Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
  • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
  • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
  • C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
• • 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
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
  • H10K50/14—Carrier transporting layers
  • H10K50/16—Electron transporting layers
  • H10K50/165—Electron transporting layers comprising dopants
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
  • H10K71/10—Deposition of organic active material
  • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
  • H10K71/30—Doping active layers, e.g. electron transporting layers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
  • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
  • H10K71/421—Thermal treatment, e.g. annealing in the presence of a solvent vapour using coherent electromagnetic radiation, e.g. laser annealing
• • 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
  • H10K85/10—Organic polymers or oligomers
  • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
  • H10K85/115—Polyfluorene; Derivatives thereof
• • 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 novel compound and a method for producing the same.
• Non-Patent Document 1 discloses an organic thin film transistor using N-DMBI as an n-type doping material
• Patent Document 1 discloses an organic EL element using N-DMBI as an n-type doping material
• 2 discloses an n-type dopant precursor for doping an organic semiconductor material.
• n-type doping material that can be formed by a coating method.
• the compounds described as n-type doping materials in the above-described prior art documents are not always sufficient in electron donating property.
• an object of the present invention is to provide a novel compound that can be suitably used as a strong n-type doping material and a method for producing the same.
• a compound represented by formula (1) [Where: A 1 represents an oxygen atom, a sulfur atom, —NR 5 — or —PR 5 —. Two A 1 s may be the same or different from each other, and at least one A 1 is —NR 5 — or —PR 5 —.
• R 1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylsulfenyl group, a cycloalkylsulfenyl group, an arylsulfenyl group, or a disubstituted amino group, and these groups —CH 2 — in the group may be substituted with an oxygen atom, a sulfur atom, —NR 5 — or —C ( ⁇ O) O—, and a part or all of the hydrogen atoms in these groups are halogen atoms. May be substituted. However, two adjacent —CH 2 — are not substituted at the same time.
• R 1 s may be the same as or different from each other.
• R 2 is an alkyl group, cycloalkyl group, aryl group, alkoxy group, cycloalkoxy group, aryloxy group, alkylsulfenyl group, cycloalkylsulfenyl group, arylsulfenyl group, monovalent heterocyclic group, halogen atom or Represents a disubstituted amino group, and —CH 2 — in these groups may be substituted with an oxygen atom, a sulfur atom, —NR 5 — or —C ( ⁇ O) O—, Some or all of the hydrogen atoms may be substituted with halogen atoms.
• R 3 is an alkyl group, cycloalkyl group, aryl group, alkoxy group, cycloalkoxy group, aryloxy group, alkylsulfenyl group, cycloalkylsulfenyl group, arylsulfenyl group, monovalent heterocyclic group, halogen atom or Represents a disubstituted amino group, and —CH 2 — in these groups may be substituted with an oxygen atom, a sulfur atom, —NR 5 — or —C ( ⁇ O) O—, Some or all of the hydrogen atoms may be substituted with halogen atoms.
• R 1 is an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylsulfenyl group, a cycloalkylsulfenyl group, an arylsulfenyl group, or A disubstituted amino group
• R 1 is an alkoxy group, a cycloalkoxy group, an aryloxy group A group, an alkylsulfenyl group, a cycloalkyl
• R 4 represents a hydrogen atom, —C (R 6 ) 3 , —OR 7 , —N (R 7 ) 2 or —Si (R 7 ) 3, and —CH 2 — in these groups represents an oxygen atom, A sulfur atom, —NR 5 — or —C ( ⁇ O) O— may be substituted, and a part or all of the hydrogen atoms in these groups may be substituted with a halogen atom. However, two adjacent —CH 2 — are not substituted at the same time.
• R 5 represents an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and —CH 2 — in these groups represents an oxygen atom, a sulfur atom, —NR 8 — or —C ( ⁇ O).
• O— may be substituted, and some or all of the hydrogen atoms in these groups may be substituted with halogen atoms. However, two adjacent —CH 2 — are not substituted at the same time.
• the plurality of R 5 may be the same as or different from each other.
• R 6 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and a part or all of the hydrogen atoms in these groups may be substituted with a halogen atom.
• a plurality of R 6 may be the same or different from each other, and two R 6 may combine to form a ring.
• R 7 represents an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and a part or all of the hydrogen atoms in these groups may be substituted with a halogen atom.
• a plurality of R 7 may be the same or different from each other, and two R 7 may be bonded to form a ring.
• R 8 represents an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and a part or all of the hydrogen atoms in these groups may be substituted with a halogen atom. When a plurality of R 8 are present, the plurality of R 8 may be the same as or different from each other.
• m represents an integer of 0 to 3.
• n represents an integer of 0 to 4.
• [2] The compound according to [1], wherein two A 1 are both —NR 5 —. [3] The compound according to [1] or [2], which is a compound represented by the formula (2).
• R 1 , R 2 , R 3 , R 4 , R 5 and n are the same as defined above, and p represents an integer of 0-2.
• [5] A composition comprising the compound according to any one of [1] to [4] and an electron transporting material.
• a method for producing the compound according to any one of [1] to [4] The manufacturing method of a compound including the process with which the compound represented by Formula (3) and the compound represented by Formula (4) are made to react.
• a 1 , R 1 , R 2 , R 3 , m and n are the same as defined above, and X ⁇ represents a counter anion for the cation.
• R 4 is the same as defined above, M 1 and M 2 each independently represent a group containing a metal atom or a metalloid atom, q represents an integer of 0 to 3, and r represents 1 to 4] And s represents an integer of 1 to 3.
• R 4 is a hydrogen atom
• M 2 is an aluminum atom.
• the compound according to the present invention is relatively stable in a solvent, can be applied to film formation by a coating method, and suitably functions as an n-type doping material.
• the compound according to the present invention can be more strongly doped with an electron transporting material by mixing with the electron transporting material than a known n-type doping material that can be formed by a coating method.
• Me represents a methyl group
• Et represents an ethyl group
• Bu represents a butyl group
• i-Pr represents an isopropyl group
• t-Bu represents a tert-butyl group
• Ph represents a phenyl group.
• the hydrogen atom may be a deuterium atom or a light hydrogen atom.
• the “alkyl group” may be linear or branched.
• the number of carbon atoms of the linear alkyl group is usually 1 to 50, preferably 1 to 10, excluding the number of carbon atoms of the substituent.
• the number of carbon atoms of the branched alkyl group is usually 3 to 50, preferably 3 to 10, excluding the number of carbon atoms of the substituent.
• the alkyl group may have a substituent.
• alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isoamyl group, 2-ethylbutyl group, hexyl group, heptyl group, octyl group, Examples include 2-ethylhexyl group, 3-propylheptyl group, decyl group, 3,7-dimethyloctyl group, 2-ethyloctyl group, 2-hexyl-decyl group, dodecyl group and the like.
• the alkyl group may be a group in which some or all of the hydrogen atoms in these groups are substituted with a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom, or the like.
• alkyl groups include trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, 3-phenylpropyl group, and 3- (4-methylphenyl) propyl.
• the number of carbon atoms of the “cycloalkyl group” is usually 3 to 50, preferably 3 to 10, not including the number of carbon atoms of the substituent.
• the cycloalkyl group may have a substituent. Examples of the cycloalkyl group include a cyclohexyl group, a cyclohexylmethyl group, and a cyclohexylethyl group.
• Aryl group means an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon.
• the number of carbon atoms of the aryl group is usually 6 to 60, preferably 6 to 20, excluding the number of carbon atoms of the substituent.
• the aryl group may have a substituent.
• Examples of the aryl group include a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, Examples include 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 2-phenylphenyl group, 3-phenylphenyl group, 4-phenylphenyl group and the like.
• the aryl group may be a group in which some or all of the hydrogen atoms in these groups are substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom, or the like.
• the “alkoxy group” may be linear or branched.
• the number of carbon atoms of the straight-chain alkoxy group is usually 1 to 50, preferably 1 to 10, not including the number of carbon atoms of the substituent.
• the number of carbon atoms of the branched alkoxy group is usually 3 to 50, preferably 3 to 10, excluding the number of carbon atoms of the substituent.
• the alkoxy group may have a substituent.
• alkoxy group examples include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, isobutyloxy group, tert-butyloxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2 -Ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group and the like.
• the alkoxy group may be a group in which part or all of the hydrogen atoms in these groups are substituted with a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom, or the like.
• the number of carbon atoms of the “cycloalkoxy group” is usually 3 to 50, preferably 3 to 10, excluding the number of carbon atoms of the substituent.
• the cycloalkoxy group may have a substituent. Examples of the cycloalkoxy group include a cyclohexyloxy group.
• the number of carbon atoms of the “aryloxy group” is usually 6 to 60, preferably 6 to 20, not including the number of carbon atoms of the substituent.
• the aryloxy group may have a substituent. Examples of the aryloxy group include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 1-anthracenyloxy group, 9-anthracenyloxy group, 1-pyrenyloxy group and the like.
• the aryloxy group may be a group in which some or all of the hydrogen atoms in these groups are substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a fluorine atom, or the like.
• alkylsulfenyl group may be linear or branched.
• the number of carbon atoms of the linear alkylsulfenyl group is usually 1 to 50, preferably 1 to 10, not including the carbon atoms of the substituent.
• the number of carbon atoms of the branched alkylsulfenyl group is usually 3 to 50, preferably 3 to 10, not including the carbon atoms of the substituent.
• the alkylsulfenyl group may have a substituent.
• alkylsulfenyl group examples include a methylsulfenyl group, an ethylsulfenyl group, a propylsulfenyl group, an isopropylsulfenyl group, a butylsulfenyl group, an isobutylsulfenyl group, a tert-butylsulfenyl group, and a pentylsulfenyl group.
• the alkylsulfenyl group may be a group in which some or all of the hydrogen atoms in these groups are substituted with a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom, or the like.
• the number of carbon atoms of the “cycloalkylsulfenyl group” is usually 3 to 50, preferably 3 to 10, not including the number of carbon atoms of the substituent.
• the cycloalkylsulfenyl group may have a substituent. Examples of the cycloalkylsulfenyl group include a cyclohexylsulfenyl group.
• the number of carbon atoms of the “arylsulfenyl group” is usually 6 to 60, preferably 6 to 20, excluding the number of carbon atoms of the substituent.
• the arylsulfenyl group may have a substituent. Examples of the arylsulfenyl group include phenylsulfenyl group, 1-naphthylsulfenyl group, 2-naphthylsulfenyl group, 1-anthracenylsulfenyl group, 9-anthracenylsulfenyl group, 1-pyrenylsulfenyl group. Groups and the like.
• the arylsulfenyl group may be a group in which some or all of the hydrogen atoms in these groups are substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a fluorine atom, or the like.
• the “monovalent heterocyclic group” means a remaining atomic group obtained by removing one hydrogen atom from hydrogen atoms directly bonded to a carbon atom or a hetero atom constituting a ring from a heterocyclic compound. To do. Among monovalent heterocyclic groups, it is the remaining atomic group obtained by removing one hydrogen atom from a hydrogen atom directly bonded to a carbon atom or a hetero atom constituting an aromatic heterocyclic compound. A “monovalent aromatic heterocyclic group” is preferable.
• “Aromatic heterocyclic compounds” include oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, dibenzosilole, dibenzophosphole A compound in which the heterocyclic ring itself is aromatic, and a heterocyclic ring such as phenoxazine, phenothiazine, dibenzoborol, dibenzosilol, benzopyran, etc. itself does not exhibit aromaticity, but the aromatic ring is condensed to the heterocyclic ring. Means a compound that has been
• the number of carbon atoms of the monovalent heterocyclic group is usually 2 to 60, preferably 2 to 20, excluding the number of carbon atoms of the substituent.
• the monovalent heterocyclic group may have a substituent. Examples of the monovalent heterocyclic group include thienyl group, pyrrolyl group, furyl group, pyridyl group, piperidyl group, quinolyl group, isoquinolyl group, pyrimidinyl group, triazinyl group and the like.
• the monovalent heterocyclic group may be a group in which some or all of the hydrogen atoms in these groups are substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, or the like.
• Halogen atom means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
• the “amino group” may have a substituent, and a substituted amino group is preferable.
• a substituent which an amino group has an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group is preferable.
• the substituted amino group is preferably a disubstituted amino group.
• the substituent of the disubstituted amino group a combination of an alkyl group, a cycloalkyl group, and an aryl group is preferable.
• a dialkylamino group and a dicycloalkylamino group are preferable, and a dialkylamino group is more preferable.
• disubstituted amino group examples include a dialkylamino group, a dicycloalkylamino group, and a diarylamino group.
• substituents of the 2-substituted amino group may be bonded to each other to form a ring.
• the number of carbon atoms of the alkyl group as a substituent of the disubstituted amino group is usually 1 to 50, preferably 1 to 10.
• disubstituted amino group examples include a dimethylamino group, a diethylamino group, a diphenylamino group, a bis (4-methylphenyl) amino group, a bis (4-tert-butylphenyl) amino group, and bis (3,5-di-).
• tert-butylphenyl) amino group pyrrolidinyl group, piperidinyl group, carbazolyl group.
• “Substituent” represents a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group or an amino group.
• the compound according to this embodiment is a compound represented by the formula (1).
• a 1 it is preferable that two A 1 are both —NR 5 — or —PR 5 —.
• Such a compound is represented, for example, by the formula (1-2).
• R 1 , R 2 , R 3 , R 4 , R 5 , n and m are the same as above, and A 2 represents a nitrogen atom or a phosphorus atom. Two A 2 may be the same or different from each other.
• a 1 it is more preferable that two A 1 are both —NR 5 —.
• R 1 is preferably a group having a strong electron donating property because the compound according to this embodiment functions as a stronger dopant. It is preferable that at least one R 1 is an alkoxy group, a cycloalkoxy group, an aryloxy group or a disubstituted amino group, and it is more preferable that at least one R 1 is an alkoxy group.
• R 1 is an alkoxy group, cycloalkoxy group, aryloxy group, alkylsulfenyl group, a cycloalkyl sulfenyl group and is an aryl sulphenyl group or a substituted amino group
• R 2 and R 3 is any of the above Even in this case, the compound according to this embodiment can function as a sufficiently strong dopant.
• two R 1 s are both an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylsulfenyl group, a cycloalkylsulfenyl group, an arylsulfenyl group, or a disubstituted amino group. It's okay.
• two R 1 s are preferably both an alkoxy group, a cycloalkoxy group, an aryloxy group or a disubstituted amino group, and more preferably an alkoxy group.
• R 2 is preferably a group having a strong electron donating property because the compound according to the present embodiment functions as a stronger dopant.
• R 2 is preferably an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylsulfenyl group, a cycloalkylsulfenyl group, an arylsulfenyl group or a disubstituted amino group, and is an alkoxy group or a disubstituted amino group. It is more preferable that it is a disubstituted amino group.
• R 3 is preferably a group having a strong electron donating property because the compound according to the present embodiment functions as a stronger dopant.
• R 3 is preferably an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylsulfenyl group, a cycloalkylsulfenyl group, an arylsulfenyl group or a disubstituted amino group, and more preferably a disubstituted amino group. preferable.
• n is 1 or more and at least one R 3 is a disubstituted amino group
• the compound according to this embodiment can be used as a sufficiently strong dopant even if R 1 and R 2 are any of the above cases.
• R 4 is preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom because synthesis is easy.
• R 5 is preferably an alkyl group or a cycloalkyl group, and more preferably an alkyl group.
• an electron-donating group is bonded to the para-position of the benzene ring that is bonded to the benzimidazoline ring.
• Such a compound is represented, for example, by the formula (2).
• R 2 bonded to the para position of the benzene ring (hereinafter also referred to as R 2 of the para position) is an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylsulfenyl group, or a cycloalkylsulfenyl.
• R 2 of the para position is an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylsulfenyl group, or a cycloalkylsulfenyl.
• Group, an arylsulfenyl group or a disubstituted amino group is preferred, an alkoxy group or a disubstituted amino group is more preferred, and a disubstituted amino group is still more preferred.
• R 1 when R 2 in the para position is a disubstituted amino group, R 1 is a hydrogen atom, an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylsulfenyl group, a cycloalkylsulfenyl group, an arylsulfur group. It is preferably a phenyl group or a disubstituted amino group.
• Two R 1 s may be the same or different from each other, but at least one R 1 is a group other than a hydrogen atom.
• the group other than a hydrogen atom in R 1 is more preferably an alkoxy group, a cycloalkoxy group, an aryloxy group or a disubstituted amino group, and further preferably an alkoxy group.
• R 1 is an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylsulfenyl group, a cycloalkylsulfenyl group, an arylsulfur group. It is preferably a phenyl group or a disubstituted amino group, more preferably an alkoxy group, a cycloalkoxy group, an aryloxy group or a disubstituted amino group, and more preferably an alkoxy group or a disubstituted amino group.
• the group other than R 2 at the para-position is preferably an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylsulfenyl group, a cycloalkylsulfenyl group, or an arylsulfenyl group, More preferably, it is an alkoxy group.
• p may be 0.
• n may be 0 to 2
• n may be 0 or 1, and may be 0.
• At least one R 1 is an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylsulfenyl group, a cycloalkylsulfenyl group, an arylsulfenyl group, or a disubstituted amino group;
• R 1 is an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkyl group
• a compound which is a sulfenyl group, a cycloalkylsulfenyl group or an arylsulfenyl group is preferred.
• an electron donating group is preferably bonded to R 2 at the para position.
• a compound is, for example, a compound represented by the formula (2), At least one R 1 is an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylsulfenyl group, a cycloalkylsulfenyl group, an arylsulfenyl group, or a disubstituted amino group; When neither R 1 nor R 2 in the para position is a disubstituted amino group, both R 1 are groups other than hydrogen atoms, and at least one R 1 is an alkoxy group, a cycloalkoxy group, an aryloxy group Group, an alkylsulfenyl group, a cycloalkylsulfenyl group or an arylsulfenyl group.
• R 2 at the para position is preferably an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylsulfenyl group, a cycloalkylsulfenyl group, an arylsulfenyl group, or a disubstituted amino group, and a disubstituted amino group. More preferably, it is a group.
• the compound according to this embodiment can be produced, for example, by reacting the compound represented by the formula (3) with the compound represented by the formula (4).
• Examples of the counter anion represented by X ⁇ include hydroxide ions, halide ions, carboxylate ions, carbonate ions, sulfate ions, nitrate ions, phosphate ions, nitrate ions, and the like. Compound ions are preferred.
• the metal atom or metalloid atom contained in M 1 may be, for example, an alkali metal atom, an alkaline earth metal atom, a transition metal atom, a zinc group atom or a boron group atom.
• M 1 is preferably a group containing an alkali metal atom or an alkaline earth metal atom, and more preferably a group containing an alkali metal atom.
• Preferable examples of the metal atom or metalloid atom contained in M 1 include a lithium atom, a sodium atom, a potassium atom, a magnesium atom, and a calcium atom.
• Metal atom or metalloid atom contained in M 2 is, for example, an alkali metal atom, an alkaline earth metal atom, a transition metal atom may be a zinc group atom or a boron group atoms.
• M 2 may be, for example, a group containing a lithium atom, sodium atom, potassium atom, magnesium atom, calcium atom, iron atom, cobalt atom, nickel atom, copper atom, zinc atom, boron atom or aluminum atom.
• Examples of the compound represented by the formula (4) include hydride reducing agents such as sodium borohydride, lithium aluminum hydride, diisopropylaluminum hydride, organolithium reagent, Grignard reagent, organozinc reagent, organoaluminum reagent, art complex, Examples thereof include metal alkoxides and metal amides.
• hydride reducing agents such as sodium borohydride, lithium aluminum hydride, diisopropylaluminum hydride, organolithium reagent, Grignard reagent, organozinc reagent, organoaluminum reagent, art complex, Examples thereof include metal alkoxides and metal amides.
• M 2 is aluminum (Al ) Is preferable, and lithium aluminum hydride (LiAlH 4 ) is more preferable.
• the compound represented by the formula (3) is useful as a synthetic intermediate for the compound represented by the formula (1).
• examples and preferred ranges of A 1 , R 1 , R 2 , R 3 , m and n in the formula (3) are A 1 , R 1 , R 2 , R 3 , m and n in the formula (1). This is the same as the examples and preferred ranges.
• Specific examples of the compound represented by the formula (3) include precursors of exemplary compounds as the compound represented by the formula (1).
• the compound according to this embodiment can be suitably used as an n-type doping material.
• the compound according to the present embodiment can be n-doped with an electron transporting material by, for example, forming a thin film by mixing with an electron transporting material and activating by heat or light irradiation.
• the thin film containing the compound and electron transport material which concern on this embodiment can be used suitably for various electronic devices, such as organic EL, polymer organic EL, an organic thin film solar cell, and an organic thin-film transistor.
• the electron transporting material is preferably a compound having a LUMO level of ⁇ 2.0 eV or less.
• the compound according to this embodiment can be n-doped with an electron transporting material having a shallower LUMO than a known N-DMBI type compound. Therefore, the electron transporting material may be a compound having a LUMO level of ⁇ 3.0 eV or more and ⁇ 2.0 eV or less.
• Electron transport materials can be classified into low molecular compounds and high molecular compounds.
• low molecular weight compound examples include metal complexes having 8-hydroxyquinoline as a ligand, oxadiazole, anthraquinodimethane, benzoquinone, naphthoquinone, anthraquinone, tetracyanoanthraquinodimethane, fluorenone, diphenyldicyanoethylene, and diphenoquinone. As well as these derivatives.
• polymer compound examples include polyphenylene, polyfluorene, polyphenylene vinylene, polythienylene vinylene, polyquinoline and polyquinoxaline, and derivatives thereof.
• the compounding amount of the compound according to this embodiment with respect to 100 parts by mass of the electron transporting material is preferably 0.1 to 200 parts by mass. Since the electron transporting material can be more efficiently doped, the amount is preferably 1 part by mass or more, and more preferably 5 parts by mass or more. Moreover, since the film formability as an electron carrying layer becomes favorable, the said compounding quantity has preferable 50 mass parts or less.
• a method for forming a thin film when a low molecular compound is used as an electron transporting material, for example, a vacuum deposition method from powder, a method of forming a film from a solution or a molten state, and the like can be mentioned. For example, a method of forming a film from a solution or a molten state can be used.
• the solvent used in the film-forming method from a solution may be any solvent that can dissolve or uniformly disperse each material.
• the solvent include chlorine solvents such as 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene; ether solvents such as THF, dioxane, anisole and 4-methylanisole; Aromatic hydrocarbon solvents such as xylene, mesitylene, ethylbenzene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, nonylbenzene, decylbenzene, undecylbenzene, dodecylbenzene, cyclohexylbenzene, trimethylbenzene, 3-phenoxytoluene; Aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane
• the solvent is preferably a chlorine solvent, an ether solvent, an aromatic hydrocarbon solvent, a ketone solvent, an ester solvent, or a combination thereof.
• Examples of the film forming method from a solution include spin coating, casting, micro gravure printing, gravure printing, bar coating, roll coating, wire bar coating, dip coating, slit coating, and cap coating.
• Examples thereof include coating methods such as a coating method, a spray coating method, a screen printing method, a flexographic printing method, an offset printing method, an ink jet printing method, and a nozzle coating method.
• the viscosity of the solution may be adjusted according to the type of film formation method. For example, when a solution such as an ink jet printing method is applied to a printing method that passes through a discharge device, clogging at the time of discharge and flight bending are less likely to occur, so the viscosity of the solution is 1 to 20 mPa ⁇ s at 25 ° C. It is preferable.
• the compounding amount of the solvent is usually 1000 to 100,000 parts by mass, preferably 2000 to 20000 parts by mass with respect to 100 parts by mass of the solute.
• the activation of the thin film can be performed by heat or light irradiation.
• the activation treatment may be performed during the production of the thin film or after the production of the thin film.
• the activation treatment is preferably performed after the thin film is formed, after the thin film is sealed and oxygen and water are blocked.
• Examples of the activation method by heat include heating by an oven, heating by a hot plate, infrared heating, heating by vacuum deposition energy, and the like.
• an activation method by light irradiation there is a method of irradiating light using a light source capable of irradiating any one of ultraviolet light, visible light and infrared light. Since it is easy to obtain the intensity of light necessary for activation, it is preferable to use a light source capable of emitting either ultraviolet light or visible light.
• compositions comprising a compound represented by formula (1) and an electron transporting material.
• the composition can be suitably used for various electronic devices such as an organic EL, a polymer organic EL, an organic thin film solar cell, and an organic thin film transistor by forming a thin film.
• one aspect of the present invention relates to a composition containing the compound represented by the formula (1), an electron transporting material, and a solvent.
• a composition containing the compound represented by the formula (1), an electron transporting material, and a solvent By using the composition, a thin film suitable for application to various electronic devices can be easily produced.
• One aspect of the present invention also relates to a compound represented by the formula (3).
• the compound represented by the formula (1) can be easily synthesized.
• one aspect of the present invention relates to a method for producing the compound represented by the formula (1), which includes a step of reacting the compound represented by the formula (3) and the compound represented by the formula (4). According to this production method, the compound represented by the formula (1) can be easily synthesized.
• NMR measurement was performed by the following method. About 10 mg of a measurement sample was dissolved in about 0.7 mL of a heavy solvent and measured using an NMR apparatus (manufactured by JEOL Ltd., product name: JNM-ECZ400S / L1).
• TLC-MS was measured by the following method.
• the measurement sample was dissolved in toluene, tetrahydrofuran or chloroform at an arbitrary concentration, and applied to a TLC plate for DART (manufactured by Techno Applications, trade name: YSK5-100) or a glass plate, and TLC-MS (manufactured by JEOL Ltd., Trade name: JMS-T100TD (The AccuTOF TLC)).
• the helium gas temperature during measurement was adjusted in the range of 200 to 400 ° C.
• Liquid chromatography mass spectrometry was performed by the following method.
• the measurement sample was dissolved in chloroform or THF to a concentration of about 2 mg / mL, and about 1 ⁇ L was injected into LC-MS (manufactured by Agilent Technologies, trade name: 1100LCMSD).
• the LC-MS mobile phase was used while changing the ratio of acetonitrile and THF, and was allowed to flow at a flow rate of 0.2 mL / min.
• the column used was SUMPAX ODS Z-CLUE ( ⁇ 4.6 ⁇ 250 mm, 3 ⁇ m, manufactured by Sumika Chemical Analysis Center).
• the polystyrene-equivalent number average molecular weight and weight average molecular weight of the polymer compound were determined by size exclusion chromatography (SEC) (manufactured by Shimadzu Corporation, trade name: LC-10Avp).
• SEC size exclusion chromatography
• the polymer compound to be measured was dissolved in tetrahydrofuran to a concentration of about 0.5% by weight, and 50 ⁇ L was injected into SEC. Tetrahydrofuran was used as the mobile phase of SEC and was allowed to flow at a flow rate of 0.6 mL / min.
• TSKgel SuperHM-H manufactured by Tosoh
• TSKgel SuperH2000 manufactured by Tosoh
• a differential refractive index detector manufactured by Shimadzu Corporation, trade name: RID-10A was used as the detector.
• Example 1 Synthesis of Compound A-1
• Compound A-1 represented by formula (A-1) was synthesized by the following method. 694 mg of N, N′-dimethyl-o-phenylenediamine and 1.28 g of 2-methoxy-4-diethylamino-benzaldehyde were dissolved in 10 ml of methanol, and a catalytic amount of acetic acid was added. After refluxing for 13 hours under air atmosphere, the reaction was concentrated. 10 ml of water was added and washed 3 times with 10 ml of toluene. The aqueous phase was concentrated and dried overnight in a 50 ° C. vacuum dryer.
• Example 2 Synthesis of Compound A-2
• Compound A-2 represented by formula (A-2) was synthesized by the following method. 500 mg of compound A-1 was taken in the flask, and the atmosphere in the flask was replaced with nitrogen. Dissolved in 10 ml of dehydrated THF, 107 mg of lithium aluminum hydride was added little by little and reacted at room temperature for 3 hours. In a separate flask, 70 ml of water was taken and cooled on ice, and the reaction product was added dropwise with a cannula. Extraction was performed 4 times with 20 ml of toluene and dehydrated with sodium sulfate. Filtration, concentration of the organic phase and drying in a vacuum oven overnight gave 356 mg of compound A-2.
• the aqueous phase was extracted three times with 125 ml of chloroform, and the organic phases were combined and washed with 100 ml of water and 100 ml of saturated brine. After drying with magnesium sulfate, the solvent was distilled off to obtain 27.85 g of a crude product. Purification by silica gel column chromatography (developing solvent hexane: ethyl acetate) gave 12.13 g of compound (3-2). The analysis results of the obtained compound (3-2) were as follows.
• Example 4 Synthesis of Compound A-4
• Compound A-4 represented by the formula (A-4) was synthesized by the following method. After taking 5.45 g of compound A-3 in the flask and replacing the atmosphere in the flask with nitrogen, 109 ml of dehydrated THF was added. While maintaining the internal temperature at 30 ° C. or lower in a water bath, 571 mg of lithium aluminum hydride was added little by little and stirred for 3 hours. 750 g of ice water was taken, and the reaction solution was added dropwise thereto. Extraction was performed three times with 750 ml of toluene, the organic phases were combined, dried over sodium sulfate, filtered, and the solvent was distilled off to obtain 2.91 g of compound A-4.
• Example 6 Synthesis of Compound A-6
• Compound A-6 represented by formula (A-6) was synthesized by the following method. After taking 280 mg of Compound A-5 and replacing the atmosphere in the flask with nitrogen, 5.6 ml of dehydrated THF was added to form a suspension. After adding 39.7 mg of lithium aluminum hydride and stirring for 7 hours at room temperature, 12.0 mg of lithium aluminum hydride was further added and stirred for 6.5 hours. 40 ml of water was taken in a 300 ml beaker and cooled in an ice bath. The reactant was added dropwise here. Extracted three times with 20 ml of toluene and dried over sodium sulfate.
• Step 1 After making the inside of the reaction vessel an inert gas atmosphere, the compound (M-1) (3.559 g), the compound (M-2) (2.900 g), bis (triphenylphosphine) palladium (II) Dichloride (3.2 mg) and toluene (50 mL) were added and heated to 105 ° C.
• Step 2 Thereafter, a 20 wt% tetraethylammonium hydroxide aqueous solution (15 mL) was added dropwise thereto and refluxed for 3 hours.
• Step 3 Thereafter, phenylboronic acid (54.9 mg) and toluene (50 mL) were added thereto and refluxed for 12 hours or more.
• Step 4 Thereafter, a sodium diethyldithiacarbamate aqueous solution was added thereto, followed by stirring at 80 ° C. for 2 hours. The resulting reaction mixture was cooled and then washed twice with water, twice with a 3 wt% aqueous acetic acid solution and twice with water. When the obtained solution was added dropwise to methanol and stirred, precipitation occurred. The obtained precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. When the obtained solution was added dropwise to methanol and stirred, precipitation occurred. The obtained precipitate was collected by filtration and dried to obtain 3.93 g of polymer compound P-1.
• the number average molecular weight (Mn) of the obtained polymer compound P-1 was 1.9 ⁇ 10 5
• the weight average molecular weight (Mw) was 5.1 ⁇ 10 5
• the theoretical value obtained from the amount of the raw material used for polymer compound P-1 was that the structural unit derived from compound (M-1) and the structural unit derived from compound (M-2) were 50: It is a copolymer formed with a molar ratio of 50.
• the compound (M-1) was synthesized according to the method described in JP 2014-224101 A.
• Compound (M-2) was synthesized according to the method described in International Publication No. 2009/131255.
• the compound according to the present invention is relatively stable in a solvent, can be applied to film formation by a coating method, and suitably functions as an n-type doping material.
• the compound according to the present invention can be more strongly doped with an electron transporting material by mixing with the electron transporting material than a known n-type doping material that can be formed by a coating method.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Electromagnetism (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Materials Engineering (AREA)
• Photovoltaic Devices (AREA)
• Electroluminescent Light Sources (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Plural Heterocyclic Compounds (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=59964315

Family Applications (1)

Country Status (3)

Families Citing this family (1)

Citations (2)

Family Cites Families (11)

• 2016
  • 2016-03-29 JP JP2016066102A patent/JP6851725B2/ja not_active Expired - Fee Related
• 2017
  • 2017-03-21 WO PCT/JP2017/011172 patent/WO2017169971A1/ja not_active Ceased
  • 2017-03-21 US US16/089,485 patent/US11046655B2/en not_active Expired - Fee Related

Patent Citations (2)

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events