WO2011108765A1 - Composé polycyclique - Google Patents

Composé polycyclique Download PDF

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WO2011108765A1
WO2011108765A1 PCT/JP2011/055568 JP2011055568W WO2011108765A1 WO 2011108765 A1 WO2011108765 A1 WO 2011108765A1 JP 2011055568 W JP2011055568 W JP 2011055568W WO 2011108765 A1 WO2011108765 A1 WO 2011108765A1
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ring
group
ring structure
atom
compound
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康生 宮田
光弘 松本
正生 柳川
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住友化学株式会社
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    • 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
    • C07D495/02—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 two hetero rings
    • C07D495/04—Ortho-condensed systems
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/008—Dyes containing a substituent, which contains a silicium atom
    • 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
    • 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
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • 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
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate

Definitions

  • the present invention relates to a polycyclic compound.
  • Organic transistors are used as elements such as electronic paper and large screen flat panel displays.
  • Such an organic transistor is composed of members such as an organic semiconductor active layer, a substrate, an insulating layer, and an electrode.
  • Examples of the compound that provides the organic semiconductor active layer include J. Org. Appl. Phys. 2002, 92 , 5259 describes pentacene, and it is also known to use a thin film obtained by vacuum deposition of pentacene as an organic semiconductor active layer.
  • the present invention [1] Formula (1) (Wherein the ring structure C is a benzene ring represented by the formula (C1), a hetero [3,2-b] heterol ring represented by the formula (C2), or a benzo [1,2- b: 4,5-b ′] represents a diheteroyl ring.
  • W, X, Y and Z are independently sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, SO 2, (R 11) -C- (R 12), (R 13) -Si- (R 14 ) Or N- (R 15 ), and at least one selected from the group consisting of W, X, Y and Z is N- (R 15 ).
  • Ring structure A and ring structure B independently represent an aromatic carbocyclic ring that may have a substituent or an aromatic heterocyclic ring that may have a substituent.
  • the ring structure A and the ring structure B may independently have a substituent.
  • R 11 , R 12 , R 13 and R 14 independently represent an alkyl group or a hydrogen atom optionally having one or more halogen atoms, and R 15 independently represents one or more halogen atoms.
  • the alkyl group which may have is represented.
  • a polycyclic compound represented by: [2] W, X, Y, and Z are each independently a sulfur atom, an oxygen atom, a selenium atom, or N— (R 15 ), and at least selected from the group consisting of W, X, Y, and Z
  • the ring structure C is a hetero [3,2-b] heterol ring represented by the formula (C2) or a benzo [1,2-b: 4,5-b ′] diheteroyl ring represented by the formula (C3)
  • the ring structure C is a benzene ring represented by the formula (C1), X and Y are independently N— (R
  • the aromatic heterocyclic ring which may be present may be a thiophene ring which may have a substituent, a benzo [b] thiophene ring which may have a substituent, or a thieno which may have a substituent.
  • the ring structure C may have a thieno [b] thiophene ring, an optionally substituted benzo [1,2-b: 4,5-b ′] dithiophene ring or a substituent.
  • Compound (1) is a compound comprising four 5-membered rings each containing W, X, Y and Z, and ring structure A, ring structure B and ring structure C.
  • W, X, Y and Z are independently a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, SO 2 , (R 11 ) -C- (R 12 ), (R 13 ) -Si- (R 14 ) Or N- (R 15 And at least one selected from the group consisting of W, X, Y and Z is N- (R 15 ).
  • R 15 Is an alkyl group which may have one or more halogen atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl.
  • n-pentyl group neopentyl group, n-hexyl group, 2-ethylhexyl group, cyclohexyl group, n-heptyl group, n-octyl group, cyclooctyl group, n-nonyl group, n-decyl group, 2-hexyl Decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n- Icosyl group, n-henicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, n-
  • W, X, Y and Z are independently a sulfur atom, an oxygen atom, a selenium atom or N- (R 15 And at least one selected from the group consisting of W, X, Y and Z is N- (R 15 And W, X, Y and Z are independently a sulfur atom, an oxygen atom, a selenium atom or N- (R 15 And at least two selected from the group consisting of W, X, Y and Z are N- (R 15 ) Is more preferable.
  • W, X, Y and Z are independently a sulfur atom or N— (R 15 And at least two selected from the group consisting of W, X, Y and Z are N- (R 15 Is particularly preferred.
  • R 11 , R 12 , R 13 And R 14 Independently represents an alkyl group which may have one or more halogen atoms or a hydrogen atom, and the alkyl group which may have one or more halogen atoms includes the above R 15 The same group is mentioned.
  • X and Y are preferably the same, and W and Z are preferably the same in that the synthesis of the compound (1) is easy.
  • the ring structure A and the ring structure B independently have an aromatic carbocycle (hereinafter abbreviated as an aromatic ring) which may have a substituent or a substituent.
  • Represents an aromatic heterocyclic ring hereinafter abbreviated as a heterocyclic ring).
  • the aromatic ring of ring structure A and ring structure B is a ring having aromaticity, and the aromatic ring of ring structure A is composed of 6 to 14 carbon atoms, and includes a 5-membered ring containing W and two carbons. A carbocycle that shares atoms.
  • the aromatic ring of ring structure B is a carbocyclic ring composed of 6 to 14 carbon atoms and sharing two carbon atoms with a 5-membered ring containing Z. Such aromatic rings may have one or more substituents.
  • Examples of the unsubstituted aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring.
  • a benzene ring and a naphthalene ring are preferable, and a benzene ring is more preferable.
  • the heterocyclic ring of ring structure A and ring structure B is a ring having aromaticity and containing at least one hetero atom.
  • the heterocyclic ring of ring structure A has 5 to 12 atoms constituting the ring. Yes, it is a carbocycle that shares two carbon atoms with a 5-membered ring containing W.
  • the heterocyclic ring of ring structure B is a carbocyclic ring having 5 to 12 atoms constituting the ring and sharing two carbon atoms with a 5-membered ring containing Z. Such a heterocycle may have one or more substituents.
  • the hetero atom include an oxygen atom, a selenium atom, a sulfur atom, and a nitrogen atom.
  • the number of hetero atoms contained in the heterocyclic ring is preferably 1 or 2.
  • the unsubstituted heterocycle includes a thiophene ring, a furan ring, a selenophene ring, a pyrrole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring and the like, and thieno [3 , 2-b] thiophene ring, furo [3,2-b] furan ring, thieno [3,2-b] furan ring, benzo [b] thiophene ring, benzo [b] furan ring, etc. Is mentioned.
  • heterocyclic ring of ring structure A and ring structure B examples include a thiophene ring, a furan ring, a selenophene ring, a pyrrole ring, a thiazole ring, a thieno [3,2-b] thiophene ring, a furo [3,2-b] furan ring, Thieno [3,2-b] furan ring, benzo [b] thiophene ring and benzo [b] furan ring are preferred, thiophene ring sharing the 2nd and 3rd carbon atoms with the ring containing W or Z, 2nd position And a thieno [3,2-b] thiophene ring that shares a 3-position carbon atom with a ring containing W or Z and a benzo [b] thiophene that shares a 2- and 3-position carbon atom with a ring containing W or Z Rings are more preferred, and thiophene rings that share
  • alkyl group As substituents of the aromatic ring and heterocyclic ring of ring structure A and ring structure B, alkyl group, alkoxy group, aryl group, alkyl-substituted aryl group, alkoxy-substituted aryl group, heteroaryl group, alkyl-substituted heteroaryl group, alkoxy-substituted Examples include heteroaryl groups, alkenyl groups, alkynyl groups, alkylthio groups, alkylcarbonyl groups, alkoxycarbonyl groups, (trialkyl) silyl groups, (dialkyl) amino groups, halogen atoms, cyano groups, and nitro groups.
  • halogen atom a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, A fluorine atom, a bromine atom, and an iodine atom are preferable.
  • alkyl group include a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, and a linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms is preferable.
  • alkyl group having one or more halogen atoms examples include groups in which some or all of the hydrogen atoms of the alkyl group have been replaced with halogen atoms.
  • alkoxy group examples include straight-chain, branched-chain, and cyclic alkoxy groups, and straight-chain, branched-chain, or cyclic alkoxy groups having 1 to 30 carbon atoms are preferable.
  • alkoxy group having 1 to 16 carbon atoms is more preferable.
  • alkoxy group having one or more halogen atoms include groups in which some or all of the hydrogen atoms of the alkoxy group are replaced with halogen atoms.
  • the aryl group include aryl groups having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group, and a phenyl group and a naphthyl group are preferable.
  • Examples of the aryl group having one or more halogen atoms include groups in which some or all of the hydrogen atoms of the aryl group are replaced with halogen atoms.
  • the heteroaryl group is preferably a monocyclic or bicyclic heteroaryl group, and a thienyl group, furyl group, thiazolyl group, thieno [3,2-b] thienyl group, furo [3,2-b] furyl group, Thieno [3,2-b] furyl group, benzo [b] thienyl group, benzo [b] furyl group, more preferably thienyl group, furyl group, thieno [3,2-b] thienyl group, benzo [ b] thienyl group and benzo [b] furyl group are more preferred.
  • heteroaryl group having one or more halogen atoms examples include groups in which some or all of the hydrogen atoms of the heteroaryl group have been replaced with halogen atoms.
  • the alkyl-substituted aryl group is a group in which one or more hydrogen atoms of the aryl group are replaced with the alkyl group.
  • the alkoxy-substituted aryl group is a group in which one or more hydrogen atoms of the aryl group are replaced with the alkoxy group.
  • the alkyl-substituted heteroaryl group is a group in which one or more hydrogen atoms of the heteroaryl group are replaced with the alkyl group.
  • the alkoxy-substituted heteroaryl group is a group in which one or more hydrogen atoms of the heteroaryl group are replaced with the alkoxy group.
  • the alkenyl group include a linear alkenyl group and a branched alkenyl group, and a linear or branched alkenyl group having 2 to 30 carbon atoms is preferable.
  • ethenyl group 1-propenyl group, 1-butenyl group, 1-pentenyl group, 1-hexenyl group, 1-cyclohexenyl group, 1-heptenyl group, 1-octenyl group, 1-nonenyl group, 1 1-decenyl group, 1-undecenyl group, 1-dodecenyl group, 1-tridecenyl group, 1-tetradecenyl group, 1-pentadecenyl group, 1-hexadecenyl group, 1-heptadecenyl group, 1-octadecenyl group, 1-nonadecenyl group, 1 -Icocenyl group, 1-henicocenyl group, 1-docosenyl group, 1-tricocenyl group, 1-tetracocenyl group, 1-pentacocenyl group, 1-hexacocenyl group, 1-heptacosen
  • alkenyl group having one or more halogen atoms include groups in which some or all of the hydrogen atoms in the alkenyl group are replaced with halogen atoms.
  • alkynyl group include a linear alkynyl group and a branched alkynyl group, and a linear or branched alkynyl group having 2 to 30 carbon atoms is preferable.
  • alkynyl group having one or more halogen atoms include groups in which some or all of the hydrogen atoms in the alkynyl group are replaced with halogen atoms.
  • alkylthio group include straight-chain, branched-chain and cyclic alkylthio groups, and straight-chain, branched-chain or cyclic alkylthio groups having 1 to 30 carbon atoms are preferable.
  • alkylthio group having one or more halogen atoms include groups in which some or all of the hydrogen atoms of the alkylthio group have been replaced with halogen atoms.
  • alkylcarbonyl group include a straight-chain alkylcarbonyl group and a branched-chain alkylcarbonyl group, preferably a straight-chain or branched-chain alkylcarbonyl group having 2 to 30 carbon atoms, 2 to 17 linear or branched alkylcarbonyl groups are more preferred.
  • alkylcarbonyl group having one or more halogen atoms include groups in which some or all of the hydrogen atoms of the alkylcarbonyl group have been replaced with halogen atoms.
  • alkoxycarbonyl group examples include a straight-chain alkoxycarbonyl group and a branched-chain alkoxycarbonyl group, preferably a straight-chain or branched-chain alkoxycarbonyl group having 2 to 30 carbon atoms, and having 2 to 17 carbon atoms.
  • the linear or branched alkoxycarbonyl group is more preferable.
  • methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, n-hexyloxycarbonyl group, n-octyloxycarbonyl group, n-dodecyloxycarbonyl group, n-pentadecyloxycarbonyl group and n- An icosyloxycarbonyl group may be mentioned.
  • alkoxycarbonyl group having one or more halogen atoms include groups in which some or all of the hydrogen atoms of the alkoxycarbonyl group have been replaced with halogen atoms.
  • Examples of the (trialkyl) silyl group include groups in which three alkyl groups having 1 to 30 carbon atoms are bonded to a silicon atom. Specifically, trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, tri-s-butylsilyl group, tri-t-butylsilyl group, tri-isobutylsilyl Group, t-butyl-dimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group and dimethyl-n-dodecylsilyl group, and three alkyl groups having 1 to 6 carbon atoms are silicon atoms A group bonded to is preferable.
  • the (trialkyl) silyl group having one or more halogen atoms is a group in which three alkyl groups are bonded to a silicon atom, and a part or all of hydrogen atoms of at least one alkyl group are converted to halogen atoms. Examples include groups that have been replaced.
  • the (dialkyl) amino group is a group in which two alkyl groups having 1 to 30 carbon atoms are bonded to a nitrogen atom, that is, two hydrogen atoms of an amino group are each an alkyl group having 1 to 30 carbon atoms. The group replaced with is mentioned.
  • a group in which two alkyl groups having 1 to 10 carbon atoms are bonded to a nitrogen atom is preferable.
  • the (dialkyl) amino group having one or more halogen atoms is a group in which two alkyl groups are bonded to a nitrogen atom, and a part or all of the hydrogen atoms of at least one alkyl group are replaced with halogen atoms.
  • the ring structure C includes a benzene ring represented by the formula (C1), a hetero [3,2-b] heterol ring represented by the formula (C2), or a benzo [1,2-b: 4 represented by the formula (C3).
  • 5-b '] represents a diheteroyl ring.
  • P and Q independently represent a sulfur atom, an oxygen atom, a selenium atom or a tellurium atom, and the benzene ring constituting the ring may have a substituent.
  • P and Q are each independently preferably a sulfur atom, an oxygen atom or a selenium atom, more preferably a sulfur atom or an oxygen atom, and a sulfur atom. Is particularly preferred.
  • substituent of the benzene ring constituting the ring represented by the formula (C1) and the formula (C3) include the same groups as the substituents of the ring structure A and the ring structure B. Preferred substituents are also described above.
  • Examples thereof include the same groups as the preferred substituents of the ring structure A and the ring structure B.
  • Examples of the ring represented by the formula (C2) include a thieno [3,2-b] thiophene ring, a furo [3,2-b] furan ring, a seleno [3,2-b] selenophene ring, and a thieno [3,2- b] Furan ring, thieno [3,2-b] selenophene ring and seleno [3,2-b] furan ring are mentioned, and thieno [3,2-b] thiophene ring is preferable.
  • Examples of the ring represented by the formula (C3) include a benzo [1,2-b: 4,5-b ′] dithiophene ring, a benzo [1,2-b: 4,5-b ′] difuran ring, and a benzo [1 , 2-b: 4,5-b ′] diselenophene ring, benzo [1,2-b: 4,5-b ′] dithiophene ring and benzo [1,2-b: 4,5-b ′].
  • a difuran ring is preferable, and a benzo [1,2-b: 4,5-b ′] dithiophene ring is more preferable.
  • the ring structure C is a benzene ring represented by the formula (C1), and X and Y are independently N- (R 15 )
  • Ring structure A and ring structure B are each independently an optionally substituted aromatic heterocyclic ring, in which case W and Z are independently a sulfur atom.
  • W and Z are independently a sulfur atom.
  • W and Z are independently a sulfur atom.
  • X and Y are the same N- (R 15 ) Is preferable.
  • X and Y are independently a sulfur atom, an oxygen atom or a selenium atom
  • W and Z are independently N-
  • R 15 X and Y are independently a sulfur atom or an oxygen atom
  • W and Z are independently N-
  • W and Z are the same N- (R 15 ) Is preferable.
  • the ring structure is a hetero [3,2-b] heterol ring represented by the formula (C2) or benzo [1,2-b: 4,5-b ′] represented by the formula (C3).
  • W and X When it is a dihetero ring, one of W and X is N- (R 15 And the other is a sulfur atom, an oxygen atom or a selenium atom, and one of Y and Z is N- (R 15 And the other is preferably a sulfur atom, an oxygen atom or a selenium atom, and one of W and X is N- (R 15 ),
  • the other is a sulfur atom or an oxygen atom, and one of Y and Z is N- (R 15 More preferably, the other is a sulfur atom or an oxygen atom, and one of W and X is N- (R 15
  • the other is a sulfur atom or an oxygen atom
  • Y is the same as X
  • Z is the same as W.
  • Ring structure C is a benzene ring represented by formula (C1), ring structure A and ring structure B are each independently an aromatic heterocyclic ring optionally having a substituent, and X and Y Are independently N- (R 15 And W and Z are independently a sulfur atom, an oxygen atom or a selenium atom (1);
  • the ring structure C is a benzene ring represented by the formula (C1), the ring structure A and the ring structure B are the same, and an optionally substituted aromatic heterocyclic ring, and X and Y is the same N- (R 15 And W and Z are independently a sulfur atom, an oxygen atom or a selenium atom (1);
  • Ring structure C is a benzene ring represented by formula (C1), ring structure A and ring structure B are the same, and optionally substituted aromatic heterocycle, and X and Y is the same N- (R 15 And W and Z are independently a sulfur atom or an oxygen atom (1);
  • Ring structure C is a benzene ring represented by formula (C1), ring structure A and ring structure B are the same, and a halogen atom, alkyl group, (trialkyl) silyl group, aryl group or heteroaryl group
  • a thiophene ring optionally having X and Y are the same N- (R 15 ) And R 15 Is an alkyl group having 1 to 30 carbon atoms, and W and Z are independently a sulfur atom, an oxygen atom or a selenium atom (1)
  • Ring structure C is a benzene ring represented by formula (C1), ring structure A and ring structure B are the same, and a halogen atom, alkyl
  • Ring structure C is a benzene ring represented by formula (C1), ring structure A and ring structure B are the same, and a halogen atom, alkyl group, (trialkyl) silyl group, aryl group or heteroaryl group
  • Ring structure C is a benzene ring represented by formula (C1), ring structure A and ring structure B are the same, and
  • Ring structure C is a benzene ring represented by formula (C1), ring structure A and ring structure B are the same, and a halogen atom, alkyl group, (trialkyl) silyl group, aryl group or heteroaryl group
  • Benzene ring optionally having W and Z are the same N- (R 15 )
  • Ring structure C is a benzene ring represented by formula (C1), ring structure A and ring structure B are the same, and a halogen atom, alkyl
  • Ring structure C is a benzene ring represented by formula (C1), ring structure A and ring structure B are the same, and a halogen atom, alkyl group, (trialkyl) silyl group, aryl group or heteroaryl group
  • W and Z are independently N- (R 15 )
  • R 15 Is an alkyl group having 1 to 30 carbon atoms
  • X and Y are independently a sulfur atom, an oxygen atom or a selenium atom (1)
  • Ring structure C is a benzene ring represented by formula (C1), ring structure A and ring structure B are the same, and a halogen atom, alkyl group having 1 to 30 carbon atoms
  • X and Y are independently a sulfur atom, an oxygen atom or a selenium atom (1)
  • Ring structure C is a benzene ring represented by formula (C1), ring structure A and ring structure B are the same, and a halogen atom, al
  • Ring structure C is a benzene ring represented by formula (C1), ring structure A and ring structure B are the same, and a halogen atom, alkyl group, (trialkyl) silyl group, aryl group or heteroaryl group
  • a thiophene ring optionally having W and Z are the same N- (R 15 )
  • R 15 Is an alkyl group having 1 to 30 carbon atoms, and X and Y are independently a sulfur atom, an oxygen atom or a selenium atom (1)
  • Ring structure C is a benzene ring represented by formula (C1), ring structure A and ring structure B are the same, and a halogen atom, alkyl
  • the ring structure C is a hetero [3,2-b] heterol ring represented by the formula (C2), and the ring structure A and the ring structure B may independently have a substituent.
  • the ring structure C is a hetero [3,2-b] heterol ring represented by the formula (C2), and the ring structure A and the ring structure B may independently have a substituent.
  • the ring structure C is a hetero [3,2-b] heterol ring represented by the formula (C2), and the ring structure A and the ring structure B may independently have a substituent.
  • the ring structure C is a hetero [3,2-b] heterol ring represented by the formula (C2), the ring structure A and the ring structure B are the same, and the aromatic group which may have a substituent A carbocyclic ring wherein one of W and X is N- (R 15 And the other is a sulfur atom or an oxygen atom, Y is the same as X, Z is the same as W, R 15 Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms;
  • the ring structure C is a hetero [3,2-b] heterol ring represented by the formula (C2), the ring structure A and the ring structure B are the same, and the aromatic group which may have a substituent A carb
  • a heterocycle wherein one of W and X is N- (R 15 And the other is a sulfur atom, an oxygen atom or a selenium atom, and one of Y and Z is N- (R 15 And the other is a sulfur atom, an oxygen atom or a selenium atom, and R 15
  • Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms;
  • the ring structure C is a hetero [3,2-b] heterol ring represented by the formula (C2), and the ring structure A and the ring structure B may independently have a substituent.
  • a heterocycle wherein one of W and X is N- (R 15 ), The other is a sulfur atom or an oxygen atom, and one of Y and Z is N- (R 15 And the other is a sulfur atom or an oxygen atom, and R 15
  • Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms;
  • the ring structure C is a hetero [3,2-b] heterol ring represented by the formula (C2), and the ring structure A and the ring structure B may independently have a substituent.
  • a heterocycle wherein one of W and X is N- (R 15 ), The other is a sulfur atom, and one of Y and Z is N- (R 15 ), The other is a sulfur atom, and R 15
  • Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms;
  • the ring structure C is a hetero [3,2-b] heterol ring represented by the formula (C2), and the ring structure A and the ring structure B may independently have a substituent.
  • a heterocycle wherein one of W and X is N- (R 15 And the other is a sulfur atom or an oxygen atom, Y is the same as X, Z is the same as W, R 15 Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms;
  • the ring structure C is a hetero [3,2-b] heterol ring represented by the formula (C2), the ring structure A and the ring structure B are the same, and the aromatic group which may have a substituent A heterocycle, and one of W and X is N- (R 15 And the other is a sulfur atom or an oxygen atom, Y is the same as X, Z is the same as W, R 15 Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms;
  • the ring structure C is a hetero [3,2-b] heterol ring represented by the formula (C2), the ring structure A and the ring structure B are the same, and the aromatic group which may have a substituent A heterocycle, and one
  • one of W and X is N- (R 15 And the other is a sulfur atom, an oxygen atom or a selenium atom, and one of Y and Z is N- (R 15 And the other is a sulfur atom, an oxygen atom or a selenium atom, and R 15
  • Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms; Ring structure C is a hetero [3,2-b] heterol ring represented by formula (C2), and ring structure A and ring structure B are independently a benzene ring optionally having a substituent.
  • one of W and X is N- (R 15 ), The other is a sulfur atom or an oxygen atom, and one of Y and Z is N- (R 15 And the other is a sulfur atom or an oxygen atom, and R 15 Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms;
  • the ring structure C is a hetero [3,2-b] heterol ring represented by the formula (C2), the ring structure A and the ring structure B are the same, and an optionally substituted benzene ring And one of W and X is N- (R 15 ),
  • the other is a sulfur atom or an oxygen atom, and one of Y and Z is N- (R 15 And the other is a sulfur atom or an oxygen atom, and R 15 Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms;
  • the ring structure C is a hetero [3,2-b] heterol ring represented by the formula (C2), the ring structure A and the ring structure
  • one of W and X is N- (R 15 And the other is a sulfur atom, an oxygen atom or a selenium atom, and one of Y and Z is N- (R 15 And the other is a sulfur atom, an oxygen atom or a selenium atom, and R 15
  • Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms; Ring structure C is a hetero [3,2-b] heterol ring represented by formula (C2), and ring structure A and ring structure B are independently a naphthalene ring optionally having a substituent.
  • one of W and X is N- (R 15 ), The other is a sulfur atom or an oxygen atom, and one of Y and Z is N- (R 15 And the other is a sulfur atom or an oxygen atom, and R 15 Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms;
  • the ring structure C is a hetero [3,2-b] heterol ring represented by the formula (C2), the ring structure A and the ring structure B are the same, and an optionally substituted naphthalene ring And one of W and X is N- (R 15 ),
  • the other is a sulfur atom or an oxygen atom, and one of Y and Z is N- (R 15 And the other is a sulfur atom or an oxygen atom, and R 15 Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms;
  • the ring structure C is a hetero [3,2-b] heterol ring represented by the formula (C2), the ring structure A and the
  • one of W and X is N- (R 15 And the other is a sulfur atom, an oxygen atom or a selenium atom, and one of Y and Z is N- (R 15 And the other is a sulfur atom, an oxygen atom or a selenium atom, and R 15
  • Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms; Ring structure C is a hetero [3,2-b] heterol ring represented by formula (C2), and ring structure A and ring structure B are each independently a thiophene ring optionally having a substituent.
  • one of W and X is N- (R 15 ), The other is a sulfur atom or an oxygen atom, and one of Y and Z is N- (R 15 And the other is a sulfur atom or an oxygen atom, and R 15 Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms;
  • the ring structure C is a hetero [3,2-b] heterol ring represented by the formula (C2), the ring structure A and the ring structure B are the same, and the thiophene ring which may have a substituent And one of W and X is N- (R 15 ),
  • the other is a sulfur atom or an oxygen atom, and one of Y and Z is N- (R 15 And the other is a sulfur atom or an oxygen atom, and R 15 Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms;
  • the ring structure C is a hetero [3,2-b] heterol ring represented by the formula (C2), the ring structure A and
  • An aromatic heterocycle which may be optionally substituted with one of W and X being N- (R 15 And the other is a sulfur atom, an oxygen atom or a selenium atom, and one of Y and Z is N- (R 15 And the other is a sulfur atom, an oxygen atom or a selenium atom, and R 15
  • Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms; Ring structure C is a benzo [1,2-b: 4,5-b ′] dihetero ring represented by formula (C3), and ring structure A and ring structure B independently have a substituent.
  • An aromatic heterocycle which may be optionally substituted with one of W and X being N- (R 15 ), The other is a sulfur atom or an oxygen atom, and one of Y and Z is N- (R 15 And the other is a sulfur atom or an oxygen atom, and R 15
  • Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms; Ring structure C is a benzo [1,2-b: 4,5-b ′] dihetero ring represented by formula (C3), and ring structure A and ring structure B independently have a substituent.
  • An aromatic heterocycle optionally having one of W and X being N- (R 15 And the other is a sulfur atom or an oxygen atom, Y is the same as X, Z is the same as W, R 15 Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms; Ring structure C is a benzo [1,2-b: 4,5-b ′] diheteroyl ring represented by formula (C3), ring structure A and ring structure B are the same, and have a substituent.
  • Ring structure C is a benzo [1,2-b: 4,5-b ′] dihetero ring represented by formula (C3), and ring structure A and ring structure B independently have a substituent.
  • An optionally substituted benzene ring wherein one of W and X is N- (R 15 And the other is a sulfur atom or an oxygen atom, Y is the same as X, Z is the same as W, R 15 Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms; Ring structure C is a benzo [1,2-b: 4,5-b ′] dihetero ring represented by formula (C3), ring structure A and ring structure B are the same, and a halogen atom, alkyl Benzene ring optionally having a group, a (trialkyl) silyl group, an aryl group or a heteroaryl group, and one of W and X is N- (R 15 And the other is a sulfur atom or an oxygen atom, Y is the same as X, Z is the same as W, R 15 Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms; Ring structure C is a benzo [1,2-b:
  • R 15 Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms; Ring structure C is a benzo [1,2-b: 4,5-b ′] dihetero ring represented by formula (C3), ring structure A and ring structure B are the same, and a halogen atom, alkyl A naphthalene ring optionally having a group, a (trialkyl) silyl group, an aryl group or a heteroaryl group, and one of W and X is N- (R 15 ), The other is a sulfur atom or an oxygen atom, and one of Y and Z is N- (R 15 And the other is a sulfur atom or an oxygen atom, and R 15 Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms; Ring structure C is a benzo [1,2-b: 4,5-b ′] dihetero ring represented by formula (C3), ring structure A and ring structure B are the same, and a halogen
  • a thiophene ring wherein one of W and X is N- (R 15 And the other is a sulfur atom, an oxygen atom or a selenium atom, and one of Y and Z is N- (R 15 And the other is a sulfur atom, an oxygen atom or a selenium atom, and R 15
  • Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms; Ring structure C is a benzo [1,2-b: 4,5-b ′] dihetero ring represented by formula (C3), and ring structure A and ring structure B independently have a substituent.
  • a thiophene ring wherein one of W and X is N- (R 15 ), The other is a sulfur atom or an oxygen atom, and one of Y and Z is N- (R 15 And the other is a sulfur atom or an oxygen atom, and R 15
  • Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms; Ring structure C is a benzo [1,2-b: 4,5-b ′] diheteroyl ring represented by formula (C3), ring structure A and ring structure B are the same, and have a substituent.
  • An optionally substituted thiophene ring wherein one of W and X is N- (R 15 And the other is a sulfur atom or an oxygen atom, Y is the same as X, Z is the same as W, R 15 Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms; Ring structure C is a benzo [1,2-b: 4,5-b ′] dihetero ring represented by formula (C3), ring structure A and ring structure B are the same, and a halogen atom, alkyl A thiophene ring optionally having a group, a (trialkyl) silyl group, an aryl group or a heteroaryl group, and one of W and X is N- (R 15 ), The other is a sulfur atom or an oxygen atom, and one of Y and Z is N- (R 15 And the other is a sulfur atom or an oxygen atom, and R 15 Compound (1) wherein is an alkyl group having 1 to 30 carbon
  • An optionally substituted thiophene ring wherein one of W and X is N- (R 15 ), The other is a sulfur atom, Y is the same as X, Z is the same as W, R 15 Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms; Ring structure C is a benzo [1,2-b: 4,5-b ′] dihetero ring represented by formula (C3), ring structure A and ring structure B are the same, and a halogen atom, alkyl A thiophene ring optionally having a group, a (trialkyl) silyl group, an aryl group or a heteroaryl group, and one of W and X is N- (R 15 ), The other is a sulfur atom, Y is the same as X, Z is the same as W, R 15 Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms; Ring structure C is a benzo [1,2-b: 4,5-b
  • An optionally substituted benzo [b] thiophene ring wherein one of W and X is N- (R 15 And the other is a sulfur atom or an oxygen atom, Y is the same as X, Z is the same as W, R 15 Compound (1) wherein is an alkyl group having 1 to 30 carbon atoms; Ring structure C is a benzo [1,2-b: 4,5-b ′] dihetero ring represented by formula (C3), ring structure A and ring structure B are the same, and a halogen atom, alkyl A benzo [b] thiophene ring optionally having a group, a (trialkyl) silyl group, an aryl group or a heteroaryl group, wherein one of W and X is N- (R 15 ), The other is a sulfur atom or an oxygen atom, and one of Y and Z is N- (R 15 And the other is a sulfur atom or an oxygen atom, and R 15 Compound (1) wherein
  • the compound (1) can form a thin film by a vacuum process. Moreover, since the compound (1) is excellent in solubility in an organic solvent, a thin film can be formed also by a method of applying to a substrate or the like.
  • the organic solvent include water; alcohol solvents such as methanol, ethanol, isopropyl alcohol, and butanol; aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene, trichlorobenzene, and fluorobenzene; dichloromethane, chloroform Halogenated aliphatic hydrocarbon solvents such as 1,2-dichloroethane, 1,1 ′, 2,2′-tetrachloroethane, tetrachloroethylene, and carbon tetrachloride; ether solvents such as diethyl ether, dioxane, tetrahydrofuran, and anisole; pent
  • the concentration of compound (1) in the solution obtained by dissolving compound (1) in an organic solvent is usually 0.001 to 50% by weight, preferably 0.01 to 10% by weight, 5% by weight is more preferred.
  • the solution may contain additives such as an antioxidant and a stabilizer as long as the carrier mobility of the thin film (organic semiconductor active layer) described later is not significantly impaired.
  • the above solution can be prepared, for example, by dissolving the compound (1) in an organic solvent, usually at 10 to 200 ° C., preferably at 20 to 150 ° C.
  • the manufacturing method of a compound (1) is demonstrated.
  • Ring structure C is a benzene ring represented by formula (C1), and X and Y are N- (R 5 Compound (1) which is a compound of formula (2): (In the formula, ring structure A, ring structure B, W and Z each have the same meaning as described above, ring structure C is a benzene ring represented by formula (C1), and R 2 And R 3 Each independently represents a halogen atom. ) (Hereinafter abbreviated as compound (2)) and formula (4): R 15 -NH 2 (4) (R 15 Is the same definition as above. ) It can manufacture by reaction with the amine compound shown below (it abbreviates as amine compound (4) hereafter).
  • Examples of the halogen atom represented by are bromine and iodine.
  • Examples of the compound (2) include the following compounds.
  • the reaction between the compound (2) and the amine compound (4) is preferably performed in an organic solvent.
  • the organic solvent may be any organic solvent inert to the above reaction, and may be an aromatic hydrocarbon solvent such as toluene or xylene, a halogenated aromatic hydrocarbon solvent such as chlorobenzene or o-dichlorobenzene, hexane or heptane.
  • Aliphatic hydrocarbon solvents such as chloroform and 1,2-dichloroethane, alcohol solvents having 1 to 4 carbon atoms such as methanol, isopropanol and t-butanol, and tetrahydrofuran, dioxane, dimethoxyethane and the like
  • Ether solvents aromatic hydrocarbon solvents and aliphatic hydrocarbon solvents are preferred, aromatic hydrocarbon solvents are more preferred, and toluene and xylene are particularly preferred. Two or more organic solvents may be used in combination.
  • the amount of the amine compound (4) to be used is generally 1 to 50 mol, preferably 2 to 20 mol, more preferably 2 to 15 mol, per 1 mol of compound (2).
  • compound (2) in the resulting solution is usually 0.0001 to 20 mol, preferably 0.001 to 10 mol, more preferably, per liter of solvent.
  • the amount of the solvent is 0.01 to 5 mol.
  • the reaction between the compound (2) and the amine compound (4) is preferably performed in the presence of a palladium catalyst and a base.
  • the amount of the palladium catalyst to be used is generally 0.0001 to 0.3 mol, preferably 0.0001 to 0.2 mol in terms of palladium atom, per 1 mol of compound (2).
  • the palladium catalyst can be usually prepared by bringing a ligand and a palladium compound into contact with each other in an organic solvent. Prior to the reaction, a palladium catalyst prepared by contacting a ligand and a palladium compound in an organic solvent may be used for the reaction. Moreover, you may prepare a palladium catalyst in a reaction system by making a ligand and a palladium compound contact in a reaction system.
  • the ligand may be coordinated to palladium and soluble in an organic solvent, and examples thereof include monodentate ligands, polydentate ligands, and carbene ligands. Are preferred, and monodentate phosphine ligands are more preferred.
  • Monodentate phosphine ligands include tri (n-butyl) phosphine, tri (t-butyl) phosphine, tricyclohexylphosphine, triphenylphosphine, tri (o-tolyl) phosphine, trinaphthylphosphine, diphenylnaphthylphosphine and dicyclohexylnaphthyl.
  • a phosphine is mentioned, A tri (t-butyl) phosphine is preferable.
  • bidentate ligand 2,2′-bis (diphenylphosphino) -1,1′-binaphthyl, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane 1,4-bis (diphenylphosphino) butane, 1,1 ′-(diphenylphosphino) ferrocene, 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene, 2,2′-bis ( Bidentate phosphine ligands having two phosphorus atoms, such as diphenylphosphino) diphenyl ether, 5,5′-bis (diphenylphosphino) -4,4′-bi (1,3-benzodioxole), and And bidentate aminophosphine ligands having one nitrogen atom and one phosphorus atom such as 2- (N, N-dimethyl)
  • the A commercially available ligand may be used, or a ligand produced by a known method may be used.
  • the amount of ligand used is usually 0.5 to 20 moles per mole of palladium atoms contained in the palladium compound.
  • Palladium compounds include palladium acetate, palladium chloride, dichlorobis (acetonitrile) palladium, palladium acetylacetonate, dichloro (cycloocta-1,5-diene) palladium, dibromobis (benzonitrile) palladium, di- ⁇ -chlorobis ( ⁇ -allyl).
  • Divalent palladium compounds such as dipalladium, dichlorobis (pyridine) palladium, dichlorobis (triphenylphosphine) palladium, dichloro- [1,1′-bis (diphenylphosphino) ferrocene] palladium / dichloromethane complex, and tris
  • Zero-valent palladium compounds such as dibenzylideneacetone) dipalladium, tris (dibenzylideneacetone) dipalladium / chloroform complex, tetrakis (triphenylphosphine) palladium
  • tris (dibenzylideneacetone) dipalladium, and tris (dibenzylideneacetone) dipalladium-chloroform complex Tris (dibenzylideneacetone) dipalladium, and tris (dibenzylideneacetone) dipalladium-chloroform complex.
  • a commercially available palladium compound may be used, or a palladium compound produced by a known method may be used.
  • Bases include alkaline earth metal hydroxides such as calcium hydroxide; alkaline metal carbonates such as potassium carbonate, sodium carbonate and cesium carbonate; alkaline earth metal carbonates such as magnesium carbonate, calcium carbonate and barium carbonate; phosphorus Alkali metal phosphates such as lithium phosphate, potassium phosphate, sodium phosphate; and sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium methoxide, potassium ethoxide, potassium t-butoxide, lithium t-butoxide
  • Alkali metal carbonates and alkali metal alkoxides are preferred, alkali metal alkoxides are more preferred, and alkali metal alkoxides having 1 to 6 carbon atoms are particularly preferred.
  • the amount of the base to be used is generally 0.1 to 25 mol, preferably 1 to 20 mol, more preferably 2 to 10 mol, per 1 mol of compound (2).
  • the reaction temperature is usually in the range of 0 ° C. to the reflux temperature of the reaction mixture, and preferably 40 to 200 ° C.
  • the reaction time is usually 1 minute to 120 hours. After carrying out the reaction for a predetermined time, the reaction can be quenched, for example, by adding water or dilute hydrochloric acid to the reaction mixture.
  • compound (1) After quenching the reaction, compound (1) can be taken out by carrying out usual post-treatment operations such as extraction and washing. The extracted compound (1) can be further purified by ordinary purification means such as recrystallization, sublimation and various chromatography.
  • Compound (2) can be produced, for example, by the method described in JP2008-081494A.
  • Ring structure C is a benzene ring represented by formula (C1), and W and Z are independently N- (R 15 Compound (1) which is a compound of formula (3) (In the formula, ring structure A, ring structure B, X and Y represent the same meaning as described above, ring structure C is a benzene ring represented by formula (C1), and R 4 And R 5 Independently represents a halogen atom.
  • the reaction between the compound (3) and the amine compound (4) is preferably performed in an organic solvent.
  • the organic solvent may be any organic solvent inert to the above reaction, and may be an aromatic hydrocarbon solvent such as toluene or xylene, a halogenated aromatic hydrocarbon solvent such as chlorobenzene or o-dichlorobenzene, hexane, heptane or dimethoxy.
  • Aliphatic hydrocarbon solvents such as ethane, halogenated aliphatic hydrocarbon solvents such as chloroform and 1,2-dichloroethane, alcohol solvents having 1 to 4 carbon atoms such as methanol, isopropanol and t-butanol, and tetrahydrofuran and dioxane Ether solvents
  • aromatic hydrocarbon solvents and aliphatic hydrocarbon solvents are preferred, aromatic hydrocarbon solvents are more preferred, and toluene and xylene are particularly preferred.
  • Two or more organic solvents may be used in combination.
  • the amount of the amine compound represented by formula (4) to be used is generally 1 to 50 mol, preferably 2 to 20 mol, and more preferably 2 to 15 mol, relative to 1 mol of compound (3).
  • compound (3) in the resulting solution is usually 0.0001 to 20 mol, preferably 0.001 to 10 mol, more preferably, per liter of solvent.
  • the amount of the solvent is 0.01 to 5 mol.
  • the reaction between the compound (3) and the amine compound (4) is preferably performed in the presence of a palladium catalyst and a base.
  • the amount of the palladium catalyst to be used is generally 0.0001 to 0.3 mol, preferably 0.0001 to 0.2 mol in terms of palladium atom, per 1 mol of compound (3).
  • the palladium catalyst can be usually prepared by bringing a ligand and a palladium compound into contact with each other in an organic solvent. Prior to the reaction, a palladium catalyst prepared by contacting a ligand and a palladium compound in an organic solvent may be used for the reaction. Moreover, you may prepare a palladium catalyst in a reaction system by making a ligand and a palladium compound contact in a reaction system.
  • a ligand the thing similar to the ligand used in reaction of the said compound (2) and an amine compound (4) is mentioned.
  • Examples of the palladium compound include those similar to the palladium compound used in the reaction between the compound (2) and the amine compound (4).
  • Examples of the base include those similar to the base used in the reaction of the compound (2) and the amine compound (4).
  • the amount of the base to be used is generally 0.1 to 25 mol, preferably 1 to 20 mol, more preferably 2 to 10 mol, per 1 mol of compound (3). It is preferable that the amount of the base used be 0.1 mol or more with respect to 1 mol of the compound (3) because the amount of unreacted amine compound tends to decrease.
  • the reaction temperature of the reaction between the compound (3) and the amine compound (4) is usually in the range of 0 ° C. to the reflux temperature of the reaction mixture, preferably 40 to 200 ° C.
  • the reaction time is usually 1 minute to 120 hours.
  • Compound (3) is, for example, formula (5): (In the formula, ring structure A, ring structure B, ring structure C, X and Y have the same definition as in formula (3), and R 6 And R 7 Independently represents a hydrogen atom or a halogen atom. However, R 6 And R 7 Any one of is a hydrogen atom.
  • the reaction between the compound (5) and the halogenating agent is preferably performed in an organic solvent.
  • an organic solvent the thing similar to the organic solvent used in reaction of a compound (3) and an amine compound (4) is mentioned, Toluene, chloroform, carbon tetrachloride and N, N-dimethylformamide are preferable.
  • halogenating agents include N-bromosuccinimide, 2-bromoacetamide, bromine, iodine, iodine-periodic acid combination, iodine monochloride-peracetic acid combination, and benzyltrimethylammonium dichloroiodide-zinc chloride (II ), And a combination of N-bromosuccinimide, bromine and iodine-periodic acid is preferable.
  • the amount of the halogenating agent to be used is generally 0.1-50 mol, preferably 0.5-20 mol, more preferably 1-10 mol, per 1 mol of compound (5).
  • compound (5) in the resulting solution is usually 0.0001 to 20 mol, preferably 0.001 to 10 mol, more preferably, per liter of solvent.
  • the amount of the solvent is 0.01 to 5 mol.
  • an additive such as benzoyl peroxide or azobisbutyronitrile may be added to the catalytic amount reaction system.
  • the reaction temperature is usually in the range of ⁇ 78 ° C. to the reflux temperature of the reaction mixture, preferably ⁇ 20 ° C. to 50 ° C.
  • the reaction time is usually 1 minute to 48 hours.
  • the reaction can be quenched, for example, by adding water or dilute hydrochloric acid to the reaction mixture.
  • the compound (3) can be taken out by carrying out ordinary post-treatment operations such as extraction and washing.
  • the extracted compound (3) can be further purified by ordinary purification means such as recrystallization, sublimation and various chromatography.
  • Compound (3) and compound (5) can be produced, for example, by the method described in JP-A-2008-081494.
  • Ring structure C is a benzene ring represented by formula (C1), and W and Z are independently N- (R 5 Compound (1) which is a compound of formula (6) (In the formula, ring structure A, ring structure B, X and Y represent the same meaning as described above, and ring structure C represents a benzene ring represented by formula (C1).)
  • a compound represented by formula hereinafter abbreviated as compound (6)
  • compound (6) was cyclized, and the resulting compound and formula (7): R 15 -X 1 (7) (R 15 Represents the same meaning as above, and X 1 Represents a halogen atom. ) It can also manufacture by making the compound shown below (it abbreviates as a compound (7) hereafter) react.
  • halogen atom represented by are bromine atom and iodine atom.
  • the cyclization reaction of compound (6) is described in, for example, Org. Lett. , 2010, 12, 3164, by heating the compound (6) in the presence of phosphonates such as triethyl phosphonate.
  • the reaction between the compound obtained by the cyclization reaction of compound (6) and compound (7) is usually carried out under the same conditions as the alkylation reaction of the amino group.
  • Examples of the compound (6) include the following compounds.
  • Compound (6) is, for example, formula (X): (Wherein X and Y represent the same meaning as described above, ring structure C represents a benzene ring represented by formula (C1), and R 50 And R 51 Independently represents a halogen atom.
  • ring structure A represents the same meaning as described above, and R 52 And R 53 Each independently represents a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an aryloxy group having 6 to 20 carbon atoms, or R 52 And R 53 Combine to form a boron-containing ring with the boron atom to which they are bonded.
  • compound (Y) (Hereinafter abbreviated as compound (Y)) and a Suzuki coupling reaction.
  • R 50 And R 51 Examples of the halogen atom represented by the formula include a chlorine atom, a bromine atom and an iodine atom.
  • R 52 And R 53 Examples of the alkyl group having 1 to 10 carbon atoms represented by: methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group , Cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, 1,2-dimethylpropyl group, etc., linear, branched or cyclic Of the alkyl group.
  • alkoxy group having 1 to 10 carbon atoms examples include methoxy group, ethoxy group, n-propoxy group, n-butoxy group, and n-hexanoxy group.
  • aryloxy group having 6 to 20 carbon atoms examples include phenoxy group, 1-naphthoxy group, and 2-naphthoxy group.
  • benzo [1,2-b: 4,5-b ′] diheteroal is reacted with n-butyllithium, and the resulting product and tetrahalomethane are reacted. It can be produced by reacting.
  • a compound in which the ring structure C is a hetero [3,2-b] heterol ring represented by the formula (C2) or a benzo [1,2-b: 4,5-b ′] diheterol ring represented by the formula (C3) (1) is, for example, the formula (8): (In the formula, ring structure A, ring structure B, W and Z represent the same meaning as described above, and ring structure C represents a hetero [3,2-b] heterol ring represented by formula (C2) or formula (C3).
  • a benzo [1,2-b: 4,5-b ′] diheteroyl ring represented by 8 And R 9 Independently represents a halogen atom.
  • the ring structure C is a hetero [3,2-b] heterol ring represented by the formula (C2) or a benzo [1,2-b: 4,5-b ′] diheteroyl ring represented by the formula (C3).
  • Certain compounds (1) have the formula (9): (In the formula, ring structure A, ring structure B, W and Z have the same meaning as described above, and ring structure C represents a hetero [3,2-b] heterol ring represented by formula (C2) or formula (C3).
  • a benzo [1,2-b: 4,5-b ′] diheteroyl ring represented by 8 And R 9 Represents the same meaning as above.
  • It can manufacture also by the method of making the compound (henceforth abbreviating as a compound (9)) shown by these, and an amine compound (4) react.
  • R 8 And R 9 Examples of the halogen atom represented by are bromine atom and iodine atom.
  • Examples of the compound (8) and the compound (9) include the following compounds.
  • the reaction between the compound (8) and the amine compound (4) and the reaction between the compound (9) and the amine compound (4) are the same as the reaction between the compound (2) and the amine compound (4). Can be implemented.
  • the amount of the amine compound (4) to be used is generally 1-50 mol, preferably 2-20 mol, more preferably 2-15 mol, per 1 mol of compound (8) or compound (9). is there.
  • the compound (8) or the compound (9) is dissolved in the organic solvent, the compound (8) or the compound (9) in the resulting solution is usually 0.0001 to 20 mol, preferably, The solvent is used in an amount of 0.001 to 10 mol, more preferably 0.01 to 5 mol.
  • the above reaction is preferably performed in the presence of a palladium catalyst and a base.
  • the amount of the palladium catalyst to be used is generally 0.0001 to 0.3 mol, preferably 0.0001 to 0.2 mol in terms of palladium atom, per 1 mol of compound (8) or compound (9). is there.
  • the palladium catalyst can be usually prepared by bringing a ligand and a palladium compound into contact with each other in an organic solvent. Prior to the reaction, a palladium catalyst prepared by contacting a ligand and a palladium compound in an organic solvent may be used for the reaction. Moreover, you may prepare a palladium catalyst in a reaction system by making a ligand and a palladium compound contact in a reaction system.
  • the thing similar to the ligand used in reaction of the said compound (2) and an amine compound (4) is mentioned.
  • the palladium compound include those similar to the palladium compound used in the reaction between the compound (2) and the amine compound (4).
  • the base include those similar to the base used in the reaction of the compound (2) and the amine compound (4).
  • the amount of the base to be used is generally 0.1 to 25 mol, preferably 1 to 20 mol, more preferably 2 to 10 mol, per 1 mol of compound (8) or compound (9). It is preferable that the amount of the base used is 0.1 mol or more with respect to 1 mol of the compound (8) or the compound (9) because the amount of unreacted amine compound tends to decrease.
  • the reaction temperature of the reaction between the compound (3) and the amine compound (4) is usually in the range of 0 ° C. to the reflux temperature of the reaction mixture, preferably 40 to 200 ° C.
  • the reaction time is usually 1 minute to 120 hours.
  • the reaction can be quenched, for example, by adding water or dilute hydrochloric acid to the reaction mixture.
  • compound (1) can be taken out by carrying out usual post-treatment operations such as extraction and washing.
  • the extracted compound (1) can be further purified by ordinary purification means such as recrystallization, sublimation and various chromatography.
  • Compound (8) is, for example, formula (10): (In the formula, ring structure A, ring structure B, ring structure C, W and Z have the same meaning as described above, and R 20 And R 21 Independently represents a hydrogen atom or a halogen atom. However, R 20 And R 21 Any one of these is a hydrogen atom. ) It can manufacture by reaction with the compound (henceforth abbreviated as compound (10)) shown by these, and a halogenating agent.
  • Compound (9) is represented, for example, by the formula (11): (In the formula, ring structure A, ring structure B, ring structure C, X, Y, R 20 And R 21 Represents the same meaning as above.
  • the reaction between the compound (10) and the halogenating agent and the reaction between the compound (11) and the halogenating agent are each preferably carried out in an organic solvent.
  • the organic solvent include the same organic solvents as those used in the reaction between the compound (5) and the halogenating agent, and toluene, chloroform, carbon tetrachloride and N, N-dimethylformamide are preferable.
  • the amount of the halogenating agent to be used is generally 0.1-50 mol, preferably 0.5-20 mol, more preferably 1-10 mol, per 1 mol of compound (10) or compound (11). Is a mole.
  • compound (10) or compound (11) in the resulting solution is usually 0.0001 to 20 mol, preferably The solvent is used in an amount of 0.001 to 10 mol, more preferably 0.01 to 5 mol.
  • Halogenating agents include N-bromosuccinimide, 2-bromoacetamide, bromine, iodine, iodine-periodic acid combination, iodine monochloride-peracetic acid combination, and benzyltrimethylammonium dichloroiodide-zinc chloride (II ) And the like, and is a combination of N-bromosuccinimide, bromine, and iodine-periodic acid.
  • an additive such as benzoyl peroxide or azobisbutyronitrile may be added to the catalytic amount reaction system.
  • the reaction temperature is usually in the range of ⁇ 78 ° C. to the reflux temperature of the reaction mixture, preferably ⁇ 20 ° C. to 50 ° C.
  • the reaction time is usually 1 minute to 48 hours.
  • the reaction can be quenched, for example, by adding water to the reaction mixture.
  • compound (1) can be taken out by carrying out usual post-treatment operations such as extraction and washing.
  • the extracted compound (1) can be further purified by ordinary purification means such as recrystallization, sublimation and various chromatography.
  • Compound (8) and compound (9) can also be produced, for example, by the method described in JP2008-081494A. Since the compound (1) of the present invention is soluble in an organic solvent, a solution containing the compound (1) and the organic solvent is prepared by applying a thin film (organic semiconductor active layer) of the present invention to be described later by coating film formation. It is preferable from obtaining.
  • organic solvent capable of dissolving the compound (1) examples include aromatic hydrocarbon solvents such as benzene, toluene, xylene, tetralin, mesitylene, chlorobenzene, o-dichlorobenzene, trichlorobenzene, fluorobenzene, anisole, dichloromethane, chloroform, 1 , 2-dichloroethane, 1,1 ′, 2,2′-tetrachloroethane, tetrachloroethylene, carbon tetrachloride and other halogenated aliphatic hydrocarbon solvents, diethyl ether, dioxane, tetrahydrofuran and other ether solvents, pentane, hexane, heptane, Aliphatic hydrocarbon solvents such as octane and cyclohexane, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl
  • the concentration of compound (1) in the solution in which compound (1) is dissolved is usually 0.001 to 50% by weight, preferably 0.01 to 10% by weight, and more preferably 0.1 to 5% by weight.
  • the solution may contain only the compound (1), or an antioxidant, a stabilizer, and an organic semiconductor material different from the compound (1) as long as the mobility of the thin film described later is not significantly impaired.
  • an organic insulating material or the like may be included.
  • the organic semiconductor material different from the compound (1) may be a low molecular material or a polymer material.
  • the polymer material may be one obtained by crosslinking a polymer.
  • a polymer material is used. Specific examples include polyacetylene and derivatives thereof, polythiophene and derivatives thereof, polythienylene vinylene and derivatives thereof, polyphenylene and derivatives thereof, polyphenylene vinylene and derivatives thereof, polypyrrole and derivatives thereof, polyaniline and derivatives thereof, polytriarylamine and derivatives thereof.
  • the content of the compound (1) is preferably 10% by weight or more, more preferably 20% by weight or more with respect to 100% by weight of the total of the organic semiconductor material different from the compound (1) and the compound (1).
  • the organic insulating material may be a low molecular material or a polymer material.
  • the polymer material may be a polymer obtained by crosslinking a polymer. Preferably, a polymer material is used.
  • polystyrene polycarbonate, polydimethylsiloxane, nylon, polyimide, cyclic olefin copolymer, epoxy polymer, cellulose, polyoxymethylene, polyolefin polymer, polyvinyl polymer, polyester polymer, polyether polymer, polyamide polymer.
  • Fluoropolymers biodegradable plastics, phenolic resins, amino resins, unsaturated polyester resins, diallyl phthalate resins, epoxy resins, polyimide resins, polyurethane resins, silicone resins, and copolymers combining various polymer units. .
  • the content of the compound (1) with respect to the total of 100% by weight of the organic insulating material and the compound (1) is preferably 10% by weight or more, and more preferably 20% by weight or more.
  • a solution containing the compound (1) and an organic solvent can be prepared by mixing and dissolving the compound (1) in a solvent, usually at about 10 ° C. to 200 ° C., preferably at about 20 ° C. to 150 ° C. it can. Then, the thin film and organic-semiconductor device of this invention are demonstrated.
  • the thin film of this invention is a thin film containing a compound (1), and the thin film which consists only of a compound (1) is preferable.
  • the thickness of the thin film is usually 1 nm to 10 ⁇ m, preferably 5 nm to 1 ⁇ m.
  • the thin film of the present invention may exhibit luminescence, and in that case, it can be used as a luminescent thin film.
  • the “luminescent thin film” means a thin film that emits light under conditions of light or electrical stimulation.
  • a light-emitting thin film is useful as a material for a light-emitting element, and a light-emitting element having a light-emitting thin film is one of the present invention.
  • the light emitting device of the present invention is useful as a material for organic light emitting diodes and the like.
  • the “light emitting element” means a device using a light emitting thin film.
  • the thin film of this invention may show the same electroconductivity as a semiconductor, In that case, it can be used as a conductive thin film.
  • the “conductive thin film” means a thin film that exhibits conductivity under conditions of light and electrical stimulation.
  • a conductive thin film having the same conductivity as that of a semiconductor may be used as the organic semiconductor active layer.
  • the conductive thin film is useful as a material for an organic semiconductor device such as an organic transistor described later.
  • Examples of the method for forming a thin film of the present invention include coating film formation.
  • the coating film forming process means a film forming process including a step of dissolving the compound (1) in a solvent and applying the obtained solution to a substrate or an insulator layer.
  • Examples of the coating method include a casting method, a dip coating method, a die coater method, a roll coater method, a bar coater method, a spin coating method, an ink jet method, a screen printing method, an offset printing method, and a micro contact printing method. These techniques may be used alone or in combination of two or more.
  • a solution containing the compound (1) and an organic solvent is applied to a substrate or an insulating layer to form a coating film, and then the solvent contained in the coating film is removed to form a thin film on the substrate or the insulating layer. Is formed.
  • the organic solvent is usually removed by natural drying, heat drying, reduced pressure drying, ventilation drying or the like. You may remove an organic solvent combining these 2 or more types of drying.
  • Natural drying or heat drying is preferred in that the operation is simple.
  • the removal of the organic solvent is carried out, for example, by standing in the atmosphere or heating the substrate with a hot plate (for example, 40 ° C. to 250 ° C., preferably 50 ° C. to 200 ° C.).
  • the thin film of the present invention can also be formed by coating film formation using a dispersion liquid in which the compound (1) is dispersed in a solvent. Also in this case, it can be carried out in the same manner as the coating film forming process using the solution of the compound (1). In this case, water can be used as the solvent in addition to the organic solvent.
  • the thin film of the present invention can be formed by a simple method such as the above-described coating film forming process.
  • the thin film of the present invention can also be formed by a method of forming the thin film by subjecting the compound (1) to a vacuum process such as a vacuum deposition method, a sputtering method, a CVD method, or a molecular beam epitaxial growth method.
  • the method for forming a thin film by a vacuum deposition method is a method in which the compound (1) is heated in a crucible or a metal boat under vacuum, and the evaporated compound (1) is deposited on a substrate or an insulator material.
  • the degree of vacuum during vapor deposition is usually 1 ⁇ 10 -1 Pa or less, preferably 1 ⁇ 10 -3 Pa or less.
  • the substrate temperature during vapor deposition is usually 0 ° C.
  • the deposition rate is usually 0.001 nm / sec to 10 nm / sec, preferably 0.01 nm / sec to 1 nm / sec.
  • the film thickness of the thin film containing the compound (1) obtained by the coating film forming process or the vacuum process can be appropriately adjusted depending on the element structure of the organic semiconductor device, but is preferably 1 nm to 10 ⁇ m, and more preferably Is 5 nm to 1 ⁇ m.
  • the organic transistor of the present invention includes the thin film of the present invention as an organic semiconductor active layer.
  • the organic transistor contains the compound (1) of the present invention, it has a high carrier mobility, preferably 10 -6 cm 2
  • the carrier mobility is higher than / Vs.
  • the carrier mobility can be calculated from the measurement result and the following formula (a) by measuring the drain current and the gate voltage using a parameter analyzer or the like.
  • Id (W / 2L) ⁇ Ci (Vg ⁇ Vt) 2 (A) (Where, Id is the drain current in the saturation region of the electrical characteristics, L is the channel length of the organic transistor, W is the channel width of the organic transistor, and Ci is the capacitance per unit area of the gate insulating film) Vg represents the gate voltage, and Vt represents the threshold voltage of the gate voltage.)
  • An organic field effect transistor is mentioned as an organic transistor of this invention.
  • the organic field effect transistor usually has a structure in which a source electrode and a drain electrode are in contact with an organic semiconductor active layer (hereinafter abbreviated as a semiconductor layer), and further, a source electrode and a drain electrode, or a semiconductor layer
  • an insulating layer dielectric layer
  • a gate electrode may be in contact with the insulating layer. Examples of the element structure of such an organic transistor include the following structures (1) to (4).
  • (1) Structure comprising substrate / gate electrode / insulator layer / source electrode / drain electrode / semiconductor layer; (2) Structure comprising substrate / gate electrode / insulator layer / semiconductor layer / source electrode / drain electrode; (3) Structure consisting of substrate / semiconductor layer + source electrode / drain electrode / insulator layer / gate electrode; (4) Structure consisting of substrate / source electrode (or drain electrode) / semiconductor layer + insulator layer + gate electrode / drain electrode (or source electrode), When there are two or more semiconductor layers in each structure, the respective semiconductor layers may be provided in the same plane, or the semiconductor layers may be stacked. In each of the above structures, two or more source electrodes, drain electrodes, and gate electrodes may exist.
  • the material constituting the source electrode, the drain electrode and the gate electrode is not limited as long as it is a conductive material generally used in the organic transistor field.
  • a conductive material generally used in the organic transistor field.
  • conductive polymers whose conductivity has been improved by doping or the like, conductive polyaniline, conductive polypyrrole, conductive polythiophene, polyethylenedioxythiophene and polystyrenesulfonic acid complex. Among them, those having a small electric resistance at the contact surface with the semiconductor layer are preferable.
  • Two or more electrode materials may be used in combination.
  • the film thickness of the electrode varies depending on the material, but is usually from 0.1 nm to 10 ⁇ m, preferably from 0.5 nm to 5 ⁇ m, more preferably from 1 nm to 3 ⁇ m.
  • the thickness of the gate electrode may be larger than the above thickness.
  • a method for forming the electrode film various known methods may be mentioned. Specific examples include a vacuum deposition method, a sputtering method, a coating method, a thermal transfer method, a printing method, and a sol-gel method. It is preferable to perform patterning as needed during film formation or after film formation. Various methods can be used as a patterning method. Specifically, a photolithographic method combining photoresist patterning and etching may be used. In addition, printing methods such as ink jet printing, screen printing, offset printing, letterpress printing, and soft lithography techniques such as a microcontact printing method are also included. It is also possible to perform patterning by combining two or more patterning methods.
  • the source electrode and drain electrode used in the organic transistor of the present invention may be subjected to surface treatment. It is preferable that the surface of the electrode in contact with the thin film (organic semiconductor active layer) of the present invention is subjected to surface treatment because the transistor characteristics of the organic transistor including the thin film tend to be improved.
  • Surface treatment includes 1-octylthiol, 1-perfluorooctylthiol, 1-octadecylthiol, saturated hydrocarbon compounds having a thiol group (—SH) such as 1-perfluorooctadecylthiol, benzenethiol, perfluorobenzenethiol
  • a thiol compound such as an aromatic compound having a thiol group such as a heterocyclic aromatic compound having a thiol group such as thienyl thiol or perfluorothienyl thiol in an alcohol solvent
  • the electrode is The method of immersing is mentioned.
  • Inorganic oxides include silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, tin oxide, vanadium oxide, barium strontium titanate, barium zirconate titanate, lead zirconate titanate, lead lanthanum titanate, strontium titanate, Examples thereof include barium titanate, barium magnesium fluoride, bismuth titanate, strontium bismuth titanate, strontium bismuth tantalate, bismuth tantalate niobate and yttrium trioxide, with silicon oxide, aluminum oxide, tantalum oxide and titanium oxide being preferred.
  • organic compound films include polystyrene, polyimide, polyamide, polyester, polyacrylate, photo-curing resin based on radical photopolymerization or photocation polymerization, copolymers containing structural units derived from acrylonitrile, polyvinylphenol, polyvinyl alcohol , Novolak resin and cyanoethyl pullulan, and polystyrene, polyimide, polyvinylphenol and polyvinyl alcohol are preferred. Two or more insulating layer materials may be used in combination.
  • the thickness of the insulating layer varies depending on the material, but is usually from 0.1 nm to 100 ⁇ m, preferably from 0.5 nm to 50 ⁇ m, more preferably from 5 nm to 10 ⁇ m.
  • Various known methods can be used as a method for forming the insulating layer. Specifically, spin coating, spray coating, dip coating, casting, bar coating, blade coating and other coating methods, screen printing, offset printing, inkjet printing methods, vacuum deposition methods, molecular beam epitaxial growth methods, ion cluster beams And dry process methods such as ion plating, sputtering, atmospheric pressure plasma, and CVD.
  • Examples thereof include a sol-gel method, alumite on aluminum, and a method of forming an oxide film on a metal such as a thermal oxide film of silicon.
  • substrate the board or sheet
  • Resin sheets include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), cellulose triacetate (TAC) and cellulose acetate propionate (CAP).
  • the thickness of the substrate is preferably 1 ⁇ m to 10 mm, and more preferably 5 ⁇ m to 5 mm.
  • an insulator layer or substrate that has been subjected to surface treatment may be used as the insulator layer or substrate in contact with the semiconductor layer. By performing surface treatment on the insulator layer on which the semiconductor layer is stacked, transistor characteristics of the element can be improved.
  • Surface treatment includes hydrophobic treatment with hexamethyldisilazane, octadecyltrichlorosilane, octyltrichlorosilane, phenethyltrichlorosilane, acid treatment with hydrochloric acid, sulfuric acid, hydrogen peroxide, sodium hydroxide, potassium hydroxide, hydroxylation Alkaline treatment with calcium, ammonia, etc., ozone treatment, fluorination treatment, plasma treatment with oxygen, argon, etc., formation treatment of Langmuir / Blodgett film, other insulators and semiconductor thin film formation treatment, mechanical treatment, Examples include electrical treatment such as corona discharge, rubbing treatment using fibers, and the like, and two or more treatment methods may be used in combination.
  • Examples of the surface treatment method include a vacuum deposition method, a sputtering method, a coating method, a printing method, a sol-gel method, and the like.
  • a protective film made of a resin or an inorganic compound may be provided on the semiconductor layer. By forming the protective film, the influence of outside air can be suppressed and the driving of the transistor can be stabilized.
  • the organic transistor of this invention can be used for organic devices, such as a liquid crystal display element, an organic electroluminescent element, an electronic paper, a sensor, and RFIDs (radio frequency identification cards).
  • Apparatus LC-250HS manufactured by Nippon Analytical Industrial Co., Ltd.
  • the obtained product was identified based on the measurement result of 1 H-NMR, HRMS and / or LC-HRMS.
  • 1 H-NMR measurement apparatus EX270 manufactured by JEOL Ltd. or DPX300 manufactured by BRUKER HRMS measurement device: JEOL Ltd.
  • Example 1 Production of 3,6-dibromo-2,5-diiodothieno [3,2-b] thiophene] 2,5-Dibromothieno [3,2-b] thiophene was prepared by reacting thieno [3,2-b] thiophene with N-bromosuccinimide (see Dalton Trans., 2005, 874).
  • 3,6-Dibromothieno [3,2-b] thiophene was prepared by reacting 2,5-dibromothieno [3,2-b] thiophene with lithium diisopropylamide (Org. Lett., 2007, 9 , 1005).
  • 12.00 g of 3,6-dibromothieno [3,2-b] thiophene 8.18 g of iodine, 3.54 g of iodic acid, 0.39 g of sulfuric acid, four 132 ml of carbon chloride, 264 ml of acetic acid and 41 ml of water were charged.
  • the resulting mixture was stirred at 45 ° C. for 20 hours under a nitrogen atmosphere.
  • 0.45 g of iodine and 0.20 g of iodic acid were added, and the mixture was further stirred at 45 ° C. for 10 hours in a nitrogen atmosphere.
  • the resulting reaction mixture was cooled to room temperature and then filtered.
  • the obtained solid was washed with water and methanol, and then dried under reduced pressure. Further, recrystallization (solvent: monochlorobenzene) was performed, and 3,6-dibromo-2,5-diiodhieno [ 19.5 g of white crystals of 3,2-b] thiophene were obtained with a yield of 88%.
  • Example 2 Production of 3,6-dibromo-2,5-bis (3-bromobenzo [b] thiophen-2-yl) -thieno [3,2-b] thiophene In a 500 mL four-necked flask equipped with a stirrer, a thermometer, a condenser and a dropping funnel, 22.5 g of 2,3-dibromobenzo [b] thiophene (manufactured by Aldrich) was charged.
  • the resulting mixture was heated to reflux under a nitrogen atmosphere and then refluxed for 24 hours.
  • the obtained reaction mixture was cooled to room temperature, water was added, and the mixture was extracted with toluene.
  • the obtained organic layer was dried over magnesium sulfate and filtered.
  • the resulting filtrate was concentrated under reduced pressure.
  • the obtained residue was purified by silica gel chromatography using a mixed solvent of hexane and toluene to which 0.2% volume ratio of triethylamine was added. The obtained solid was recrystallized from toluene.
  • the thickness of the chromium layer was 5 nm and the thickness of the gold layer was 40 nm.
  • the substrate was ultrasonically cleaned with acetone and isopropyl alcohol, dried, cleaned with oxygen plasma, and further heated at 80 ° C. for 5 minutes.
  • the channel width was 2 mm and the channel length was 50 ⁇ m.
  • the channel portion was treated with phenethyltrichlorosilane, the electrode portion was treated with pentafluorobenzenethiol, and then a 0.5 wt / vol% tetralin solution of the compound prepared in [Example 3] was added under a nitrogen atmosphere.
  • the film was dropped and a thin film (organic semiconductor active layer) was formed by spin coating.
  • a solution containing a fluorine-based polymer was dropped on the thin film, and an insulating layer was formed by spin coating.
  • the thickness of the thin film was 25 nm, and the thickness of the insulating layer was 300 nm.
  • chromium and aluminum were vapor-deposited in this order to provide a gate electrode, and an organic transistor as shown in FIG. 2 was manufactured.
  • the thickness of the chromium layer was 5 nm, and the thickness of the aluminum layer was 200 nm. The electrical characteristics of the obtained organic transistor were measured.
  • the change curve of the drain current (Id) with respect to the drain voltage (Vd) was favorable at a certain gate voltage (Vg), and had a saturation region at a high drain voltage. Further, when the negative gate voltage applied to the gate electrode is increased, the negative drain current is also increased. Therefore, it was confirmed that the obtained organic transistor was a p-type organic transistor. Furthermore, when the carrier mobility ⁇ of the organic transistor was calculated by the formula (a), the carrier mobility was 0.25 cm 2 / Vs.
  • Example 4 Production of 5,5′-dibromobenzo [1,2-b; 4,5-b ′] dithiophene Chem. Mater.
  • the obtained solution was cooled to ⁇ 78 ° C., and 8.73 ml of hexane solution of t-butyllithium (concentration: 1.59 M, manufactured by Kanto Chemical) was added over 5 minutes while maintaining about ⁇ 78 ° C. .
  • the resulting mixture was further stirred at the same temperature for 1 hour to obtain a reaction mixture A.
  • a solution obtained by dissolving 4.60 g of carbon tetrabromide (manufactured by Tokyo Chemical Industry) in 20 ml of dehydrated tetrohydrofuran was added to the reaction mixture A adjusted to ⁇ 78 ° C. over 10 minutes. The resulting mixture was stirred at the same temperature for an additional 4 hours.
  • the resulting mixture was heated to reflux under a nitrogen atmosphere and then refluxed for 4 hours. After cooling the obtained reaction mixture to room temperature, water and toluene were added and liquid-separated. The obtained organic layer was dried over magnesium sulfate and filtered. The resulting filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel chromatography using a mixed solvent of hexane and toluene to which triethylamine having a volume ratio of 0.2% was added. The obtained solid was recrystallized (solvent: toluene) to obtain 0.13 g of a yellow crystal of a compound represented by the following formula. Yield: 21%.
  • the substrate surface was subjected to silane treatment by immersing the UV irradiated substrate in a toluene solution containing phenylethyltrichlorosilane for 2 minutes.
  • a xylene solution containing the compound produced in [Example 7] at a concentration of 0.7% by weight was prepared, and the xylene solution was filtered through a membrane filter to prepare a coating solution.
  • the obtained coating solution was applied by spin coating on the surface of the silicon oxide film, source electrode and drain electrode of the silane-treated substrate.
  • the substrate with the surface coated with the coating solution is dried for 30 minutes on a hot plate at 50 ° C. in a nitrogen atmosphere, so that a thin film (organic semiconductor active layer, FIG.
  • Example 8 30 mL of a tetrahydrofuran solution of 3-bromo-2-iodothieno [3,2-b] thiophene (10 mmol) was cooled to ⁇ 78 ° C., and n-butyllithium (1.6 M, hexane solution) (10 mmol) was added dropwise to obtain The resulting mixture is stirred for 1 hour. Bu 3 SnCl (10 mmol) is added dropwise to the resulting solution, and the resulting mixture is stirred, then heated to 25 ° C. and further stirred for 1 hour.
  • Example 9 Compound (5 mmol) obtained in [Example 8], n-dodecylamine (25 mmol), tris (dibenzylideneacetone) dipalladium (1 mmol), sodium tert-butoxide (50 mmol), ( ⁇ ) -2,2 ′
  • a mixture of bis (diphenylphosphino) -1,1′-binaphthyl (4 mmol) and toluene (100 mL) is refluxed for 21 hours under a nitrogen atmosphere. The resulting reaction mixture is allowed to cool to room temperature, water is added, and the mixture is extracted with chloroform.
  • the resulting organic layer is dried over magnesium sulfate and filtered, and the resulting filtrate is concentrated under reduced pressure.
  • the compound shown by Formula (2-7) is obtained by refine
  • the compound represented by formula (2-7) is purified by sublimation.
  • [Manufacturing Example 3 of Thin Film and Organic Transistor Using the Thin Film as an Organic Semiconductor Active Layer] A metal mask for forming an organic semiconductor layer is placed on an n-doped silicon wafer with an SiO 2 thermal oxide film of 200 nm subjected to octyltrichlorosilane treatment to obtain a masked silicon wafer.
  • a tungsten boat containing the wafer and the compound represented by the formula (2-7) obtained in Example 9 in a chamber set to a vacuum degree of 1 ⁇ 10 ⁇ 3 Pascal or less The wafer is heated to a temperature in the range of room temperature (24 ° C.) to 150 ° C. while heating the boat, and a thin film of the compound represented by the formula (2-7) is formed on the portion not covered with the metal mask.
  • An organic semiconductor layer can be formed.
  • a metal mask for forming a source electrode and a drain electrode is placed on the surface of the organic semiconductor layer, and a 40 nm-thick gold layer is formed on the organic semiconductor layer by a similar vacuum evaporation method.
  • the organic transistor as shown in FIG. 1 can be manufactured by forming a source electrode and a drain electrode.
  • the compound represented by the formula (2-7) obtained in Example 9 is dissolved in o-xylene to prepare a solution having a concentration of the compound represented by the formula (2-7) of 0.3% by weight.
  • a metal mask for forming an organic semiconductor layer is placed on an n-doped silicon wafer with a SiO 2 thermal oxide film subjected to phenethyltrichlorosilane treatment to obtain a masked silicon wafer.
  • the above solution is applied to the wafer by a spin coating method to form a thin film made of the compound represented by formula (2-7). Furthermore, the thin film to be formed can be kept at 80 ° C. for 30 minutes, and an organic semiconductor layer made of a thin film of the compound represented by the formula (2-7) can be formed in a portion where the metal mask is not formed. Subsequently, after removing the metal mask, a metal mask for forming the source electrode and the drain electrode is placed on the surface of the organic semiconductor layer, and a 40 nm-thick gold layer is formed on the organic semiconductor layer by the same vacuum deposition method.
  • the organic transistor as shown in FIG. 1 can be manufactured by forming a source electrode and a drain electrode.
  • a polycyclic compound capable of providing a thin film suitable as an organic semiconductor active layer can be provided.

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Abstract

L'invention concerne un composé polycyclique représenté par la formule (1) [dans laquelle la structure cyclique C représente un noyau benzénique représenté par la formule (C1), un hétérocycle hétéro[3,2-b] représenté par la formule (C2), ou un dihétérocycle benzo[1,2-b:4,5-b'] représenté par la formule (C3) (dans laquelle P et Q représentent indépendamment un atome de soufre ou similaire); W, X, Y et Z représentant indépendamment un atome de soufre, N-(R15) ou similaire, au moins un reste choisi dans le groupe consistant en W, X, Y et Z représentant N-(R15); les structures cycliques A et B représentant indépendamment un cycle carboné aromatique ou similaire, les structures cycliques A et B représentant indépendamment un hétérocycle aromatique qui peut avoir un substituant lorsque la structure cyclique C représente un noyau benzénique représenté par la formule (C1) et X et Y représentant tous deux N-(R15); et les R15 représentant indépendamment un groupe alkyle ou similaire].
PCT/JP2011/055568 2010-03-05 2011-03-03 Composé polycyclique WO2011108765A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150144847A1 (en) * 2012-04-25 2015-05-28 Merck Patent Gmbh Conjugated polymers
CN105315298A (zh) * 2014-08-04 2016-02-10 中国科学院化学研究所 基于七并稠环单元的a-d-a共轭分子及其制备方法和应用
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