limited, but is preferably ⁇ 50 ° C. to 200 ° C.
  • the time for reaction B is not particularly limited, but is preferably 1 minute to 48 hours.
  • the crude product is preferably purified by a known method (for example, extraction, chromatography).
  • a compound in which n is 1, and a part or all of ring A, ring B and ring C is a 5-membered or 6-membered aromatic heterocycle other than the thiophene ring (hereinafter abbreviated as “other ring”) ( 1) can be produced by using, as a starting material, a compound in which part or all of the thiophene ring is replaced with another ring in the above reaction A instead of the compound (4).
  • Examples of other rings include pyrrole ring, furan ring, selenophene ring, silole ring, gelmol ring, imidazole ring, pyrazole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, pyridine ring, pyrazine ring, pyrimidine ring. Etc.
  • compound (1) wherein n is 2 to 4 can be produced in the same manner as in the production method of compound (2).
  • the starting material used in the method for producing compound (1) can be produced by a method well known in the field of synthetic organic chemistry.
  • the polymer of the present invention has a constitution derived from the compound (2) (preferably the compound (3)) in which at least two of W 1 to W 4 are each independently a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom. The unit is included.
  • the average molecular weight of the polymer is not particularly limited.
  • the polymer of the present invention has a rigid structural unit in which five or more aromatic heterocycles derived from the compound (2) (preferably the compound (3)) are condensed, many of the polymers of the present invention Does not dissolve in the solvent, and the average molecular weight cannot be measured by GPC or the like.
  • the weight average molecular weight of a general polymer is in the range of 1000 to 1,000,000.
  • a dopant may be added to the polymer of the present invention.
  • the polymer of the present invention is preferably a cation and the dopant is preferably an anion.
  • the dopant which is an anion functions as a counter anion with respect to the polymer of the present invention which is a cation.
  • the dopant include a halogenated anion of a Group 5B element such as PF 6 ⁇ , SbF 6 ⁇ , AsF 6 ⁇ ; a halogenated anion of a Group 3B element such as BF 4 ⁇ ; I ⁇ (I 3 ⁇ ), Br ⁇ .
  • Halogen anions such as Cl 2 ⁇ ; Halogen anions such as ClO 4 ⁇ ; Metal halide anions such as AlCl 4 ⁇ , FeCl 4 ⁇ , SnCl 5 ⁇ ; Nitrate anions (NO 3 ⁇ ); Sulfate anions (SO 4 2 ⁇ ); Organic sulfonate anions such as p-toluenesulfonate anion, naphthalenesulfonate anion, CH 3 SO 3 ⁇ , CF 3 SO 3 — ; carboxylate anions such as CF 3 COO ⁇ , C 6 H 5 COO ⁇ ; and And modified polymers having the above anionic species in the main chain or side chain. These dopants may be used independently and may use 2 or more types together.
  • the method for adding the dopant is not particularly limited.
  • a desired dopant may be appropriately added to the obtained polymer after polymerizing the monomer.
  • an anion derived from an oxidant used for polymerization or doping can be used as a dopant.
  • an anion derived from an electrolyte used for polymerization or doping can be used as a dopant.
  • the addition amount of the dopant can be arbitrarily adjusted depending on the dopant to be used, but is preferably 1 to 1000 parts by weight, more preferably 1 to 200 parts by weight with respect to 100 parts by weight of the polymer.
  • the polymer of the present invention is produced by chemical oxidative polymerization or electrochemical polymerization of the polymerizable compound (2) (preferably compound (3)) of the present invention and, if necessary, other monomers. It is preferable. Hereinafter, polymerization will be described together with doping.
  • the solvent used in the chemical oxidative polymerization or chemical oxidative doping is not particularly limited.
  • methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, acetonitrile, benzonitrile, propylene carbonate, nitromethane, tetrohydrofuran, methanol, Water etc. are mentioned.
  • the oxidizing agent used in chemical oxidative polymerization or chemical oxidative doping is not particularly limited, but is preferably a halogen or a transition metal salt.
  • the oxidizing agent include halogens such as I 2 , Br 2 , and Cl 2 ; ferric chloride (FeCl 3 ), ferric perchlorate (Fe (ClO 4 ) 3 ), and ferric sulfate (Fe 2).
  • ferric salt that is, iron (III) salt
  • a salt in which iron (III) is replaced with cerium (IV), copper (II), manganese (VII), ruthenium (III) can be used as an oxidizing agent.
  • oxidizing agent Only one type of oxidizing agent may be used, or two or more types may be used in combination.
  • the combination of oxidizing agents used in combination include, for example, a combination of oxidizing agents having a dopant action; a combination of oxidizing agents having no dopant action; an oxidizing agent having a dopant action (for example, one or more kinds having a dopant action)
  • a combination of a ferric salt) and an oxidizing agent having no dopant action for example, one or more ferric salts having no dopant action.
  • the amount of oxidant in the solvent is preferably 0.001 to 10 mol / L.
  • the amount of monomer in the solvent (that is, “molar amount of monomer / volume of solvent”) can be appropriately set depending on the polymerization conditions and the like to be employed. 001 to 10 mol / L.
  • the reaction temperature in chemical oxidative polymerization or chemical oxidative doping is not particularly limited, but is preferably ⁇ 50 ° C. to 200 ° C.
  • the reaction time in chemical oxidative polymerization or chemical oxidative doping is not particularly limited, but is preferably 1 minute to 48 hours.
  • a supporting salt may be used as an additive.
  • the supporting salt is not particularly limited.
  • perchlorate ion, boron tetrafluoride ion, phosphorus hexafluoride ion, halide ion, arsenic hexafluoride ion, antimony hexafluoride ion, sulfate ion, hydrogen sulfate ion examples thereof include support salts containing anions such as alkyl sulfonate ions, benzene sulfonate ions, alkyl benzene sulfonate ions, naphthalene sulfonate ions, alkyl naphthalene sulfonate ions, polystyrene sulfonate ions, and polyvinyl sulfonate ions.
  • solvent used in electrochemical polymerization or electrochemical doping examples include nitromethane, acetonitrile, propylene carbonate, nitrobenzene, cyanobenzene, o-dichlorobenzene, dimethyl sulfoxide, and ⁇ -butyrolactone.
  • Examples of the supporting electrolyte used in electrochemical polymerization or electrochemical doping include (a) alkali metal ions such as lithium ion, potassium ion and sodium ion, cations such as quaternary ammonium ion, and (b) perchlorine.
  • Examples thereof include support electrolytes composed of a combination with anions such as acid ions, boron tetrafluoride ions, phosphorus hexafluoride ions, halide ions, arsenic hexafluoride ions, antimony hexafluoride ions, sulfate ions and hydrogen sulfate ions.
  • the supporting electrolyte may be used alone or in combination of two or more.
  • electrolytic solution used in electrochemical polymerization or electrochemical doping examples include an electrolytic solution composed of the solvent and the supporting electrolyte.
  • ionic liquids such as an alkyl imidazolium salt and an alkyl pyridinium salt, can also be used as an electrolytic solution.
  • the amount of the monomer in the electrolytic solution (that is, “molar amount of monomer / volume of the electrolytic solution”) can be appropriately set depending on the polymerization conditions to be employed, etc. 0.001 to 10 mol / L.
  • the amount of the supporting electrolyte in the electrolytic solution is preferably 0.001 to 10 mol / L.
  • electrode materials used in electrochemical polymerization or electrochemical doping include platinum, gold, nickel, ITO, and the like.
  • the voltage at the time of application in electrochemical polymerization or electrochemical doping can be appropriately set depending on the conditions employed, etc., but is preferably 0.1 to 1.5 V (vs Ag / Ag + ), more The voltage is preferably 0.3 to 1.2 V (vs Ag / Ag + ).
  • the temperature at which the voltage is applied is preferably ⁇ 50 to 50 ° C., more preferably ⁇ 30 to 30 ° C.
  • the reaction temperature in electrochemical polymerization or electrochemical doping is not particularly limited, but is preferably ⁇ 50 ° C. to 200 ° C.
  • the reaction time in electrochemical polymerization or electrochemical doping is not particularly limited, but is preferably 1 minute to 48 hours.
  • the compounds and polymers of the present invention are useful for organic electronics members as semiconductive materials or conductive materials. Accordingly, the present invention also relates to an organic electronic member comprising the compound of the present invention; the composition comprising the compound of the present invention and a dopant; the polymer of the present invention; the composition comprising the polymer and the dopant of the present invention; or a mixture thereof.
  • organic electronics members include electrodes, solid electrolytic capacitors, thermoelectric elements, piezoelectric elements, actuators, sensors, organic thin film solar cells, dye-sensitized solar cells, organic thin film transistors, individual identification (RFID) devices using radio waves, field effect transistors (FET), integrated circuit (IC), organic electroluminescence element (OLED), organic semiconductor element and the like.
  • Example 1 To a Schlenk dried under reduced pressure and substituted with argon, 0.052 g (0.05 mmol) of tris (dibenzylideneacetone) dipalladium (0) chloroform adduct, 0.111 g of 1,1-bis (diphenylphosphino) ferrocene ( 0.20 mmol), sodium tert-butoxide 0.770 g (8.0 mmol), compound (10) 0.282 g (0.50 mmol), and toluene 3.0 mL were added. The mixture was stirred at room temperature for 20 minutes.
  • Example 2 The Schlenk dried under reduced pressure and substituted with argon was charged with 0.029 g (0.05 mmol) of bis (dibenzylideneacetone) dipalladium, 0.111 g (0.20 mmol) of 1,1-bis (diphenylphosphino) ferrocene, sodium Tert-butoxide 0.770 g (8.0 mmol), 0.282 g (0.50 mmol) of compound (10) and 3.5 mL of toluene were added. The mixture was stirred at room temperature for 20 minutes. Thereafter, 0.180 g (1.2 mmol) of 4-butylaniline was added to make Schlenk sealed, and the reaction mixture was stirred at 110 ° C. for 6 hours.
  • Example 3 In the same manner as in Example 2 except that 0.148 g (1.2 mmol) of p-anisidine was added instead of 0.180 g (1.2 mmol) of 4-butylaniline, 181 mg ( 0.371 mmol, 74%).
  • Example 4 In the same manner as in Example 2, except that 0.130 g (1.22 mmol) of benzylamine was added instead of 0.180 g (1.2 mmol) of 4-butylaniline and the reaction mixture was stirred at 90 ° C. for 4 hours. 14) The compound shown by 175 mg (0.385 mmol, 77%) was obtained.
  • Example 5 In the same manner as in Example 2 except that 0.081 g (1.20 mmol) of methylamine hydrochloride was added instead of 0.180 g (1.2 mmol) of 4-butylaniline and the reaction mixture was stirred at 90 ° C. for 2 hours. 78 mg (0.257 mmol, 51%) of the compound represented by the formula (15) was obtained.
  • Example 6 In the same manner as in Example 2 except that 0.098 g (1.34 mmol) of butylamine was added instead of 0.180 g (1.2 mmol) of 4-butylaniline, and the reaction mixture was stirred at 90 ° C. for 6 hours. ) Was obtained in 139 mg (0.374 mmol, 74%).
  • Example 7 85 mg of the compound represented by the formula (17) was obtained in the same manner as in Example 2 except that 0.121 g (1.20 mmol) of n-hexylamine was added instead of 0.180 g (1.2 mmol) of 4-butylaniline. (0.193 mmol, 39%).
  • Example 8 In the same manner as in Example 2 except that 0.157 g (1.20 mmol) of n-octylamine was added instead of 0.180 g (1.2 mmol) of 4-butylaniline, and the reaction mixture was stirred at 110 ° C. for 4 hours. 109 mg (0.218 mmol, 44%) of the compound represented by formula (18) was obtained.
  • Example 9 Using the compound (11), an organic thin film transistor was produced by the following procedure.
  • the substrate (silicon wafer) itself becomes the gate electrode, and the SiO 2 insulating layer becomes the gate insulating layer.
  • This substrate was ultrasonically washed with acetone, methanol and ultrapure water for 5 minutes each, immersed in a mixed solution of concentrated sulfuric acid-hydrogen peroxide solution for 1 minute, and then washed with running water.
  • the surface treatment of the substrate was performed in a hexamethyldisilazane (HMDS) atmosphere.
  • the compound (11) was vacuum-deposited under vacuum (10 ⁇ 6 torr) at a deposition rate of 0.2 to form an organic semiconductor layer having a thickness of 23 nm.
  • gold having a thickness of 48 nm was vacuum deposited to form a source electrode and a drain electrode, thereby obtaining an organic thin film transistor.
  • the channel width was 2058 ⁇ m and the channel length was 30 ⁇ m.
  • a gate voltage of ⁇ 150 V was applied to the gate electrode of the obtained organic thin film transistor, a voltage was further applied between the source electrode and the drain electrode, and a current was passed to evaluate the transistor characteristics.
  • Table 1 The results are shown in Table 1.
  • Example 10 In the same manner as in Example 9, an organic thin film transistor was produced using the compound (15).
  • the obtained organic thin film transistor had a channel width of 1470 ⁇ m and a channel length of 30 ⁇ m.
  • a gate voltage of ⁇ 100 V was applied to the gate electrode of the obtained organic thin film transistor, a voltage was further applied between the source electrode and the drain electrode, and a current was passed to evaluate the transistor characteristics. The results are shown in Table 1.
  • Example 11 Using the compound (11), an organic thin film transistor was produced by the following procedure. First, the same substrate as that used in Example 9 was ultrasonically cleaned with acetone, methanol, and ultrapure water for 5 minutes each. Next, a 0.5 wt% solution of the compound (11) in chloroform was applied onto the substrate using a spin coater (Kyowa Riken: K359S-1), and the film was removed by removing the solvent. A 3 nm organic semiconductor layer was formed. Further, using a mask, gold having a thickness of 43 nm was deposited on the organic semiconductor layer to form a source electrode and a drain electrode, thereby obtaining an organic thin film transistor. The channel width was 1220 ⁇ m and the channel length was 30 ⁇ m. A gate voltage of ⁇ 150 V was applied to the gate electrode of the obtained organic thin film transistor, a voltage was further applied between the source electrode and the drain electrode, and a current was passed to evaluate the transistor characteristics. The results are shown in Table 1.
  • Example 12 In a 50 mL three-necked flask equipped with a thermometer, compound (11) 20 mg (0.044 mmol), ferric perchlorate / n hydrate (anhydride content of 70 wt% or more), 78 mg, 10 mL of benzonitrile was added and the reaction mixture was stirred at 25 ° C. for 24 hours. After completion of the reaction, the reaction mixture was filtered to obtain 13.6 mg of a polymer. The obtained polymer was dried and then compression molded on a glass substrate to produce an electrode. The conductivity of the electrode (polymer) was measured by a four-probe method and found to be 4.27 ⁇ 10 ⁇ 2 S / cm.
  • the obtained polymer was immersed in an aqueous solution of 10% by weight of hydrazine monohydrate for 10 minutes to prepare a dedoping polymer.
  • the obtained dedoping polymer was dried and its conductivity was measured by a four-probe method. As a result, no conductivity was confirmed. This is a phenomenon peculiar to a conductive polymer whose conductivity is changed by doping and dedoping.
  • the condensed heterocyclic compound and the polymer thereof according to the present invention are, for example, inks, antistatic agents, organic electronics members (for example, electrodes, solid electrolytic capacitors, thermoelectric elements, piezoelectric elements, actuators) as semiconductive materials or conductive materials.
  • organic electronics members for example, electrodes, solid electrolytic capacitors, thermoelectric elements, piezoelectric elements, actuators
  • Sensors organic thin film solar cells, dye-sensitized solar cells, organic thin film transistors, radio wave identification (RFID) devices, field effect transistors (FETs), integrated circuits (ICs), organic electroluminescence devices (OLEDs), organic semiconductor devices Etc.).
  • RFID radio wave identification
  • FETs field effect transistors
  • ICs integrated circuits
  • OLEDs organic electroluminescence devices
  • organic semiconductor devices Etc. organic semiconductor devices

Abstract

La présente invention concerne un composé représenté par la formule (1) et un polymère de celui-ci. [Dans la formule, le groupe R1 et chaque groupe R2 sont chacun indépendamment un atome d'hydrogène, un groupe alkyle facultativement substitué, un groupe aryle facultativement substitué, un groupe hétéroaryle facultativement substitué ou -CO-R (dans cette formule, R est un groupe alkyle facultativement substitué, un groupe aryle facultativement substitué ou un groupe hétéroaryle facultativement substitué), le cycle A, le cycle B et le cycle C sont chacun indépendamment un cycle hétérocyclique aromatique de 5 chaînons ou 6 chaînons facultativement substitué, et n est un entier compris entre 1 et 4.]
PCT/JP2012/065780 2011-06-22 2012-06-20 Composé hétérocyclique condensé et polymère de celui-ci WO2012176820A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2011-138932 2011-06-22
JP2011138932 2011-06-22
JP2012-049806 2012-03-06
JP2012049806 2012-03-06

Publications (1)

Publication Number Publication Date
WO2012176820A1 true WO2012176820A1 (fr) 2012-12-27

Family

ID=47422651

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/065780 WO2012176820A1 (fr) 2011-06-22 2012-06-20 Composé hétérocyclique condensé et polymère de celui-ci

Country Status (2)

Country Link
JP (1) JPWO2012176820A1 (fr)
WO (1) WO2012176820A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013028750A (ja) * 2011-07-29 2013-02-07 Sumitomo Chemical Co Ltd 高分子化合物及びそれを用いた有機トランジスタ
JP2013235904A (ja) * 2012-05-07 2013-11-21 Fujifilm Corp 有機薄膜太陽電池、これに用いられる有機半導体材料用組成物および単量体
US20150090994A1 (en) * 2013-10-02 2015-04-02 Pusan National University Industry-University Cooperation Foundation Organic compound and organic light emitting diode device including the same
EP2903047A1 (fr) * 2014-01-31 2015-08-05 Ecole Polytechnique Fédérale de Lausanne (EPFL) Matériau de transport de trous et d'absorption de lumière pour cellules solaires à l'état solide
KR20160065885A (ko) * 2013-09-27 2016-06-09 헬리아텍 게엠베하 광전자 부품들을 위한 광활성 유기 재료
CN105837598A (zh) * 2016-03-28 2016-08-10 大连理工大学 并噻吩并吡咯醌式化合物、制备方法及包含该材料的半导体设备
CN106977528A (zh) * 2017-03-29 2017-07-25 淮阴工学院 含三噻吩并吡咯‑噻吩的有机染料及其在染料敏化太阳能电池中的应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009063780A1 (fr) * 2007-11-12 2009-05-22 Mitsui Chemicals, Inc. Transistor organique
JP2009190999A (ja) * 2008-02-13 2009-08-27 Osaka Univ 縮合環化合物及びその製造方法、重合体、これらを含む有機薄膜、並びに、これを備える有機薄膜素子及び有機薄膜トランジスタ。
JP2010034449A (ja) * 2008-07-31 2010-02-12 Mitsui Chemicals Inc 有機トランジスタ
WO2010061176A1 (fr) * 2008-11-28 2010-06-03 Cambridge Display Technology Limited Semi-conducteurs organiques

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009063780A1 (fr) * 2007-11-12 2009-05-22 Mitsui Chemicals, Inc. Transistor organique
JP2009190999A (ja) * 2008-02-13 2009-08-27 Osaka Univ 縮合環化合物及びその製造方法、重合体、これらを含む有機薄膜、並びに、これを備える有機薄膜素子及び有機薄膜トランジスタ。
JP2010034449A (ja) * 2008-07-31 2010-02-12 Mitsui Chemicals Inc 有機トランジスタ
WO2010061176A1 (fr) * 2008-11-28 2010-06-03 Cambridge Display Technology Limited Semi-conducteurs organiques

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FIROUZI, R.: "Linear regression analysis of molecular energy properties for poly heterocyclic compounds", JOURNAL OF MOLECULAR STRUCTURE: THEOCHEM, vol. 906, no. 1-3, 2009, pages 35 - 40 *
MITSUDO, K.: "Synthesis of Nitrogen-Bridged Terthiophenes by Tandem Buchwald-Hartwig Coupling and Their Properties", ORGANIC LETTERS, vol. 14, no. 11, 17 May 2012 (2012-05-17), pages 2702 - 2705 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013028750A (ja) * 2011-07-29 2013-02-07 Sumitomo Chemical Co Ltd 高分子化合物及びそれを用いた有機トランジスタ
JP2013235904A (ja) * 2012-05-07 2013-11-21 Fujifilm Corp 有機薄膜太陽電池、これに用いられる有機半導体材料用組成物および単量体
KR20160065885A (ko) * 2013-09-27 2016-06-09 헬리아텍 게엠베하 광전자 부품들을 위한 광활성 유기 재료
KR102233924B1 (ko) 2013-09-27 2021-03-30 헬리아텍 게엠베하 광전자 부품들을 위한 광활성 유기 재료
KR20150039459A (ko) * 2013-10-02 2015-04-10 삼성디스플레이 주식회사 유기 화합물 및 이를 포함하는 유기 발광 장치
US9666811B2 (en) * 2013-10-02 2017-05-30 Samsung Display Co., Ltd. Organic compound and organic light emitting diode device including the same
KR102111031B1 (ko) * 2013-10-02 2020-05-15 삼성디스플레이 주식회사 유기 화합물 및 이를 포함하는 유기 발광 장치
US20150090994A1 (en) * 2013-10-02 2015-04-02 Pusan National University Industry-University Cooperation Foundation Organic compound and organic light emitting diode device including the same
WO2015114521A1 (fr) * 2014-01-31 2015-08-06 Ecole Polytechnique Federale De Lausanne (Epfl) Matériau de transport de trous absorbant la lumière pour cellules solaires à semi-conducteurs
EP2903047A1 (fr) * 2014-01-31 2015-08-05 Ecole Polytechnique Fédérale de Lausanne (EPFL) Matériau de transport de trous et d'absorption de lumière pour cellules solaires à l'état solide
CN106062984A (zh) * 2014-01-31 2016-10-26 洛桑联邦理工学院 用于固态太阳能电池的空穴传输和光吸收材料
US20160351342A1 (en) * 2014-01-31 2016-12-01 Ecole Polytechnique Federale De Lausanne (Epfl) Hole transporting and light absorbing material for solid state solar cells
CN105837598A (zh) * 2016-03-28 2016-08-10 大连理工大学 并噻吩并吡咯醌式化合物、制备方法及包含该材料的半导体设备
CN106977528A (zh) * 2017-03-29 2017-07-25 淮阴工学院 含三噻吩并吡咯‑噻吩的有机染料及其在染料敏化太阳能电池中的应用

Also Published As

Publication number Publication date
JPWO2012176820A1 (ja) 2015-02-23

Similar Documents

Publication Publication Date Title
WO2012176820A1 (fr) Composé hétérocyclique condensé et polymère de celui-ci
Zou et al. Unexpected Propeller‐Like Hexakis (fluoren‐2‐yl) benzene Cores for Six‐Arm Star‐Shaped Oligofluorenes: Highly Efficient Deep‐Blue Fluorescent Emitters and Good Hole‐Transporting Materials
TWI675033B (zh) 含有雜環的化合物、使用該化合物的聚合物及其用途
Ye et al. Cyanated diazatetracene diimides with ultrahigh electron affinity for n-channel field effect transistors
US8378338B2 (en) Conjugated compound, nitrogenated condensed-ring compound, nitrogenated condensed-ring polymer, organic thin film, and organic thin film element
EP1997821A1 (fr) Compose fluore et son procede de production, polymere fluore, film mince organique et dispositif de film mince organique
JP4931118B2 (ja) フッ素化シクロペンタン環と芳香環との縮合したユニットを含む重合体、並びにこれを用いた有機薄膜及び有機薄膜素子
WO2003010778A1 (fr) Semi-conducteurs de type n au thiophene
Lin et al. Ambipolar organic field-effect transistors based on diketopyrrolopyrrole derivatives containing different π-conjugating spacers
JP2008255097A (ja) 含フッ素多環芳香族化合物、含フッ素重合体、有機薄膜及び有機薄膜素子
JP2008248228A (ja) ジフルオロシクロペンタンジオン環と芳香環との縮合したユニットを含む重合体、並びにこれを用いた有機薄膜及び有機薄膜素子
JP2011079827A (ja) ベンゾジチオフェンを製造する方法および半導体ポリマを製造する方法
WO2011120951A1 (fr) Copolymères de dithiophènes annelés
Li et al. Two Regioisomeric π‐Conjugated Small Molecules: Synthesis, Photophysical, Packing, and Optoelectronic Properties
Gao et al. Approaching high charge carrier mobility by alkylating both donor and acceptor units at the optimized position in conjugated polymers
Kang et al. Aqueous-alcohol-processable high-mobility semiconducting copolymers with engineered oligo (ethylene glycol) side chains
Funahashi Anisotropic electrical conductivity of n-doped thin films of polymerizable liquid-crystalline perylene bisimide bearing a triethylene oxide chain and cyclotetrasiloxane rings
WO2010104131A1 (fr) Composé conjugué ainsi que film mince organique et élément à film mince organique qui le comprennent chacun
US20150021526A1 (en) Semiconductor composition
Wang et al. Direct C–H arylation for various Ar-cored diketopyrrolopyrrole containing small molecules in solution-processed field-effect transistors
WO2021221039A1 (fr) Matériau conducteur
JP2009040903A (ja) イソチアナフテン構造含有高分子及びその製造方法、並びに電荷輸送材料及び有機電子デバイス
JP2012214730A (ja) チエノチオフェン共重合体及びその製造方法
Fan et al. Synthesis and photovoltaic properties of two star-shaped molecules involving phenylquinoxaline as core and triphenylamine and thiophene units as arms
Molji et al. Macroscopically oriented (3-pentadecyl phenol) dangled fluorene based conductive polymer through side chain engineering for microelectronics.

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12803012

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2013521609

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12803012

Country of ref document: EP

Kind code of ref document: A1