WO2019198698A1 - フッ素置換多環芳香族化合物 - Google Patents

フッ素置換多環芳香族化合物 Download PDF

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WO2019198698A1
WO2019198698A1 PCT/JP2019/015409 JP2019015409W WO2019198698A1 WO 2019198698 A1 WO2019198698 A1 WO 2019198698A1 JP 2019015409 W JP2019015409 W JP 2019015409W WO 2019198698 A1 WO2019198698 A1 WO 2019198698A1
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ring
aryl
substituted
carbon atoms
formula
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PCT/JP2019/015409
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English (en)
French (fr)
Japanese (ja)
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琢次 畠山
一志 枝連
田中　裕之
国防 王
馬場　大輔
笹田　康幸
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学校法人関西学院
Jnc株式会社
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Application filed by 学校法人関西学院, Jnc株式会社 filed Critical 学校法人関西学院
Priority to JP2020513400A priority Critical patent/JP7398711B2/ja
Priority to KR1020207025497A priority patent/KR20200141983A/ko
Priority to CN201980012785.5A priority patent/CN112601753A/zh
Publication of WO2019198698A1 publication Critical patent/WO2019198698A1/ja
Priority to JP2023198754A priority patent/JP2024037733A/ja

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    • 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
    • H10K85/658—Organoboranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
    • 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]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
    • 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

Definitions

  • the present invention relates to a fluorine-substituted polycyclic aromatic compound, an organic electroluminescence device using the same, an organic field effect transistor, an organic thin film solar cell, a display device and a lighting device.
  • organic electroluminescent device may be referred to as “organic EL device” or simply “device”.
  • the organic EL element has a structure composed of a pair of electrodes composed of an anode and a cathode, and one layer or a plurality of layers including an organic compound disposed between the pair of electrodes.
  • the layer containing an organic compound include a light-emitting layer and a charge transport / injection layer that transports or injects charges such as holes and electrons.
  • Various organic materials suitable for these layers have been developed.
  • a benzofluorene compound has been developed (International Publication No. 2004/061047).
  • a hole transport material for example, a triphenylamine compound has been developed (Japanese Patent Laid-Open No. 2001-172232).
  • an anthracene compound has been developed (Japanese Patent Laid-Open No. 2005-170911).
  • the charge transport property of a NO-linked compound (Compound 1 on page 63) is evaluated, but a method for producing a material other than the NO-linked compound is not described, and the element to be linked is not described. Since the electronic state of the entire compound is different if it is different, the characteristics obtained from materials other than NO-linked compounds are not yet known. Other examples of such compounds can be found (WO 2011/107186).
  • a compound having a conjugated structure with a large triplet exciton energy (T1) can emit phosphorescence having a shorter wavelength, and thus is useful as a blue light-emitting layer material.
  • a compound having a novel conjugated structure having a large T1 is also required as an electron transport material or a hole transport material sandwiching the light emitting layer.
  • the host material of the organic EL element is generally a molecule in which a plurality of existing aromatic rings such as benzene and carbazole are connected by a single bond, phosphorus atom or silicon atom. This is because a large HOMO-LUMO gap (band gap Eg in a thin film) required for the host material is secured by connecting a large number of relatively conjugated aromatic rings. Furthermore, a host material of an organic EL device using a phosphorescent material or a thermally activated delayed fluorescent material also requires high triplet excitation energy (E T ), but the molecule has a donor or acceptor aromatic ring or substituent.
  • E T triplet excitation energy
  • Patent Document 6 a polycyclic aromatic compound containing boron and an organic EL device using the same are reported.
  • layer materials particularly dopant materials.
  • the present inventors have arranged a layer containing a polycyclic aromatic compound into which a fluorine atom has been introduced between a pair of electrodes, for example, to constitute an organic EL element,
  • the inventors have found that an excellent organic EL device can be obtained, and completed the present invention. That is, the present invention is for organic devices such as the following fluorine-substituted polycyclic aromatic compounds or multimers thereof, and further organic EL element materials containing the following fluorine-substituted polycyclic aromatic compounds or multimers thereof. Provide material.
  • the chemical structure or substituent may be represented by the number of carbons.
  • the number of carbons in the case where a substituent is substituted on the chemical structure or the substituent is further substituted on the chemical group is the chemical structure.
  • the number of carbon atoms of each substituent and does not mean the total number of carbon atoms of the chemical structure and the substituent, or the total number of carbon atoms of the substituent and the substituent.
  • “substituent B of carbon number Y substituted by substituent A of carbon number X” means that “substituent B of carbon number Y” is substituted for “substituent B of carbon number Y”.
  • the carbon number Y is not the total carbon number of the substituent A and the substituent B.
  • substituted with substituent A means that “substituent A having no carbon number” is substituted for “substituent B having carbon number Y”.
  • the carbon number Y is not the total carbon number of the substituent A and the substituent B.
  • a ring, B ring and C ring are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings may be substituted;
  • Y 1 is B, P, P ⁇ O, P ⁇ S, Al, Ga, As, Si—R or Ge—R, wherein R in Si—R and Ge—R is aryl, alkyl or cycloalkyl
  • X 1 and X 2 are each independently O, N—R, S or Se, wherein R in the N—R is an optionally substituted aryl, an optionally substituted heteroaryl, a substituted
  • the optionally substituted alkyl or the optionally substituted cycloalkyl, and R in the N—R may be bonded to the A ring, the B ring and / or the C ring by a linking group or
  • At least one hydrogen in the compound or structure represented by formula (1) may be substituted with cyano, chlorine, bromine, iodine or deuterium; and At least one hydrogen in the compound or structure represented by formula (1) is substituted with fluorine.
  • a ring, B ring and C ring are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings is substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted Or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboryl (the two aryls are bonded via a single bond or a linking group).
  • Y 1 A 5-membered ring sharing a bond with the fused bicyclic structure in the center of the above formula, consisting of X 1 and X 2 Or a 6-membered ring Y 1 is B, P, P ⁇ O, P ⁇ S, Al, Ga, As, Si—R or Ge—R, wherein R in Si—R and Ge—R is aryl, alkyl or cycloalkyl And X 1 and X 2 are each independently O, N—R, S or Se, and R in N—R is aryl, alkyl or cycloalkyl optionally substituted with alkyl or cycloalkyl.
  • Optionally substituted heteroaryl, alkyl or cycloalkyl, and R in the N—R is —O—, —S—, —C (—R) 2 — or a single bond to the A ring, B Which may be bonded to a ring and / or a C ring, R in the —C (—R) 2 — is hydrogen, alkyl or cycloalkyl; At least one hydrogen in the compound or structure represented by formula (1) may be substituted with cyano, chlorine, bromine, iodine or deuterium; In the case of a multimer, it is a dimer or trimer having 2 or 3 structures represented by the general formula (1), and At least one hydrogen in the compound or structure represented by formula (1) is substituted with fluorine, Item 9.
  • Item 3 The polycyclic aromatic compound or a multimer thereof according to item 1, represented by the following general formula (2): (In the above formula (2), R 1 to R 11 are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (the two aryls are bonded via a single bond or a linking group).
  • X 1 and X 2 are each independently O, N—R, S or Se, and R in N—R is aryl having 6 to 12 carbons, heteroaryl having 2 to 15 carbons, carbon
  • R in the —C (—R) 2 — is alkyl having 1 to 6 carbons or cycloalkyl having 3 to 14 carbons
  • At least one hydrogen in the compound of formula (2) may be substituted with cyano, chlorine, bromine, iodine or deuterium; and At least one hydrogen in the compound represented by the formula (2) is substituted with fluorine.
  • R 1 to R 11 are each independently hydrogen, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 12 carbon atoms), diarylboryl (provided that Aryl is aryl having 6 to 12 carbons, and two aryls may be bonded via a single bond or a linking group), alkyl having 1 to 24 carbons or cycloalkyl having 3 to 24 carbons
  • adjacent groups of R 1 to R 11 are bonded to form an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms together with the a ring, b ring or c ring.
  • At least one hydrogen in the ring formed may be substituted with aryl having 6 to 10 carbon atoms, alkyl having 1 to 12 carbon atoms or cycloalkyl having 3 to 16 carbon atoms.
  • Y 1 is B, P, P ⁇ O, P ⁇ S or Si—R, wherein R in Si—R is aryl having 6 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms, or 5 to 5 carbon atoms.
  • 10 cycloalkyl, X 1 and X 2 are each independently O, N—R or S, wherein R in N—R is aryl having 6 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms or carbon atoms having 5 to 5 carbon atoms.
  • At least one hydrogen in the compound of formula (2) may be substituted with cyano, chlorine, bromine, iodine or deuterium; and At least one hydrogen in the compound represented by the formula (2) is substituted with fluorine, Item 4.
  • R 1 to R 11 are each independently hydrogen, aryl having 6 to 16 carbon atoms, diarylamino (where aryl is aryl having 6 to 10 carbon atoms), diarylboryl (where aryl is aryl having 6 to 10 carbon atoms) And two aryls may be bonded via a single bond or a linking group), alkyl having 1 to 12 carbons or cycloalkyl having 3 to 16 carbons, Y 1 is B, X 1 and X 2 are both N—R, or X 1 is N—R and X 2 is O, and R in N—R is aryl having 6 to 10 carbon atoms, carbon number 1 to 4 alkyl or cycloalkyl having 5 to 10 carbon atoms, and At least one hydrogen in the compound represented by the formula (2) is substituted with fluorine, Item 4.
  • Item 7 The polycyclic aromatic compound or the multimer thereof according to any one of Items 1 to 6, wherein R in N—R is fluorine-substituted aryl or heteroaryl.
  • Item 8 The polycyclic aromatic compound or the multimer thereof according to Item 7, wherein R in N—R is phenyl substituted with fluorine.
  • Item 9 Fluorine-substituted alkyl group or cycloalkyl group, fluorine-substituted alkoxy group, fluorine-substituted diarylamino group, fluorine-substituted diarylboryl group (the two aryls are bonded via a single bond or a linking group)
  • the polycyclic aromatic compound or a multimer thereof according to any one of Items 1 to 8, which is substituted with a fluorine-substituted carbazolyl group or a fluorine-substituted benzocarbazolyl group.
  • Item 10 The polycyclic aromatic compound or the multimer thereof according to Item 9, which is substituted with a fluorine-substituted diarylamino group.
  • Item 11 The polycyclic aromatic compound or the multimer thereof according to Item 10, which is substituted with a fluorine-substituted diphenylamino group.
  • Item 12. The polycyclic aromatic compound according to Item 1, represented by any one of the following structural formulas. (“TBu” in the above structural formulas represents a t-butyl group.)
  • Item 13 The polycyclic aromatic compound according to Item 1, represented by any one of the following structural formulas. ("Me" in the above structural formulas represents a methyl group.)
  • Item 14 An organic device material comprising the polycyclic aromatic compound or the multimer thereof according to any one of Items 1 to 13.
  • Item 15 The organic device material according to Item 14, wherein the organic device material is an organic electroluminescent element material, an organic field effect transistor material, or an organic thin film solar cell material.
  • Item 16 The organic electroluminescent element material according to Item 15, which is a light emitting layer material.
  • An organic electroluminescence device comprising: a pair of electrodes composed of an anode and a cathode; and a light emitting layer disposed between the pair of electrodes and containing the light emitting layer material described in Item 16.
  • Item 18 The organic electroluminescent element according to Item 17, wherein the light-emitting layer includes a host and the light-emitting layer material as a dopant.
  • Item 19 The organic electroluminescence device according to Item 18, wherein the host is an anthracene compound, a fluorene compound, or a dibenzochrysene compound.
  • Item 20 An electron transport layer and / or an electron injection layer disposed between the cathode and the light emitting layer, wherein at least one of the electron transport layer and the electron injection layer is a borane derivative, a pyridine derivative, a fluoranthene derivative, BO Item 17 containing at least one selected from the group consisting of a series derivative, anthracene derivative, benzofluorene derivative, phosphine oxide derivative, pyrimidine derivative, carbazole derivative, triazine derivative, benzimidazole derivative, phenanthroline derivative, and quinolinol metal complex 20.
  • the organic electroluminescent device as described in any one of 1 to 19.
  • the electron transport layer and / or the electron injection layer further includes an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, or an alkaline earth metal.
  • Item 20 contains at least one selected from the group consisting of halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes, and rare earth metal organic complexes.
  • Item 22 A display device or illumination device comprising the organic electroluminescent element according to any one of Items 17 to 21.
  • a novel fluorine-substituted polycyclic aromatic compound that can be used as a material for an organic device such as a material for an organic EL element can be provided.
  • An organic device such as an excellent organic EL element can be provided by using the compound.
  • a polycyclic aromatic compound (basic skeleton portion) in which aromatic rings are connected with heteroelements such as boron, phosphorus, oxygen, nitrogen, and sulfur has a large HOMO-LUMO gap (in a thin film). It has been found that it has a band gap Eg) and a high triplet excitation energy (E T ). This is because a 6-membered ring containing a hetero element has low aromaticity, so that the reduction of the HOMO-LUMO gap accompanying expansion of the conjugated system is suppressed, and the triplet excited state (T1) is caused by electronic perturbation of the hetero element. ) SOMO1 and SOMO2 are considered to be localized.
  • the polycyclic aromatic compound (basic skeleton portion) containing a hetero element according to the present invention has less exchange interaction between both orbitals due to localization of SOMO1 and SOMO2 in the triplet excited state (T1). Therefore, since the energy difference between the triplet excited state (T1) and the singlet excited state (S1) is small and shows thermally activated delayed fluorescence, it is also useful as a fluorescent material for organic EL elements.
  • a material having a high triplet excitation energy (E T ) is also useful as an electron transport layer or a hole transport layer of a phosphorescent organic EL device or an organic EL device using thermally activated delayed fluorescence.
  • these polycyclic aromatic compounds (basic skeleton parts) can move the energy of HOMO and LUMO arbitrarily by introducing substituents, the ionization potential and electron affinity are optimized according to the surrounding materials. It is possible.
  • the compound of the present invention can be expected to lower the sublimation temperature due to the decrease in molecular polarity by introducing fluorine atoms.
  • sublimation purification which is almost indispensable as a purification method for materials for organic devices such as organic EL elements that require high purity, can be purified at a relatively low temperature, so that thermal decomposition of the material can be avoided.
  • vacuum deposition process which is an effective means for producing organic devices such as organic EL elements, and the process can be carried out at a relatively low temperature, so that thermal decomposition of the material can be avoided.
  • High performance organic devices can be obtained.
  • Halogen includes chlorine, bromine and iodine in addition to fluorine.
  • chlorine, bromine and iodine when chlorine, bromine and iodine are substituted, the carbon bond is active, so it is slightly unstable chemically or electrochemically. When used as a material, drive deterioration may occur.
  • the carbon-fluorine bond is inactive and chemically and electrochemically stable, it is suitable as an organic device material.
  • the emission wavelength can be shortened by introducing an electron-accepting fluorine atom. This is particularly important in display applications that require high color purity blue emission.
  • the present invention relates to a polycyclic aromatic compound represented by the following general formula (1) or a polycycle having a plurality of structures represented by the following general formula (1)
  • a multimer of aromatic compounds preferably a polycyclic aromatic compound represented by the following general formula (2) or a large amount of polycyclic aromatic compounds having a plurality of structures represented by the following general formula (2)
  • at least one hydrogen in these compounds or structures is replaced by fluorine.
  • “B” in the ring together with “A” and “C” are symbols indicating the ring structure represented by the ring, and the other symbols are the same as those defined above.
  • the A ring, B ring and C ring in the general formula (1) are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings may be substituted with a substituent.
  • This substituent is substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino (with aryl Amino group having heteroaryl), substituted or unsubstituted diarylboryl (two aryls may be bonded via a single bond or a linking group), substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl Preferred are substituted or unsubstituted alkoxy or substituted or unsubstituted aryloxy.
  • substituents include aryl, heteroaryl, alkyl and cycloalkyl.
  • the aryl ring or heteroaryl ring may have a 5-membered or 6-membered ring sharing a bond with the central condensed bicyclic structure composed of Y 1 , X 1 and X 2. preferable.
  • the “fused bicyclic structure” means a structure in which two saturated hydrocarbon rings composed of Y 1 , X 1 and X 2 shown in the center of the general formula (1) are condensed.
  • the “six-membered ring sharing a bond with the condensed bicyclic structure” means, for example, an a ring (benzene ring (6-membered ring)) condensed to the condensed bicyclic structure as shown in the general formula (2). means.
  • the aryl ring or heteroaryl ring (which is A ring) has this 6-membered ring” means that the A ring is formed only by this 6-membered ring or includes this 6-membered ring.
  • aryl ring or heteroaryl ring having a 6-membered ring means that a 6-membered ring constituting all or part of the A ring is fused to the condensed bicyclic structure.
  • a ring (or B ring, C ring) in the general formula (1) is a ring in the general formula (2) and its substituents R 1 to R 3 (or b ring and its substituents R 8 to R 11 , c Corresponding to the ring and its substituents R 4 to R 7 ). That is, the general formula (2) corresponds to a structure in which “A to C rings having a 6-membered ring” are selected as the A to C rings of the general formula (1). In that sense, each ring of the general formula (2) is represented by lower case letters a to c.
  • adjacent groups of the substituents R 1 to R 11 of the a ring, b ring, and c ring are bonded to each other to form an aryl ring or a heteroaryl ring together with the a ring, b ring, or c ring.
  • at least one hydrogen in the formed ring is aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls are connected via a single bond or a linking group).
  • the polycyclic aromatic compound represented by the general formula (2) has the following formulas (2-1) and (2-2) depending on the mutual bonding form of the substituents in the a-ring, b-ring and c-ring. As shown, the ring structure constituting the compound changes. A ′ ring, B ′ ring and C ′ ring in each formula correspond to A ring, B ring and C ring in general formula (1), respectively. In addition, the definitions of R 1 to R 11 , a, b, c, Y 1 , X 1 and X 2 in each formula are the same as those in the general formula (2).
  • the A ′ ring, the B ′ ring and the C ′ ring are adjacent to the substituents R 1 to R 11 in the general formula (2).
  • the aryl ring or heteroaryl ring formed together with the a ring, b ring and c ring, respectively the condensed ring formed by condensing another ring structure to the a ring, b ring or c ring. It can also be said).
  • b-ring R 8 and c-ring R 7 , b-ring R 11 and a-ring R 1 , c-ring R 1 R 4 and R 3 in the a ring do not correspond to “adjacent groups” and they are not bonded. That is, “adjacent group” means an adjacent group on the same ring.
  • the compound represented by the above formula (2-1) or formula (2-2) is, for example, a benzene ring, an indole ring, a pyrrole ring, a benzofuran ring with respect to a benzene ring which is a ring (or b ring or c ring).
  • a compound having an A ′ ring (or B ′ ring or C ′ ring) formed by condensation of a benzothiophene ring, and a formed condensed ring A ′ (or condensed ring B ′ or condensed ring C ′) are respectively a naphthalene ring, a carbazole ring, an indole ring, a dibenzofuran ring or a dibenzothiophene ring.
  • Y 1 in the general formula (1) is B, P, P ⁇ O, P ⁇ S, Al, Ga, As, Si—R or Ge—R, and R in Si—R and Ge—R is Aryl, alkyl or cycloalkyl.
  • the atom bonded to the A ring, B ring or C ring is P, Si or Ge.
  • Y 1 is preferably B, P, P ⁇ O, P ⁇ S or Si—R, and particularly preferably B. This explanation is the same for Y 1 in the general formula (2).
  • X 1 and X 2 in the general formula (1) are each independently O, N—R, S, or Se, and R in the N—R is aryl which may be substituted, A heteroaryl, an optionally substituted alkyl or an optionally substituted cycloalkyl, wherein R in the N—R is bonded to the B ring and / or the C ring by a linking group or a single bond.
  • R in the “—C (—R) 2 —” is hydrogen, alkyl, or cycloalkyl. This description is the same for X 1 and X 2 in the general formula (2).
  • the definition that “the R in N—R is bonded to the A ring, B ring and / or C ring by a linking group or a single bond” is defined by the general formula (2)
  • the R of the N—R is bonded to the a ring, b ring and / or c ring by —O—, —S—, —C (—R) 2 — or a single bond”.
  • This definition can be expressed by a compound having a ring structure represented by the following formula (2-3-1) in which X 1 and X 2 are incorporated into the condensed ring B ′ and the condensed ring C ′. That is, for example, a B ′ ring (or a ring formed by condensation of another ring so as to incorporate X 1 (or X 2 ) into the benzene ring which is the b ring (or c ring) in the general formula (2) (or C ′ ring).
  • the formed condensed ring B ′ (or condensed ring C ′) is, for example, a phenoxazine ring, a phenothiazine ring or an acridine ring.
  • the above definition is a compound having a ring structure in which X 1 and / or X 2 is incorporated into the condensed ring A ′, which is represented by the following formula (2-3-2) or formula (2-3-3) But it can be expressed. That is, for example, a compound having an A ′ ring formed by condensing another ring so as to incorporate X 1 (and / or X 2 ) into the benzene ring which is the a ring in the general formula (2). .
  • the formed condensed ring A ′ is, for example, a phenoxazine ring, a phenothiazine ring or an acridine ring.
  • Examples of the “aryl ring” that is A ring, B ring and C ring in the general formula (1) include aryl rings having 6 to 30 carbon atoms, preferably aryl rings having 6 to 16 carbon atoms, An aryl ring having 6 to 12 carbon atoms is more preferable, and an aryl ring having 6 to 10 carbon atoms is particularly preferable.
  • the “aryl ring” is defined as “an aryl ring formed by bonding adjacent groups of R 1 to R 11 together with a ring, b ring or c ring” defined in the general formula (2).
  • the total number of carbon atoms of the condensed ring in which a 5-membered ring is condensed is a carbon having a lower limit. Number.
  • aryl rings include monocyclic benzene rings, bicyclic biphenyl rings, condensed bicyclic naphthalene rings, tricyclic terphenyl rings (m-terphenyl, o -Terphenyl, p-terphenyl), condensed tricyclic systems such as acenaphthylene ring, fluorene ring, phenalene ring, phenanthrene ring, condensed tetracyclic systems such as triphenylene ring, pyrene ring, naphthacene ring, condensed pentacyclic system Examples include a perylene ring and a pentacene ring.
  • heteroaryl ring that is A ring, B ring and C ring in the general formula (1) include heteroaryl rings having 2 to 30 carbon atoms, preferably heteroaryl rings having 2 to 25 carbon atoms.
  • a heteroaryl ring having 2 to 20 carbon atoms is more preferable, a heteroaryl ring having 2 to 15 carbon atoms is more preferable, and a heteroaryl ring having 2 to 10 carbon atoms is particularly preferable.
  • heteroaryl ring include a heterocycle containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring constituent atom.
  • the “heteroaryl ring” is a heteroaryl formed together with a ring, b ring or c ring by bonding adjacent groups of “R 1 to R 11 ” defined in the general formula (2).
  • the a ring (or b ring, c ring) is already composed of a benzene ring having 6 carbon atoms, the total number of carbon atoms of the condensed ring in which a 5-membered ring is condensed is lower limit. The number of carbons.
  • heteroaryl ring examples include pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, oxadiazole ring, thiadiazole ring, triazole ring, tetrazole ring, pyrazole ring, Pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring Cinnoline ring, quinazoline ring, quinoxaline ring, phthalazine ring, naphthyridine ring, purine ring, p
  • At least one hydrogen in the above “aryl ring” or “heteroaryl ring” is the first substituent, which is substituted or unsubstituted “aryl”, substituted or unsubstituted “heteroaryl”, substituted or unsubstituted “Diarylamino”, substituted or unsubstituted “diheteroarylamino”, substituted or unsubstituted “arylheteroarylamino”, substituted or unsubstituted “diarylboryl” (two aryls are connected via a single bond or a linking group)
  • Optionally substituted) ", substituted or unsubstituted” alkyl ", substituted or unsubstituted” cycloalkyl ", substituted or unsubstituted” alkoxy ", or substituted or unsubstituted” aryloxy "
  • an aryl group such as “aryl”, “heteroaryl”, or “diarylamin
  • alkyl as the first substituent may be either linear or branched, and examples thereof include linear alkyl having 1 to 24 carbon atoms and branched alkyl having 3 to 24 carbon atoms.
  • Alkyl having 1 to 18 carbons (branched alkyl having 3 to 18 carbons) is preferable, alkyl having 1 to 12 carbons (branched alkyl having 3 to 12 carbons) is more preferable, and alkyl having 1 to 6 carbons. (Branched alkyl having 3 to 6 carbon atoms) is more preferable, and alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms) is particularly preferable.
  • alkyl examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, and 1-methyl.
  • Pentyl 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propyl Pentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n- Tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-hepta Sill, n- octadecyl, such as n- eicosyl, and the like
  • Cycloalkyl as the first substituent includes cycloalkyl having 3 to 24 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, cycloalkyl having 3 to 16 carbon atoms, and cycloalkyl having 3 to 14 carbon atoms. Cycloalkyl having 5 to 10 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, cycloalkyl having 5 carbon atoms and the like.
  • cycloalkyl examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and their alkyl (particularly methyl) substituents having 1 to 4 carbon atoms, norbornenyl, bicyclo [1 .0.1] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.0.1] pentyl, bicyclo [1.2.1] hexyl, bicyclo [3.0.1] hexyl, bicyclo [2 1.2] heptyl, bicyclo [2.2.2] octyl, adamantyl, diamantyl, decahydronaphthalenyl, decahydroazulenyl and the like.
  • alkoxy as the first substituent includes, for example, straight-chain alkoxy having 1 to 24 carbon atoms or branched alkoxy having 3 to 24 carbon atoms.
  • C1-C18 alkoxy (C3-C18 branched alkoxy) is preferred, C1-C12 alkoxy (C3-C12 branched alkoxy) is more preferred, and C1-C6 Of alkoxy (C3-C6 branched chain alkoxy) is more preferable, and C1-C4 alkoxy (C3-C4 branched chain alkoxy) is particularly preferable.
  • alkoxy examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and the like.
  • aryl in the “diarylboryl” as the first substituent, the above description of aryl can be cited.
  • the two aryls may be bonded via a single bond or a linking group (eg,> C (—R) 2 ,>O,> S or> N—R).
  • R in> C (—R) 2 and> N—R is aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, or aryloxy (hereinafter, the first substituent), and the first The substituent may be further substituted with aryl, heteroaryl, alkyl or cycloalkyl (hereinafter, the second substituent).
  • Specific examples of these groups include aryl, hetero as the first substituent described above. References can be made to aryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy.
  • the emission wavelength can be adjusted by the steric hindrance, electron donating property, and electron withdrawing property of the structure of the first substituent, and preferably the following structural formulas (S-1) to (S-94) And more preferably a group represented by formula (S-1), formula (S-2), formula (S-5), formula (S-9) to formula (S-19), A group represented by any one of formulas (S-24) to (S-50) and (S-51) to (S-94), more preferably formula (S-1), (S-2), Formula (S-5), Formula (S-9), Formula (S-10), Formula (S-15), Formula (S-16), Formula (S-24), Formula (S-30), formula (S-46), formula (S-48), formula (S-50), formula (S-51), formula (S-56) to formula (S-58), formula (S -70), formula (S-71), formula (S-73), formula S-74), formula (S-76), formula (S-79), formula (S-80), a group represented by any one of formulas (S-1)
  • aryl or “heteroaryl ring”.
  • alkyl or “cycloalkyl” as the first substituent.
  • aryl or heteroaryl as the second substituent at least one hydrogen in them is aryl such as phenyl (specific examples are the groups described above), alkyl such as methyl (specific examples are the groups described above) or Groups substituted with cycloalkyl such as cyclohexyl (specific examples are the groups described above) are also included in aryl and heteroaryl as the second substituent.
  • aryl such as phenyl
  • alkyl such as methyl
  • cycloalkyl specifically examples are the groups described above
  • alkyl, cycloalkyl or alkoxy in R 1 to R 11 see the description of “alkyl”, “cycloalkyl” or “alkoxy” as the first substituent in the description of the general formula (1). can do.
  • aryl, heteroaryl, alkyl or cycloalkyl as a substituent for these groups.
  • adjacent groups of R 1 to R 11 are bonded to form an aryl ring or a heteroaryl ring together with a ring, b ring or c ring, heteroaryl which is a substituent for these rings.
  • R in Si—R and Ge—R in Y 1 in the general formula (1) is aryl, alkyl or cycloalkyl, and examples of the aryl, alkyl or cycloalkyl include the groups described above.
  • aryl having 6 to 10 carbon atoms eg, phenyl, naphthyl, etc.
  • alkyl having 1 to 4 carbon atoms eg, methyl, ethyl, etc.
  • cycloalkyl having 5 to 10 carbon atoms preferably cyclohexyl or adamantyl
  • R of N—R in X 1 and X 2 of the general formula (1) is aryl, heteroaryl, alkyl or cycloalkyl, which may be substituted with the second substituent described above, and in aryl or heteroaryl At least one hydrogen may be substituted, for example with alkyl or cycloalkyl.
  • the aryl, heteroaryl, alkyl and cycloalkyl include the groups described above.
  • aryl having 6 to 10 carbon atoms for example, phenyl, naphthyl and the like
  • heteroaryl having 2 to 15 carbon atoms for example, carbazolyl and the like
  • alkyl having 1 to 4 carbon atoms for example, methyl, ethyl and the like
  • 5 to 10 carbon atoms Cycloalkyl (preferably cyclohexyl or adamantyl) is preferred. This description is the same for X 1 and X 2 in the general formula (2).
  • R in “—C (—R) 2 —” as the linking group in the general formula (1) is hydrogen, alkyl or cycloalkyl.
  • alkyl and cycloalkyl include the groups described above.
  • alkyl having 1 to 4 carbon atoms for example, methyl, ethyl, etc.
  • cycloalkyl having 5 to 10 carbon atoms preferably cyclohexyl or adamantyl
  • This explanation is the same for “—C (—R) 2 —” which is a linking group in the general formula (2).
  • the present invention also provides a multimer of polycyclic aromatic compounds having a plurality of unit structures represented by the general formula (1), preferably a polycyclic aromatic having a plurality of unit structures represented by the general formula (2).
  • the multimer is preferably a dimer to hexamer, more preferably a dimer to trimer, and particularly preferably a dimer.
  • the multimer may be in a form having a plurality of the unit structures in one compound.
  • the unit structure is a linking group such as a single bond, an alkylene group having 1 to 3 carbon atoms, a phenylene group, or a naphthylene group.
  • any ring (A ring, B ring or C ring, a ring, b ring or c ring) contained in the unit structure is shared by the multiple unit structures
  • the bonded form (ring-shared multimer) may be used, and any ring (A ring, B ring or C ring, a ring, b ring or c ring) included in the unit structure may be May be combined in a condensed form (ring-condensed multimer), but a ring-shared multimer and a ring-condensed multimer are preferable, and a ring-shared multimer is more preferable.
  • Examples of such multimers include the following formula (2-4), formula (2-4-1), formula (2-4-2), formula (2-5-1) to formula (2-5). -4) or a multimeric compound represented by formula (2-6).
  • the multimeric compound represented by the following formula (2-4) can be represented by a plurality of general formulas (2) so as to share a benzene ring which is a ring, as explained by the general formula (2). It is a multimeric compound (ring-shared multimer) having a unit structure in one compound.
  • the multimeric compound represented by the following formula (2-4-1) can be expressed by two general formulas (2) so as to share a benzene ring which is a ring, as explained by the general formula (2).
  • the multimeric compound represented by the following formula (2-4-2) can be described by the general formula (2), so that the benzene ring as the a ring is shared, so that the three general formulas (2)
  • the multimeric compound represented by the following formulas (2-5-1) to (2-5-4) can be represented by the general formula (2) as a benzene ring which is a b ring (or a c ring). Is a multimeric compound (ring-sharing multimer) having a plurality of unit structures represented by the general formula (2) in one compound.
  • the multimeric compound represented by the following formula (2-6) can be represented by the general formula (2), for example, a benzene ring which is a b ring (or a ring or c ring) having a certain unit structure and a certain unit.
  • Type multimer ).
  • the multimeric compound includes a multimerized form represented by formula (2-4), formula (2-4-1) or formula (2-4-2), and formulas (2-5-1) to (2) -5-4) or a multimer in combination with a multimerized form represented by formula (2-6) may be used, and may be represented by formula (2-5-1) to formula (2-5) 4) may be a multimer in which the multimerized form represented by any one of 4) and the multimerized form represented by formula (2-6) are combined.
  • Formula (2-4) and formula (2) -4-1) or the multimerized form represented by formula (2-4-2) and the multimerized form represented by any of formulas (2-5-1) to (2-5-4) A multimer combined with the multimerized form represented by the formula (2-6) may be used.
  • the hydrogen in the chemical structure of the polycyclic aromatic compound represented by the general formula (1) or (2) and its multimer is all or part of cyano, chlorine, bromine, iodine or deuterium. May be.
  • deuterium may be substituted, and among these, an embodiment in which all or part of hydrogen in aryl or heteroaryl is substituted with cyano, chlorine, bromine, iodine or deuterium can be mentioned.
  • chlorine, bromine or iodine chlorine or bromine is preferable, and chlorine is more preferable.
  • the polycyclic aromatic compound and its multimer according to the present invention can be used as a material for organic devices.
  • an organic device an organic electroluminescent element, an organic field effect transistor, an organic thin film solar cell, etc. are mention
  • Y 1 is B
  • X 1 and X 2 are N—R compounds
  • Y 1 is B
  • X 1 is O
  • X 2 is N—R.
  • At least one hydrogen in the chemical structure of the polycyclic aromatic compound represented by the general formula (1) or (2) and its multimer is fluorine-substituted, and all or some of the hydrogen is fluorine. It may be.
  • Aryl in addition to the form in which the A to C rings in the formula (1) are directly substituted with fluorine, or the form in which the hydrogen selected as R 1 to R 11 in the formula (2) is substituted with fluorine, Aryl, heteroaryl (especially carbazolyl group or benzocarbazolyl group), diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls are a single bond or a linkage) At least one of the alkyl, cycloalkyl, alkoxy or aryloxy hydrogens, the second substituent as described above, the aryl, heteroaryl, alkyl or cycloalkyl hydrogens.
  • At least one of them may be substituted with fluorine.
  • at least one of hydrogens in aryl, heteroaryl, alkyl, or cycloalkyl (hereinafter referred to as the first substituent), or a substituent (second substituent) thereto as R of N—R is fluorine. It may be a substituted form.
  • Other examples include a pentafluorosulfanyl group (—SF 5 ) and the like.
  • the polycyclic aromatic compound represented by the general formula (1) or (2) and a multimer thereof include, for example, a fluorine-substituted aryl group, a fluorine-substituted alkyl group, or a cyclohexane.
  • aryl group examples include those described above as the “first substituent”.
  • substitution form of fluorine to the diarylamino group, diarylboryl group, carbazolyl group, and benzocarbazolyl group examples include examples in which some or all of the hydrogens of the aryl ring or benzene ring in these groups are substituted with fluorine. It is done.
  • X 1 and X 2 are preferably N—R, and R is preferably fluorine-substituted aryl (particularly fluorine-substituted phenyl). It is preferable that the aryl of the diarylamino group as the substituent or the second substituent is a fluorine-substituted aryl (particularly fluorine-substituted phenyl), and X 1 and X 2 are N—R, More preferably, R is fluorine-substituted aryl (particularly fluorine-substituted phenyl).
  • Aryl substituted with fluorine includes a group in which at least one hydrogen of the aryl is substituted with fluorine.
  • any of the following structural formulas (S-100) to (S-110) Group represented by a group represented by any of the formulas (S-100) to (S-107) is preferable, and a formula (S-100), a formula (S-103), a formula (S -104) and a group represented by formula (S-105).
  • This explanation also applies when the aryl moiety of “diarylamino”, “arylheteroarylamino”, “diarylboryl” or “aryloxy” is substituted by fluorine.
  • Alkyl substituted with fluorine includes a group in which at least one hydrogen of the alkyl is substituted with fluorine, and specific examples thereof include trifluoromethyl, difluoromethyl, monofluoromethyl, pentafluoroethyl and the like. And trifluoromethyl is preferred. This explanation also applies when fluorine is substituted at the alkyl moiety of “alkoxy (alkyloxy)”.
  • Examples of “cycloalkyl” substituted with fluorine include groups in which at least one hydrogen of the cycloalkyl is substituted with fluorine.
  • R 2 in the polycyclic aromatic compound represented by the general formula (2) and its multimer is a fluorine-substituted diarylamino group, a fluorine-substituted diarylboryl group (2 Examples where the two aryls may be bonded via a single bond or a linking group) or a fluorinated carbazolyl group.
  • An example of this is a polycyclic aromatic compound represented by the following general formula (2-A) or a multimer of polycyclic aromatic compounds having a plurality of structures represented by the following general formula (2-A). .
  • the definition of each symbol in the structural formula is the same as the definition of each symbol in the general formula (2).
  • fluorine-substituted polycyclic aromatic compound and the multimer thereof according to the present invention include at least one hydrogen atom in one or more aromatic rings in the compound having one or more fluorine atoms.
  • examples thereof include compounds substituted with 1 to 2 fluorine atoms.
  • N in the following structural formulas are each independently 0 to 2, preferably 1.
  • F represents fluorine
  • OPh represents a phenoxy group
  • Me represents a methyl group.
  • fluorine-substituted polycyclic aromatic compound of the present invention include compounds represented by the following structural formula.
  • F represents fluorine
  • D represents deuterium
  • Me represents a methyl group
  • Et represents an ethyl group
  • tBu represents a t-butyl group.
  • the polycyclic aromatic compound represented by the general formulas (1) and (2) and the multimer thereof are first composed of ring A (a Ring) and B ring (b ring) and C ring (c ring) are bonded to each other with a linking group (a group containing X 1 and X 2 ) (first reaction), and then A
  • the final product can be produced by bonding the ring (a ring), the B ring (b ring) and the C ring (c ring) with a linking group (a group containing Y 1 ) (second reaction).
  • a general reaction such as a nucleophilic substitution reaction and an Ullmann reaction can be used for an etherification reaction, and a general reaction such as a Buchwald-Hartwig reaction can be used for an amination reaction.
  • a tandem hetero Friedel-Crafts reaction continuous aromatic electrophilic substitution reaction, the same applies hereinafter
  • the compound of the present invention in which a desired position is fluorinated by using a fluorinated raw material or adding a fluorination or fluorine-containing substituent introduction step somewhere in these reaction steps Can be manufactured.
  • the second reaction is a reaction for introducing Y 1 that connects the A ring (a ring), the B ring (b ring), and the C ring (c ring).
  • Y 1 is a boron atom and X 1 and X 2 are oxygen atoms is shown below.
  • a hydrogen atom and n- butyllithium between X 1 and X 2 ortho-metalated with sec- butyllithium or t- butyl lithium, and the like.
  • the said scheme (1) and (2) mainly show the manufacturing method of the polycyclic aromatic compound represented by General formula (1) or (2), about the multimer, about several It can manufacture by using the intermediate body which has A ring (a ring), B ring (b ring), and C ring (c ring). Details will be described in the following schemes (3) to (5).
  • the target product can be obtained by setting the amount of the reagent such as butyl lithium to be doubled or tripled.
  • lithium is introduced into a desired position by orthometalation.
  • a bromine atom or the like is introduced at a position where lithium is to be introduced, and halogen-metal exchange is also performed.
  • Lithium can be introduced at the desired location.
  • a halogen such as a bromine atom or a chlorine atom is introduced at a position where lithium is to be introduced as in the above schemes (6) and (7).
  • Lithium can be introduced into a desired position also by exchange (the following schemes (8), (9) and (10)).
  • This method is useful because the target product can be synthesized even in the case where ortho-metalation is not possible due to the influence of substituents.
  • the desired position is fluorinated, has a substituent at the desired position, Y 1 is a boron atom, and X 1 and X 2 are oxygen. It is possible to synthesize polycyclic aromatic compounds that are atoms and multimers thereof.
  • Y 1 is a boron atom and X 1 and X 2 are nitrogen atoms is shown in the following schemes (11) and (12).
  • X 1 and X 2 are oxygen atoms
  • the hydrogen atom between X 1 and X 2 is first ortho-metalated with n-butyllithium or the like.
  • boron tribromide and the like are added, and after lithium-boron metal exchange, Brensted base such as N, N-diisopropylethylamine is added to cause tandem Bora Friedel-Crafts reaction to obtain the target product.
  • a Lewis acid such as aluminum trichloride may be added to promote the reaction.
  • the target product can be obtained only with boron tribromide.
  • the compound of the present invention in which a desired position is fluorinated by using a fluorinated raw material or adding a fluorination or fluorine-containing substituent introduction step somewhere in these reaction steps Can be manufactured.
  • a halogen such as a bromine atom or a chlorine atom is introduced at the position where lithium is to be introduced as in the above schemes (6) and (7).
  • lithium can be introduced into the desired position also by halogen-metal exchange (Schemes (13), (14) and (15) below).
  • Scheme (13 ′) when boron triiodide and triphenylborane are used and Y 1 is a boron atom and X 1 and X 2 are nitrogen atoms without using halogen-metal exchange, Multimers can also be synthesized.
  • m-CPBA m-chloroperbenzoic acid
  • Y 1 phosphorus oxide
  • triethylphosphine Y 1 becomes phosphorus Compounds that are atoms
  • the compound of the present invention in which a desired position is fluorinated by using a fluorinated raw material or adding a fluorination or fluorine-containing substituent introduction step somewhere in these reaction steps Can be manufactured.
  • a halogen such as a bromine atom or a chlorine atom is located at a position where lithium is to be introduced as in the above schemes (6) and (7). And lithium can be introduced into a desired position also by halogen-metal exchange (the following schemes (20), (21) and (22)).
  • the thus-produced multimer in which Y 1 is a phosphorous sulfide and X 1 and X 2 are oxygen atoms is also represented by m-chloroperbenzoic acid (in the above schemes (18) and (19)).
  • a compound in which Y 1 is a phosphorus oxide can be obtained by treatment with m-CPBA), and a compound in which Y 1 is a phosphorus atom can be obtained by treatment with triethylphosphine.
  • Y 1 is B, P, P ⁇ O or P ⁇ S, and X 1 and X 2 are O or NR is described.
  • Y 1 is A compound in which Al, Ga, As, Si—R or Ge—R, or X 1 and X 2 are S can also be synthesized.
  • halogen-metal exchange or a coupling reaction is used as an example of a process for producing the target product.
  • Halogen includes fluorine atoms, but the carbon-fluorine bond is generally very inactive. Therefore, when fluorine is used as the halogen, generally halogen-metal exchange and coupling reactions are not performed. Does not happen. Therefore, in most cases, even if fluorine atoms coexist, the reaction proceeds selectively at the position of chlorine, bromine or iodine, so that the above-described reaction progress is inhibited even when a raw material containing fluorine atoms is used. Rather, the compound of the present invention in which the desired position is fluorinated can be produced.
  • a raw material substituted with a fluorine-substituted alkyl group, a fluorine-substituted aryl group, a fluorine-substituted heteroaryl group, a fluorine-substituted aryloxy group, or a pentafluorosulfanyl group (—SF 5 ) is used.
  • the compound of the present invention in which a desired position is fluorinated can be produced by using or adding a step for introducing these functional groups.
  • solvent used in the above reaction examples include t-butylbenzene and xylene.
  • the polycyclic aromatic compound represented by the general formula (2) has the formula (2-) in the following schemes (23) and (24) depending on the mutual bonding form of the substituents in the a-ring, b-ring and c-ring. As shown in 1) and formula (2-2), the ring structure constituting the compound changes.
  • the A ′ ring, the B ′ ring and the C ′ ring are formed by bonding adjacent groups of the substituents R 1 to R 11 to each of a An aryl ring or a heteroaryl ring formed together with a ring, b ring and c ring is shown (also referred to as a condensed ring formed by condensing another ring structure to the a ring, b ring or c ring).
  • R in N—R is bonded to the a ring, b ring and / or c ring by —O—, —S—, —C (—R) 2 — or a single bond.
  • it can be represented by a compound having a ring structure represented by formula (2-3-2) or formula (2-3-3) in which X 1 or X 2 is incorporated into condensed ring A ′.
  • Y 1 is phosphorus-based, as shown in the following schemes (26) and (27), the hydrogen atom between X 1 and X 2 (O in the following formula) is replaced with n-butyllithium, sec- Orthometalation with butyllithium or t-butyllithium, etc., followed by addition of bisdiethylaminochlorophosphine, metal exchange of lithium-phosphorus, and addition of Lewis acid such as aluminum trichloride
  • the target product can be obtained by reaction. This reaction method is also described in International Publication No. 2010/104047 (for example, page 27). Further, the compound of the present invention in which a desired position is fluorinated by using a fluorinated raw material or adding a fluorination or fluorine-containing substituent introduction step somewhere in these reaction steps Can be manufactured.
  • a multimeric compound is synthesized by using an orthometalation reagent such as butyl lithium in a molar amount twice or three times that of the intermediate 1. can do. Further, by introducing a halogen such as a bromine atom or a chlorine atom in advance at a position where a metal such as lithium is to be introduced, and replacing the halogen-metal, the metal can be introduced at a desired position.
  • an orthometalation reagent such as butyl lithium in a molar amount twice or three times that of the intermediate 1.
  • the intermediate before cyclization in Scheme (28) can also be synthesized by the method shown in Scheme (1) and the like. That is, an intermediate having a desired substituent can be synthesized by appropriately combining Buchwald-Hartwig reaction, Suzuki coupling reaction, or etherification reaction such as nucleophilic substitution reaction or Ullmann reaction. In these reactions, a commercially available product can be used as a raw material to be a fluorinated precursor.
  • the compound of the general formula (2-A) having a fluorinated diphenylamino group can also be synthesized, for example, by the following method. That is, after introducing a diphenylamino group fluorinated by amination reaction such as Buchwald-Hartwig reaction between commercially available bromopentafluorophenylbenzene and trihalogenated aniline, X 1 and X 2 are N—R.
  • amination reaction such as Buchwald-Hartwig reaction between commercially available bromopentafluorophenylbenzene and trihalogenated aniline
  • the orthometalation reagents used in the above schemes (1) to (28) include alkyllithiums such as methyllithium, n-butyllithium, sec-butyllithium, and t-butyllithium, lithium diisopropylamide, and lithium tetramethyl. And organic alkali compounds such as piperidide, lithium hexamethyldisilazide, and potassium hexamethyldisilazide.
  • the metal exchange reagent for metal-Y 1 used in the above schemes (1) to (28) includes Y 1 trifluoride, Y 1 trichloride, Y 1 tribromide, Y 1 triiodide.
  • halides of Y 1 such as halide, CIPN (NEt 2) 2 amination halide Y 1, such as, alkoxides of Y 1, an aryloxy compound of Y 1 and the like.
  • the Bronsted base used in the above schemes (1) to (28) includes N, N-diisopropylethylamine, triethylamine, 2,2,6,6-tetramethylpiperidine, 1,2,2,6,6. -Pentamethylpiperidine, N, N-dimethylaniline, N, N-dimethyltoluidine, 2,6-lutidine, sodium tetraphenylborate, potassium tetraphenylborate, triphenylborane, tetraphenylsilane, Ar 4 BNa, Ar 4 BK, Ar 3 B, Ar 4 Si (where Ar is an aryl such as phenyl) and the like.
  • a Bronsted base or a Lewis acid may be used to promote the tandem heterofriedel crafts reaction.
  • Y 1 halides such as Y 1 trifluoride, Y 1 trichloride, Y 1 tribromide, Y 1 triiodide
  • an acid such as hydrogen fluoride, hydrogen chloride, hydrogen bromide, or hydrogen iodide is generated, it is effective to use a Bronsted base that captures the acid.
  • the polycyclic aromatic compound or multimer thereof of the present invention includes a structure in which at least a part of hydrogen atoms are substituted with cyano, a structure in which halogens such as chlorine, bromine and iodine are substituted, and deuterium.
  • halogens such as chlorine, bromine and iodine are substituted
  • deuterium a structure in which halogens such as chlorine, bromine and iodine are substituted
  • Substituted structures are also included, but such compounds can be synthesized in the same way as described above using raw materials in which the desired position is cyanated, chlorinated, brominated, iodinated or deuterated. Can do.
  • the fluorine-substituted polycyclic aromatic compound according to the present invention can be used as a material for an organic device.
  • an organic device an organic electroluminescent element, an organic field effect transistor, an organic thin film solar cell, etc. are mention
  • FIG. 1 is a schematic cross-sectional view showing an organic EL element according to this embodiment.
  • An organic EL element 100 shown in FIG. 1 includes a substrate 101, an anode 102 provided on the substrate 101, a hole injection layer 103 provided on the anode 102, and a hole injection layer 103.
  • the hole transport layer 104 provided, the light emitting layer 105 provided on the hole transport layer 104, the electron transport layer 106 provided on the light emitting layer 105, and the electron transport layer 106 are provided.
  • the electron injection layer 107 and the cathode 108 provided on the electron injection layer 107 are provided.
  • the organic EL element 100 is manufactured in the reverse order, for example, the substrate 101, the cathode 108 provided on the substrate 101, the electron injection layer 107 provided on the cathode 108, and the electron injection layer 107.
  • An electron transport layer 106 provided on the light emitting layer 105, a light emitting layer 105 provided on the electron transport layer 106, a hole transport layer 104 provided on the light emitting layer 105, and a hole transport layer 104.
  • the hole injection layer 103 provided on the hole injection layer 103 and the anode 102 provided on the hole injection layer 103 may be used.
  • each said layer may consist of a single layer, respectively, and may consist of multiple layers.
  • the layer constituting the organic EL element in addition to the above-described configuration aspect of “substrate / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode”, “Substrate / anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode”, “substrate / anode / hole injection layer / light emitting layer / electron transport layer / electron injection layer / cathode”, “substrate / Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode ”,“ substrate / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode ”,“ substrate / Anode / light emitting layer / electron transport layer / electron injection layer / cathode ”,“ substrate / Anode /
  • the substrate 101 is a support for the organic EL element 100, and quartz, glass, metal, plastic, or the like is usually used.
  • the substrate 101 is formed into a plate shape, a film shape, or a sheet shape according to the purpose.
  • a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, or the like is used.
  • glass plates and transparent synthetic resin plates such as polyester, polymethacrylate, polycarbonate, polysulfone and the like are preferable.
  • soda lime glass, non-alkali glass, or the like is used, and the thickness only needs to be sufficient to maintain the mechanical strength.
  • the upper limit value of the thickness is, for example, 2 mm or less, preferably 1 mm or less.
  • the glass material is preferably alkali-free glass because it is better to have less ions eluted from the glass.
  • soda lime glass with a barrier coat such as SiO 2 is also commercially available, so it can be used. it can.
  • the substrate 101 may be provided with a gas barrier film such as a dense silicon oxide film on at least one surface in order to improve the gas barrier property, and a synthetic resin plate, film or sheet having a low gas barrier property is used as the substrate 101. When used, it is preferable to provide a gas barrier film.
  • the anode 102 serves to inject holes into the light emitting layer 105.
  • the hole injection layer 103 and / or the hole transport layer 104 are provided between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 through these layers. .
  • Examples of the material for forming the anode 102 include inorganic compounds and organic compounds.
  • Examples of inorganic compounds include metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (indium oxide, tin oxide, indium-tin oxide (ITO), indium-zinc oxide) Products (IZO), metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass, Nesa glass, and the like.
  • Examples of the organic compound include polythiophene such as poly (3-methylthiophene), conductive polymer such as polypyrrole and polyaniline, and the like. In addition, it can select suitably from the substances used as an anode of an organic EL element.
  • the resistance of the transparent electrode is not limited as long as it can supply a sufficient current for light emission of the light emitting element, but is preferably low resistance from the viewpoint of power consumption of the light emitting element.
  • an ITO substrate of 300 ⁇ / ⁇ or less functions as an element electrode, but at present, since it is possible to supply a substrate of about 10 ⁇ / ⁇ , for example, 100 to 5 ⁇ / ⁇ , preferably 50 to 5 ⁇ . It is particularly desirable to use a low resistance product of / ⁇ .
  • the thickness of ITO can be arbitrarily selected according to the resistance value, but is usually used in a range of 50 to 300 nm.
  • the hole injection layer 103 plays a role of efficiently injecting holes moving from the anode 102 into the light emitting layer 105 or the hole transport layer 104.
  • the hole transport layer 104 serves to efficiently transport holes injected from the anode 102 or holes injected from the anode 102 via the hole injection layer 103 to the light emitting layer 105.
  • the hole injection layer 103 and the hole transport layer 104 are each formed by laminating and mixing one kind or two or more kinds of hole injection / transport materials or a mixture of the hole injection / transport material and the polymer binder. Is done.
  • an inorganic salt such as iron (III) chloride may be added to the hole injection / transport material to form a layer.
  • a hole injection / transport material As a hole injection / transport material, it is necessary to efficiently inject and transport holes from the positive electrode between electrodes to which an electric field is applied. The hole injection efficiency is high, and the injected holes are transported efficiently. It is desirable to do. For this purpose, it is preferable to use a substance that has a low ionization potential, a high hole mobility, excellent stability, and is less likely to generate trapping impurities during production and use.
  • a compound conventionally used as a charge transport material for holes in a photoconductive material, a p-type semiconductor, and a hole injection layer of an organic EL element are used.
  • any compound can be selected and used from known compounds used in the hole transport layer. Specific examples thereof include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis (N-arylcarbazole) or bis (N-alkylcarbazole), triarylamine derivatives (aromatic tertiary class).
  • polycarbonates, styrene derivatives, polyvinylcarbazole, polysilanes, etc. having the aforementioned monomers in the side chain are preferred, but light emitting devices There is no particular limitation as long as it is a compound that can form a thin film necessary for the fabrication, inject holes from the anode, and further transport holes.
  • organic semiconductors are strongly influenced by the doping.
  • Such an organic semiconductor matrix material is composed of a compound having a good electron donating property or a compound having a good electron accepting property.
  • Strong electron acceptors such as tetracyanoquinone dimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinone dimethane (F4TCNQ) are known for doping of electron donor materials.
  • TCNQ tetracyanoquinone dimethane
  • F4TCNQ 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinone dimethane
  • the light-emitting layer 105 is a layer that emits light by recombining holes injected from the anode 102 and electrons injected from the cathode 108 between electrodes to which an electric field is applied.
  • the material for forming the light-emitting layer 105 may be a compound that emits light by being excited by recombination of holes and electrons (a light-emitting compound), can form a stable thin film shape, and is in a solid state It is preferable that the compound exhibits a strong light emission (fluorescence) efficiency.
  • a host material and, for example, a polycyclic aromatic compound represented by the general formula (1) as a dopant material can be used as the material for the light emitting layer.
  • the light emitting layer may be either a single layer or a plurality of layers, each formed of a light emitting layer material (host material, dopant material).
  • a light emitting layer material host material, dopant material
  • Each of the host material and the dopant material may be one kind or a plurality of combinations.
  • the dopant material may be included in the host material as a whole, or may be included partially.
  • As a doping method it can be formed by a co-evaporation method with a host material, but it may be pre-mixed with the host material and then simultaneously deposited.
  • the amount of host material used depends on the type of host material and can be determined according to the characteristics of the host material.
  • the standard of the amount of the host material used is preferably 50 to 99.999% by weight of the entire light emitting layer material, more preferably 80 to 99.95% by weight, and still more preferably 90 to 99.9% by weight. It is.
  • the amount of dopant material used depends on the type of dopant material, and can be determined according to the characteristics of the dopant material.
  • the standard of the amount of dopant used is preferably 0.001 to 50% by weight, more preferably 0.05 to 20% by weight, and further preferably 0.1 to 10% by weight of the entire material for the light emitting layer. is there.
  • the above range is preferable in that, for example, the concentration quenching phenomenon can be prevented.
  • Host materials include fused ring derivatives such as anthracene, pyrene, dibenzochrysene or fluorene that have been known as light emitters, bisstyryl derivatives such as bisstyrylanthracene derivatives and distyrylbenzene derivatives, tetraphenylbutadiene derivatives, and cyclopentadiene derivatives.
  • fused ring derivatives such as anthracene, pyrene, dibenzochrysene or fluorene that have been known as light emitters
  • bisstyryl derivatives such as bisstyrylanthracene derivatives and distyrylbenzene derivatives
  • tetraphenylbutadiene derivatives tetraphenylbutadiene derivatives
  • cyclopentadiene derivatives cyclopentadiene derivatives.
  • an anthracene compound, a fluorene compound, or a dibenzochrysene compound
  • An anthracene compound as a host is, for example, a compound represented by the following general formula (3).
  • each X is independently a group represented by the above formula (3-X1), formula (3-X2) or formula (3-X3), and the formula (3-X1), formula (3)
  • the group represented by (3-X2) or formula (3-X3) is bonded to the anthracene ring of formula (3) at *.
  • two Xs do not become a group represented by the formula (3-X3) at the same time. More preferably, two Xs do not simultaneously become a group represented by the formula (3-X2).
  • a multimer may be formed with the structure represented by the formula (3) as a unit structure.
  • X include a single bond, arylene (such as phenylene, biphenylene, and naphthylene), and heteroarylene (a pyridine ring, A group having a divalent valence such as a dibenzofuran ring, a dibenzothiophene ring, a carbazole ring, a benzocarbazole ring and a phenyl-substituted carbazole ring).
  • the naphthylene moiety in formula (3-X1) and formula (3-X2) may be condensed with one benzene ring.
  • the structure thus condensed is as follows.
  • Ar 1 and Ar 2 are each independently hydrogen, phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, chrycenyl, triphenylenyl, pyrenylyl, or the above formula (A) Represented groups (including carbazolyl, benzocarbazolyl and phenyl-substituted carbazolyl groups).
  • the group represented by the formula (A) is the same as that in the formula (3-X1) or (3-X2) Bonds with the naphthalene ring.
  • Ar 3 is phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, chrysenyl, triphenylenyl, pyrenylyl, or a group represented by the above formula (A) (carbazolyl group, benzocarbyl group) A zolyl group and a phenyl-substituted carbazolyl group).
  • Ar 3 is a group represented by the formula (A)
  • the group represented by the formula (A) is bonded to a single bond represented by a straight line in the formula (3-X3) at *. . That is, the anthracene ring of formula (3) and the group represented by formula (A) are directly bonded.
  • Ar 3 may have a substituent, and at least one hydrogen in Ar 3 is further alkyl having 1 to 4 carbons, cycloalkyl having 5 to 10 carbons, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl. , Fluorenyl, chrycenyl, triphenylenyl, pyrenylyl, or a group represented by the above formula (A) (including a carbazolyl group and a phenyl-substituted carbazolyl group). Note that when the substituent that Ar 3 has is a group represented by the formula (A), the group represented by the formula (A) is bonded to Ar 3 in the formula (3-X3) at *.
  • Ar 4 is each independently substituted with hydrogen, phenyl, biphenylyl, terphenylyl, naphthyl, or alkyl having 1 to 4 carbon atoms (methyl, ethyl, t-butyl, etc.) and / or cycloalkyl having 5 to 10 carbon atoms. Has been silyl.
  • alkyl having 1 to 4 carbon atoms to be substituted with silyl examples include methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl, cyclobutyl and the like. Are substituted with these alkyls.
  • sil substituted with alkyl having 1 to 4 carbon atoms include trimethylsilyl, triethylsilyl, tripropylsilyl, trii-propylsilyl, tributylsilyl, trisec-butylsilyl, tri-t-butylsilyl, ethyl Dimethylsilyl, propyldimethylsilyl, i-propyldimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, t-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, i-propyldiethylsilyl, butyldiethylsilyl, sec-butyl Diethylsilyl, t-butyldiethylsilyl, methyldipropylsilyl, ethyldipropylsilyl, buty
  • Cycloalkyl having 5 to 10 carbon atoms to be substituted with silyl is cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornenyl, bicyclo [1.1.1] pentyl, bicyclo [2.0.1] pentyl, Bicyclo [1.2.1] hexyl, bicyclo [3.0.1] hexyl, bicyclo [2.1.2] heptyl, bicyclo [2.2.2] octyl, adamantyl, decahydronaphthalenyl, decahydro Azulenyl and the like, and the three hydrogens in silyl are each independently substituted with these cycloalkyls.
  • sil substituted with a cycloalkyl having 5 to 10 carbon atoms include tricyclopentylsilyl, tricyclohexylsilyl and the like.
  • Substituted silyls include dialkylcycloalkylsilyl substituted with two alkyls and one cycloalkyl, and alkyldicycloalkylsilyl substituted with one alkyl and two cycloalkyls.
  • Substituted alkyls and cycloalkyls Specific examples of these include the groups described above.
  • hydrogen in the chemical structure of the anthracene compound represented by the general formula (3) may be substituted with a group represented by the above formula (A).
  • the group represented by formula (A) substitutes at least one hydrogen in the compound represented by formula (3) at *.
  • the group represented by the formula (A) is one of the substituents that the anthracene compound represented by the formula (3) may have.
  • Y is —O—, —S— or> N—R 29
  • R 21 to R 28 are each independently hydrogen, optionally substituted alkyl, or optionally substituted.
  • R 29 may be hydrogen or substituted A reel.
  • alkyl of “optionally substituted alkyl” in R 21 to R 28 may be either linear or branched, for example, linear alkyl having 1 to 24 carbon atoms or having 3 to 24 carbon atoms.
  • Alkyl having 1 to 18 carbons (branched alkyl having 3 to 18 carbons) is preferable, alkyl having 1 to 12 carbons (branched alkyl having 3 to 12 carbons) is more preferable, and alkyl having 1 to 6 carbons. (Branched alkyl having 3 to 6 carbon atoms) is more preferable, and alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms) is particularly preferable.
  • alkyl examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1 -Methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2 -Propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecy
  • Cycloalkyl of “optionally substituted cycloalkyl” for R 21 to R 28 is cycloalkyl having 3 to 24 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, or cycloalkyl having 3 to 16 carbon atoms. Cycloalkyl having 3 to 14 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, cycloalkyl having 5 carbon atoms, and the like.
  • cycloalkyl examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and alkyl (especially methyl) substituents thereof having 1 to 4 carbon atoms, norbornenyl, bicyclo [1.0.1] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.0.1] pentyl, bicyclo [1.2.1] hexyl, bicyclo [3.0.1] hexyl, bicyclo [2.1.2] heptyl, bicyclo [2.2.2] octyl, adamantyl, diamantyl, decahydronaphthalenyl, decahydroazurenyl and the like.
  • Examples of the “aryl” of “optionally substituted aryl” in R 21 to R 28 include aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 16 carbon atoms, and 6 to 12 carbon atoms. Are more preferable, and aryl having 6 to 10 carbon atoms is particularly preferable.
  • aryl includes monocyclic phenyl, bicyclic biphenylyl, fused bicyclic naphthyl, tricyclic terphenylyl (m-terphenylyl, o-terphenylyl, p-terphenylyl) And condensed tricyclic systems such as acenaphthylenyl, fluorenyl, phenalenyl, phenanthrenyl, condensed tetracyclic systems such as triphenylenyl, pyrenyl, naphthacenyl, and condensed pentacyclic systems such as perylenyl and pentacenyl.
  • heteroaryl in the “optionally substituted heteroaryl” in R 21 to R 28 include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, A heteroaryl having 2 to 20 carbon atoms is more preferred, a heteroaryl having 2 to 15 carbon atoms is more preferred, and a heteroaryl having 2 to 10 carbon atoms is particularly preferred.
  • heteroaryl include heterocycles containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.
  • heteroaryl examples include pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H— Indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxaziny
  • alkoxy of “optionally substituted alkoxy” in R 21 to R 28 include straight-chain alkoxy having 1 to 24 carbon atoms or branched alkoxy having 3 to 24 carbon atoms.
  • C1-C18 alkoxy (C3-C18 branched alkoxy) is preferred, C1-C12 alkoxy (C3-C12 branched alkoxy) is more preferred, and C1-C6 Of alkoxy (C3-C6 branched chain alkoxy) is more preferable, and C1-C4 alkoxy (C3-C4 branched chain alkoxy) is particularly preferable.
  • alkoxy examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and the like.
  • Aryloxy of “optionally substituted aryloxy” in R 21 to R 28 is a group in which hydrogen of —OH group is substituted with aryl, and this aryl is the above-mentioned R 21 to R 28 . Reference may be made to groups described as “aryl”.
  • arylthio of the “optionally substituted arylthio” in R 21 to R 28 is a group in which the hydrogen of the —SH group is substituted with aryl, and this aryl is the “aryl” in R 21 to R 28 described above. Can be cited.
  • Examples of “trialkylsilyl” in R 21 to R 28 include groups in which three hydrogens in the silyl group are each independently substituted with alkyl, and this alkyl is referred to as “alkyl” in R 21 to R 28 described above.
  • the groups described can be cited.
  • Preferable alkyl for substitution is alkyl having 1 to 4 carbon atoms, and specific examples include methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl, cyclobutyl and the like.
  • trialkylsilyl include trimethylsilyl, triethylsilyl, tripropylsilyl, tri-i-propylsilyl, tributylsilyl, trisec-butylsilyl, tri-t-butylsilyl, ethyldimethylsilyl, propyldimethylsilyl, i-propyl Dimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, t-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, i-propyldiethylsilyl, butyldiethylsilyl, sec-butyldiethylsilyl, t-butyldiethylsilyl, methyl Dipropylsilyl, ethyldipropylsilyl, butyldipropylsilyl, butyl
  • Preferred cycloalkyl for substitution is cycloalkyl having 5 to 10 carbon atoms, specifically, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclo [1.1.1] pentyl, bicyclo [ 2.0.1] pentyl, bicyclo [1.2.1] hexyl, bicyclo [3.0.1] hexyl, bicyclo [2.1.2] heptyl, bicyclo [2.2.2] octyl, adamantyl, Decahydronaphthalenyl, decahydroazulenyl and the like can be mentioned.
  • tricycloalkylsilyl includes tricyclopentylsilyl, tricyclohexylsilyl and the like.
  • dialkylcycloalkylsilyl substituted with two alkyls and one cycloalkyl and alkyldicycloalkylsilyl substituted with one alkyl and two cycloalkyls are selected from the specific alkyls and cycloalkyls described above And silyl substituted with the above group.
  • Examples of the “substituted amino” of the “optionally substituted amino” in R 21 to R 28 include an amino group in which two hydrogens are substituted with aryl or heteroaryl.
  • An amino in which two hydrogens are substituted with aryl is a diaryl-substituted amino
  • an amino in which two hydrogens are substituted with a heteroaryl is a diheteroaryl-substituted amino
  • an amino in which two hydrogens are substituted with aryl and heteroaryl Is an arylheteroaryl-substituted amino.
  • the groups described as “aryl” and “heteroaryl” in R 21 to R 28 described above can be cited.
  • substituted amino include diphenylamino, dinaphthylamino, phenylnaphthylamino, dipyridylamino, phenylpyridylamino, naphthylpyridylamino, and the like.
  • halogen in R 21 to R 28 include fluorine, chlorine, bromine and iodine.
  • R 21 to R 28 some may be substituted as described above, and examples of the substituent in this case include alkyl, cycloalkyl, aryl, and heteroaryl.
  • This alkyl, cycloalkyl, aryl or heteroaryl can refer to the groups described as “alkyl”, “cycloalkyl”, “aryl” or “heteroaryl” in R 21 to R 28 described above.
  • R 29 in the "> N-R 29" as Y is hydrogen or aryl which may be substituted, it is cited a group described as the "aryl” in R 21 ⁇ R 28 described above as the aryl Further, as the substituent, the groups described as the substituents for R 21 to R 28 can be cited.
  • Adjacent groups of R 21 to R 28 may be bonded to each other to form a hydrocarbon ring, an aryl ring or a heteroaryl ring.
  • the case where no ring is formed is a group represented by the following formula (A-1), and the case where a ring is formed includes, for example, groups represented by the following formulas (A-2) to (A-14): It is done.
  • At least one hydrogen in the group represented by any of formulas (A-1) to (A-14) is alkyl, cycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, arylthio, trialkylsilyl, It may be substituted with tricycloalkylsilyl, dialkylcycloalkylsilyl, alkyldicycloalkylsilyl, diaryl-substituted amino, diheteroaryl-substituted amino, arylheteroaryl-substituted amino, halogen, hydroxy or cyano.
  • Examples of the ring formed by bonding adjacent groups to each other include a cyclohexane ring as long as it is a hydrocarbon ring, and examples of the aryl ring and heteroaryl ring include “aryl” and “heteroaryl” in R 21 to R 28 described above. And the ring is formed so as to be condensed with one or two benzene rings in the above formula (A-1).
  • Examples of the group represented by the formula (A) include groups represented by any of the above formulas (A-1) to (A-14), and the above formulas (A-1) to (A ⁇ 5) and a group represented by any of formulas (A-12) to (A-14) are preferred, and a group represented by any of the above formulas (A-1) to (A-4) Is more preferable, a group represented by any one of the above formulas (A-1), (A-3) and (A-4) is more preferable, and a group represented by the above formula (A-1) is more preferable. Particularly preferred.
  • the group represented by the formula (A) is represented by * in the formula (A), a naphthalene ring in the formula (3-X1) or the formula (3-X2), a single bond in the formula (3-X3), a formula As described above, it binds to Ar 3 in (3-X3) and substitutes at least one hydrogen in the compound represented by formula (3).
  • formula (3-X1) Alternatively, a form in which the naphthalene ring in the formula (3-X2), the single bond in the formula (3-X3) and / or Ar 3 in the formula (3-X3) is bonded is preferable.
  • the position at which Ar 3 is bonded to at least one hydrogen in the compound represented by the formula (3) is Any one of the two benzene rings in the structure of the formula (A) or an adjacent group among R 21 to R 28 in the structure of the formula (A) Any ring formed by bonding to each other, or any position in R 29 in “> NR 29 ” as Y in the structure of formula (A) can be bonded.
  • Examples of the group represented by the formula (A) include the following groups. Y and * in the formula are as defined above.
  • all or part of the hydrogen in the chemical structure of the anthracene compound represented by the general formula (3) may be deuterium.
  • anthracene compound examples include compounds represented by the following formulas (3-1) to (3-72).
  • “Me” represents a methyl group
  • “D” represents deuterium
  • “tBu” represents a t-butyl group.
  • the anthracene compound represented by the formula (3) includes a compound having a reactive group at a desired position of the anthracene skeleton and a compound having a reactive group in a partial structure such as the structure of X, Ar 4 and the formula (A) Can be produced by applying Suzuki coupling, Negishi coupling, and other known coupling reactions.
  • Examples of the reactive group of these reactive compounds include halogen and boronic acid.
  • the synthesis method in paragraphs [0089] to [0175] of International Publication No. 2014/141725 can be referred to.
  • R 1 to R 10 are each independently hydrogen, aryl, heteroaryl (the heteroaryl may be bonded to the fluorene skeleton in the above formula (4) via a linking group), diarylamino, dihetero Arylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy, wherein at least one hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl; R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 or R 9 and R 10 are bonded independently.
  • Examples of the alkenyl in R 1 to R 10 include alkenyl having 2 to 30 carbon atoms, preferably alkenyl having 2 to 20 carbon atoms, more preferably alkenyl having 2 to 10 carbon atoms, and 2 to 6 carbon atoms. Alkenyl is more preferable, and alkenyl having 2 to 4 carbon atoms is particularly preferable.
  • Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl.
  • any one of the compounds of the following formula (4-Ar1), formula (4-Ar2), formula (4-Ar3), formula (4-Ar4) or formula (4-Ar5) may be used. Also included are monovalent groups represented by removing one hydrogen atom.
  • Y 1 is each independently O, S or N—R, R is phenyl, biphenylyl, naphthyl, anthracenyl or hydrogen; At least one hydrogen in the structures of the above formulas (4-Ar1) to (4-Ar5) may be substituted with phenyl, biphenylyl, naphthyl, anthracenyl, phenanthrenyl, methyl, ethyl, propyl, or butyl.
  • heteroaryls may be bonded to the fluorene skeleton in the above formula (4) via a linking group. That is, not only the fluorene skeleton in the formula (4) and the heteroaryl are directly bonded but also a bond between them may be bonded.
  • this linking group include phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, —OCH 2 CH 2 —, —CH 2 CH 2 O—, or —OCH 2 CH 2 O—.
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 are bonded independently.
  • R 9 and R 10 may be combined to form a spiro ring.
  • the condensed ring formed by R 1 to R 8 is a ring condensed with the benzene ring in formula (4), and is an aliphatic ring or an aromatic ring.
  • An aromatic ring is preferred, and examples of the structure including the benzene ring in formula (4) include a naphthalene ring and a phenanthrene ring.
  • the spiro ring formed by R 9 and R 10 is a ring that is spiro-bonded to the 5-membered ring in formula (4), and is an aliphatic ring or an aromatic ring. Preferred is an aromatic ring, such as a fluorene ring.
  • the compound represented by the general formula (4) is preferably a compound represented by the following formula (4-1), formula (4-2), or formula (4-3). ) In which R 1 and R 2 are combined to form a condensed benzene ring, in general formula (4), a compound in which R 3 and R 4 are combined to form a condensed benzene ring, general formula (4 ) In which none of R 1 to R 8 is bonded.
  • R 1 to R 10 in Formula (4-1), Formula (4-2), and Formula (4-3) are the same as the corresponding R 1 to R 10 in Formula (4).
  • the definitions of R 11 to R 14 in 1) and formula (4-2) are the same as R 1 to R 10 in formula (4).
  • the compound represented by the general formula (4) is more preferably a compound represented by the following formula (4-1A), formula (4-2A), or formula (4-3A). -1), a compound having a spiro-fluorene ring formed by combining R 9 and R 10 in formula (4-1) or formula (4-3).
  • R 2 to R 7 in formula (4-1A), formula (4-2A), and formula (4-3A) are defined in formula (4-1), formula (4-2), and formula (4-3). corresponding the same from R 2 and R 7, R in the formula also defined formula (4-1) of the R 14 from R 11 in (4-1A) and (4-2A) and (4-2) 11 from is the same as R 14.
  • all or part of the hydrogen in the compound represented by the formula (4) may be substituted with halogen, cyano or deuterium.
  • the dibenzochrysene-type compound as a host is a compound represented, for example by following General formula (5).
  • R 1 to R 16 are each independently hydrogen, aryl, heteroaryl (the heteroaryl may be bonded to the dibenzochrysene skeleton in the above formula (5) via a linking group), diarylamino, diaryl Heteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy, in which at least one hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl; Further, adjacent groups of R 1 to R 16 may be bonded to form a condensed ring, and at least one hydrogen in the formed ring is aryl or heteroaryl (the heteroaryl is connected via a linking group).
  • alkenyl in the definition of the above formula (5) examples include alkenyl having 2 to 30 carbon atoms, preferably alkenyl having 2 to 20 carbon atoms, more preferably alkenyl having 2 to 10 carbon atoms, and 2 to 2 carbon atoms. More preferred is alkenyl having 6 carbon atoms, and particularly preferred is alkenyl having 2 to 4 carbon atoms.
  • Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl.
  • any one of the compounds of the following formula (5-Ar1), formula (5-Ar2), formula (5-Ar3), formula (5-Ar4) or formula (5-Ar5) may be used. Also included are monovalent groups represented by removing one hydrogen atom.
  • Y 1 is each independently O, S or N—R, R is phenyl, biphenylyl, naphthyl, anthracenyl or hydrogen; At least one hydrogen in the structures of the above formulas (5-Ar1) to (5-Ar5) may be substituted with phenyl, biphenylyl, naphthyl, anthracenyl, phenanthrenyl, methyl, ethyl, propyl, or butyl.
  • heteroaryls may be bonded to the dibenzochrysene skeleton in the above formula (5) via a linking group. That is, not only the dibenzochrysene skeleton in the formula (5) and the heteroaryl are directly bonded, but may be bonded via a linking group between them. Examples of this linking group include phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, —OCH 2 CH 2 —, —CH 2 CH 2 O—, or —OCH 2 CH 2 O—.
  • R 1 , R 4 , R 5 , R 8 , R 9 , R 12 , R 13 and R 16 are preferably hydrogen.
  • R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 in formula (5) are each independently hydrogen, phenyl, biphenylyl, naphthyl, anthracenyl, phenanthrenyl.
  • a monovalent group having the structure of the above formula (5-Ar1), formula (5-Ar2), formula (5-Ar3), formula (5-Ar4) or formula (5-Ar5) (1 having the structure)
  • the valent group is represented by the above formula (5) via phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, —OCH 2 CH 2 —, —CH 2 CH 2 O—, or —OCH 2 CH 2 O—. And may be bonded to the dibenzochrysene skeleton), methyl, ethyl, propyl, or butyl.
  • the compound represented by the general formula (5) is more preferably R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 9 , R 10 , R 12 , R 13 , R 15 and R. 16 is hydrogen.
  • at least one (preferably one or two, more preferably one) of R 3 , R 6 , R 11 and R 14 in formula (5) is a single bond, phenylene, biphenylene, naphthylene, Via the anthracenylene, methylene, ethylene, —OCH 2 CH 2 —, —CH 2 CH 2 O—, or —OCH 2 CH 2 O—, the above formula (5-Ar1), formula (5-Ar2), formula A monovalent group having a structure of (5-Ar3), formula (5-Ar4) or formula (5-Ar5);
  • Other than the at least one (that is, other than the position where the monovalent group having the structure is substituted) is hydrogen, phenyl, biphenylyl, nap
  • R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 in the formula (5) are represented by the above formulas (5-Ar1) to (5-Ar5).
  • at least one hydrogen in the structure may be bonded to any one of R 1 to R 16 in formula (5) to form a single bond. .
  • the electron injection layer 107 plays a role of efficiently injecting electrons moving from the cathode 108 into the light emitting layer 105 or the electron transport layer 106.
  • the electron transport layer 106 plays a role of efficiently transporting electrons injected from the cathode 108 or electrons injected from the cathode 108 through the electron injection layer 107 to the light emitting layer 105.
  • the electron transport layer 106 and the electron injection layer 107 are each formed by laminating and mixing one or more electron transport / injection materials or a mixture of the electron transport / injection material and the polymer binder.
  • the electron injection / transport layer is a layer that is responsible for injecting electrons from the cathode and further transporting the electrons. It is desirable that the electron injection efficiency is high and the injected electrons are transported efficiently. For this purpose, it is preferable to use a substance that has a high electron affinity, a high electron mobility, excellent stability, and is unlikely to generate trapping impurities during production and use. However, considering the transport balance between holes and electrons, if the role of effectively preventing the holes from the anode from flowing to the cathode side without recombination is mainly played, the electron transport capability is much higher. Even if it is not high, the effect of improving the luminous efficiency is equivalent to that of a material having a high electron transport capability. Therefore, the electron injection / transport layer in this embodiment may include a function of a layer that can efficiently block the movement of holes.
  • a material (electron transport material) for forming the electron transport layer 106 or the electron injection layer 107 a compound conventionally used as an electron transport compound in a photoconductive material, used for an electron injection layer and an electron transport layer of an organic EL element It can be used by arbitrarily selecting from known compounds.
  • a compound composed of an aromatic ring or a heteroaromatic ring composed of one or more atoms selected from carbon, hydrogen, oxygen, sulfur, silicon and phosphorus It is preferable to contain at least one selected from pyrrole derivatives, condensed ring derivatives thereof, and metal complexes having electron-accepting nitrogen.
  • condensed ring aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives represented by 4,4′-bis (diphenylethenyl) biphenyl, perinone derivatives, coumarin derivatives, naphthalimide derivatives Quinone derivatives such as anthraquinone and diphenoquinone, phosphorus oxide derivatives, carbazole derivatives and indole derivatives.
  • metal complexes having electron-accepting nitrogen include hydroxyazole complexes such as hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. These materials can be used alone or in combination with different materials.
  • electron transfer compounds include pyridine derivatives, naphthalene derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives, perylene derivatives, oxadiazoles.
  • metal complexes having electron-accepting nitrogen can also be used, such as hydroxyazole complexes such as quinolinol-based metal complexes and hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. can give.
  • the above-mentioned materials can be used alone, but they may be mixed with different materials.
  • borane derivatives pyridine derivatives, fluoranthene derivatives, BO derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, and quinolinol metals Complexes are preferred.
  • the borane derivative is, for example, a compound represented by the following general formula (ETM-1), and is disclosed in detail in JP-A-2007-27587.
  • R 11 and R 12 are each independently hydrogen, alkyl, cycloalkyl, aryl that may be substituted, silyl that is substituted, or nitrogen that may be substituted A heterocyclic ring, or at least one of cyano
  • R 13 to R 16 are each independently an optionally substituted alkyl, an optionally substituted cycloalkyl, or an optionally substituted aryl.
  • X is an optionally substituted arylene
  • Y is an optionally substituted aryl having 16 or less carbon atoms, a substituted boryl, or an optionally substituted carbazolyl
  • n Are each independently an integer of 0 to 3.
  • substituents in the case of “optionally substituted” or “substituted” include aryl, heteroaryl, alkyl, and cycloalkyl.
  • R 11 and R 12 are each independently hydrogen, alkyl, cycloalkyl, aryl which may be substituted, silyl which is substituted, nitrogen which may be substituted
  • a heterocycle containing at least one of cyano and R 13 to R 16 are each independently an optionally substituted alkyl, an optionally substituted cycloalkyl or an optionally substituted aryl.
  • Each of R 21 and R 22 is independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano; are among 1, X 1 is a substituted carbon atoms and optionally more than 20 arylene, n is an integer of 0-3 each independently, To, m are each independently an integer of 0-4.
  • substituent in the case of “optionally substituted” or “substituted” include aryl, heteroaryl, alkyl, and cycloalkyl.
  • R 11 and R 12 are each independently hydrogen, alkyl, cycloalkyl, aryl which may be substituted, silyl which is substituted, nitrogen which may be substituted
  • a heterocycle containing at least one of cyano and R 13 to R 16 are each independently an optionally substituted alkyl, an optionally substituted cycloalkyl or an optionally substituted aryl.
  • X 1 is an optionally substituted arylene having 20 or less carbon atoms, and n is each independently an integer of 0 to 3.
  • substituent in the case of “optionally substituted” or “substituted” include aryl, heteroaryl, alkyl, and cycloalkyl.
  • X 1 include divalent groups represented by any of the following formulas (X-1) to (X-9). (In each formula, each R a is independently an alkyl group, a cycloalkyl group, or an optionally substituted phenyl group.)
  • this borane derivative include the following compounds.
  • This borane derivative can be produced using a known raw material and a known synthesis method.
  • the pyridine derivative is, for example, a compound represented by the following formula (ETM-2), preferably a compound represented by the formula (ETM-2-1) or the formula (ETM-2-2).
  • ⁇ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1 to 4 is there.
  • R 11 to R 18 are each independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbons), cycloalkyl (preferably cyclohexane having 3 to 12 carbons). Alkyl) or aryl (preferably aryl having 6 to 30 carbon atoms).
  • R 11 and R 12 are each independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably cyclohexane having 3 to 12 carbon atoms). Alkyl) or aryl (preferably aryl having 6 to 30 carbon atoms), and R 11 and R 12 may be bonded to form a ring.
  • the “pyridine substituent” is any of the following formulas (Py-1) to (Py-15), and each pyridine substituent is independently an alkyl or carbon having 1 to 4 carbon atoms. It may be substituted with cycloalkyl of several 5-10. Further, the pyridine-based substituent may be bonded to ⁇ , anthracene ring or fluorene ring in each formula through a phenylene group or a naphthylene group.
  • the pyridine-based substituent is any one of the above formulas (Py-1) to (Py-15), and among these, any of the following formulas (Py-21) to (Py-44) It is preferable.
  • At least one hydrogen in each pyridine derivative may be substituted with deuterium, and among the two “pyridine substituents” in the above formula (ETM-2-1) and formula (ETM-2-2) One of these may be replaced by aryl.
  • Alkyl in R 11 to R 18 may be either linear or branched, and examples thereof include linear alkyl having 1 to 24 carbon atoms and branched alkyl having 3 to 24 carbon atoms.
  • Preferred “alkyl” is alkyl having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon atoms). More preferable “alkyl” is alkyl having 1 to 12 carbons (branched alkyl having 3 to 12 carbons). More preferable “alkyl” is alkyl having 1 to 6 carbon atoms (branched alkyl having 3 to 6 carbon atoms). Particularly preferred “alkyl” is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms).
  • alkyl examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1 -Methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2 -Propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecy
  • alkyl having 1 to 4 carbon atoms to be substituted on the pyridine-based substituent As the above description of alkyl can be cited.
  • cycloalkyl in R 11 to R 18 examples include cycloalkyl having 3 to 12 carbon atoms. Preferred “cycloalkyl” is cycloalkyl having 3 to 10 carbon atoms. More preferred “cycloalkyl” is cycloalkyl having 3 to 8 carbon atoms. More preferred “cycloalkyl” is cycloalkyl having 3 to 6 carbon atoms. Specific examples of “cycloalkyl” include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, and dimethylcyclohexyl.
  • preferred aryl is aryl having 6 to 30 carbon atoms, more preferred aryl is aryl having 6 to 18 carbon atoms, and still more preferred is aryl having 6 to 14 carbon atoms. And particularly preferred is aryl having 6 to 12 carbon atoms.
  • aryl having 6 to 30 carbon atoms include monocyclic aryl phenyl, condensed bicyclic aryl (1-, 2-) naphthyl, condensed tricyclic aryl acenaphthylene- ( 1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalen- (1-, 2-) yl, (1-, 2 -, 3-, 4-, 9-) phenanthryl, condensed tetracyclic aryl triphenylene- (1-, 2-) yl, pyrene- (1-, 2-, 4-) yl, naphthacene- (1- , 2-, 5-) yl, perylene- (1-, 2-, 3-) yl which is a fused pentacyclic aryl, pentacene- (1-, 2-, 5-, 6-) yl and the like. .
  • aryl having 6 to 30 carbon atoms includes phenyl, naphthyl, phenanthryl, chrycenyl, triphenylenyl and the like, more preferably phenyl, 1-naphthyl, 2-naphthyl and phenanthryl, particularly preferably phenyl, 1 -Naphthyl or 2-naphthyl.
  • R 11 and R 12 in the above formula (ETM-2-2) may be bonded to form a ring.
  • the 5-membered ring of the fluorene skeleton includes cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, Cyclohexane, fluorene, indene and the like may be spiro-bonded.
  • pyridine derivative examples include the following compounds.
  • This pyridine derivative can be produced using a known raw material and a known synthesis method.
  • the fluoranthene derivative is, for example, a compound represented by the following general formula (ETM-3), and is disclosed in detail in International Publication No. 2010/134352.
  • X 12 to X 21 are hydrogen, halogen, linear, branched or cyclic alkyl, linear, branched or cyclic alkoxy, substituted or unsubstituted aryl, or substituted or unsubstituted Represents heteroaryl.
  • substituent when substituted include aryl, heteroaryl, alkyl, and cycloalkyl.
  • fluoranthene derivative examples include the following compounds.
  • the BO derivative is, for example, a polycyclic aromatic compound represented by the following formula (ETM-4) or a multimer of polycyclic aromatic compounds having a plurality of structures represented by the following formula (ETM-4).
  • R 1 to R 11 are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (the two aryls are bonded via a single bond or a linking group). It may be alkyl), cycloalkyl, alkoxy or aryloxy, in which at least one hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.
  • adjacent groups of R 1 to R 11 may be bonded to form an aryl ring or a heteroaryl ring together with the a ring, b ring or c ring, and at least one hydrogen in the formed ring Is aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls may be linked via a single bond or a linking group), alkyl, cycloalkyl, alkoxy or aryl It may be substituted with oxy and at least one hydrogen in them may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.
  • At least one hydrogen in the compound or structure represented by the formula (ETM-4) may be substituted with halogen or deuterium.
  • this BO derivative include the following compounds.
  • This BO derivative can be produced using a known raw material and a known synthesis method.
  • Anthracene derivative is a compound represented by the following formula (ETM-5-1), for example.
  • Ar is each independently divalent benzene or naphthalene, and R 1 to R 4 are each independently hydrogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons or carbon number 6 to 20 aryls.
  • Ar can be independently selected as appropriate from divalent benzene or naphthalene, and the two Ar may be different or the same, but the same from the viewpoint of the ease of synthesis of the anthracene derivative. It is preferable that Ar is bonded to pyridine to form a “part consisting of Ar and pyridine”. This part is an anthracene as a group represented by any of the following formulas (Py-1) to (Py-12), for example. Is bound to.
  • a group represented by any one of the above formulas (Py-1) to (Py-9) is preferable, and any one of the above formulas (Py-1) to (Py-6) may be used. More preferred are the groups
  • the two “sites consisting of Ar and pyridine” bonded to anthracene may have the same structure or different structures, but are preferably the same structure from the viewpoint of ease of synthesis of the anthracene derivative. However, from the viewpoint of device characteristics, it is preferable that the structures of the two “sites composed of Ar and pyridine” are the same or different.
  • the alkyl having 1 to 6 carbon atoms in R 1 to R 4 may be linear or branched. That is, it is a linear alkyl having 1 to 6 carbon atoms or a branched alkyl having 3 to 6 carbon atoms. More preferred is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms).
  • Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1-methylpentyl, Examples include 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, etc., preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl. More preferred are methyl, ethyl, or t-butyl.
  • cycloalkyl having 3 to 6 carbon atoms in R 1 to R 4 include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, and dimethylcyclohexyl.
  • the aryl having 6 to 20 carbon atoms in R 1 to R 4 is preferably an aryl having 6 to 16 carbon atoms, more preferably an aryl having 6 to 12 carbon atoms, and particularly preferably an aryl having 6 to 10 carbon atoms.
  • aryl having 6 to 20 carbon atoms include monocyclic aryl phenyl, (o-, m-, p-) tolyl, (2,3-, 2,4-, 2,5- , 2,6-, 3,4-, 3,5-) xylyl, mesityl (2,4,6-trimethylphenyl), (o-, m-, p-) cumenyl, bicyclic aryl (2 -, 3-, 4-) biphenylyl, (1-, 2-) naphthyl which is a condensed bicyclic aryl, terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4) which is a tricyclic aryl '-Yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2
  • aryl having 6 to 20 carbon atoms is phenyl, biphenylyl, terphenylyl or naphthyl, more preferably phenyl, biphenylyl, 1-naphthyl, 2-naphthyl or m-terphenyl-5′-yl. More preferred is phenyl, biphenylyl, 1-naphthyl or 2-naphthyl, and most preferred is phenyl.
  • One of the anthracene derivatives is, for example, a compound represented by the following formula (ETM-5-2).
  • Ar 1 is each independently a single bond, divalent benzene, naphthalene, anthracene, fluorene, or phenalene.
  • Ar 2 is independently an aryl having 6 to 20 carbon atoms, and the same description as “aryl having 6 to 20 carbon atoms” in the above formula (ETM-5-1) can be cited.
  • Aryl having 6 to 16 carbon atoms is preferred, aryl having 6 to 12 carbon atoms is more preferred, and aryl having 6 to 10 carbon atoms is particularly preferred.
  • Specific examples include phenyl, biphenylyl, naphthyl, terphenylyl, anthracenyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, tetracenyl, perylenyl and the like.
  • R 1 to R 4 are each independently hydrogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons or aryl having 6 to 20 carbons, and the above formula (ETM-5-1) The explanation in can be cited.
  • anthracene derivatives include the following compounds.
  • anthracene derivatives can be produced using known raw materials and known synthesis methods.
  • the benzofluorene derivative is, for example, a compound represented by the following formula (ETM-6).
  • Ar 1 is independently an aryl having 6 to 20 carbon atoms, and the same description as “aryl having 6 to 20 carbon atoms” in the above formula (ETM-5-1) can be cited.
  • Aryl having 6 to 16 carbon atoms is preferred, aryl having 6 to 12 carbon atoms is more preferred, and aryl having 6 to 10 carbon atoms is particularly preferred.
  • Specific examples include phenyl, biphenylyl, naphthyl, terphenylyl, anthracenyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, tetracenyl, perylenyl and the like.
  • Ar 2 is independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms) or aryl (preferably aryl having 6 to 30 carbon atoms). And two Ar 2 may be bonded to form a ring.
  • Alkyl in Ar 2 may be either linear or branched, and examples thereof include linear alkyl having 1 to 24 carbon atoms and branched alkyl having 3 to 24 carbon atoms.
  • Preferred “alkyl” is alkyl having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon atoms). More preferable “alkyl” is alkyl having 1 to 12 carbons (branched alkyl having 3 to 12 carbons). More preferable “alkyl” is alkyl having 1 to 6 carbon atoms (branched alkyl having 3 to 6 carbon atoms). Particularly preferred “alkyl” is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms).
  • alkyl examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1 -Methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl and the like.
  • cycloalkyl in Ar 2 examples include cycloalkyl having 3 to 12 carbon atoms. Preferred “cycloalkyl” is cycloalkyl having 3 to 10 carbon atoms. More preferred “cycloalkyl” is cycloalkyl having 3 to 8 carbon atoms. More preferred “cycloalkyl” is cycloalkyl having 3 to 6 carbon atoms. Specific examples of “cycloalkyl” include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, and dimethylcyclohexyl.
  • aryl in Ar 2 , preferred aryl is aryl having 6 to 30 carbon atoms, more preferred aryl is aryl having 6 to 18 carbon atoms, still more preferred is aryl having 6 to 14 carbon atoms, Preferred is aryl having 6 to 12 carbon atoms.
  • aryl having 6 to 30 carbon atoms include phenyl, naphthyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, naphthacenyl, perylenyl, pentacenyl and the like.
  • Two Ar 2 may be bonded to form a ring.
  • cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, fluorene, or indene is spiro-bonded to the 5-membered ring of the fluorene skeleton. May be.
  • benzofluorene derivative examples include the following compounds.
  • This benzofluorene derivative can be produced using a known raw material and a known synthesis method.
  • the phosphine oxide derivative is, for example, a compound represented by the following formula (ETM-7-1). Details are also described in International Publication No. 2013/079217.
  • R 5 is substituted or unsubstituted alkyl having 1 to 20 carbons, cycloalkyl having 3 to 20 carbons, aryl having 6 to 20 carbons, or heteroaryl having 5 to 20 carbons;
  • R 6 is CN, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, heteroalkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, or 5 to 5 carbon atoms.
  • R 7 and R 8 are each independently substituted or unsubstituted aryl having 6 to 20 carbon atoms or heteroaryl having 5 to 20 carbon atoms;
  • R 9 is oxygen or sulfur;
  • j is 0 or 1
  • k is 0 or 1
  • r is an integer of 0 to 4, and
  • q is an integer of 1 to 3.
  • substituent when substituted include aryl, heteroaryl, alkyl, and cycloalkyl.
  • the phosphine oxide derivative may be, for example, a compound represented by the following formula (ETM-7-2).
  • R 1 to R 3 may be the same or different and are hydrogen, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, cycloalkenyl group, alkynyl group, alkoxy group, alkylthio group, cycloalkylthio group, aryl ether group , Arylthioether group, aryl group, heterocyclic group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, amino group, nitro group, silyl group, and a condensed ring formed between adjacent substituents Chosen from.
  • Ar 1 may be the same or different and is an arylene group or a heteroarylene group.
  • Ar 2 may be the same or different and is an aryl group or a heteroaryl group. However, at least one of Ar 1 and Ar 2 has a substituent, or forms a condensed ring with an adjacent substituent.
  • n is an integer of 0 to 3. When n is 0, there is no unsaturated structure, and when n is 3, R 1 does not exist.
  • the alkyl group represents, for example, a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, or a butyl group, which may be unsubstituted or substituted.
  • the substituent in the case of being substituted is not particularly limited, and examples thereof include an alkyl group, an aryl group, and a heterocyclic group, and this point is common to the following description.
  • the number of carbon atoms of the alkyl group is not particularly limited, but is usually in the range of 1 to 20 from the viewpoint of availability and cost.
  • cycloalkyl group represents a saturated alicyclic hydrocarbon group such as cyclopropyl, cyclohexyl, norbornyl, adamantyl and the like, which may be unsubstituted or substituted.
  • the number of carbon atoms in the alkyl group moiety is not particularly limited, but is usually in the range of 3-20.
  • the aralkyl group refers to an aromatic hydrocarbon group via an aliphatic hydrocarbon such as a benzyl group or a phenylethyl group, and both the aliphatic hydrocarbon and the aromatic hydrocarbon are unsubstituted or substituted. It doesn't matter.
  • the number of carbon atoms in the aliphatic moiety is not particularly limited, but is usually in the range of 1-20.
  • the alkenyl group refers to an unsaturated aliphatic hydrocarbon group containing a double bond such as a vinyl group, an allyl group, or a butadienyl group, which may be unsubstituted or substituted.
  • the number of carbon atoms of the alkenyl group is not particularly limited, but is usually in the range of 2-20.
  • the cycloalkenyl group refers to an unsaturated alicyclic hydrocarbon group containing a double bond such as a cyclopentenyl group, a cyclopentadienyl group, or a cyclohexene group, which may be unsubstituted or substituted. It doesn't matter.
  • the alkynyl group represents an unsaturated aliphatic hydrocarbon group containing a triple bond such as an acetylenyl group, which may be unsubstituted or substituted.
  • the number of carbon atoms of the alkynyl group is not particularly limited, but is usually in the range of 2-20.
  • the alkoxy group represents an aliphatic hydrocarbon group via an ether bond such as a methoxy group, and the aliphatic hydrocarbon group may be unsubstituted or substituted.
  • the number of carbon atoms of the alkoxy group is not particularly limited, but is usually in the range of 1-20.
  • the alkylthio group is a group in which an oxygen atom of an ether bond of an alkoxy group is substituted with a sulfur atom.
  • the cycloalkylthio group is a group in which an oxygen atom of an ether bond of a cycloalkoxy group is substituted with a sulfur atom.
  • aryl ether group refers to an aromatic hydrocarbon group via an ether bond such as a phenoxy group, and the aromatic hydrocarbon group may be unsubstituted or substituted.
  • the number of carbon atoms of the aryl ether group is not particularly limited, but is usually in the range of 6 to 40.
  • the aryl thioether group is a group in which the oxygen atom of the ether bond of the aryl ether group is substituted with a sulfur atom.
  • the aryl group represents an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group, a terphenyl group, or a pyrenyl group.
  • the aryl group may be unsubstituted or substituted.
  • the number of carbon atoms of the aryl group is not particularly limited, but is usually in the range of 6 to 40.
  • the heterocyclic group refers to, for example, a cyclic structural group having an atom other than carbon, such as a furanyl group, a thiophenyl group, an oxazolyl group, a pyridyl group, a quinolinyl group, or a carbazolyl group, which is unsubstituted or substituted. It doesn't matter.
  • the number of carbon atoms of the heterocyclic group is not particularly limited, but is usually in the range of 2-30.
  • Halogen means fluorine, chlorine, bromine and iodine.
  • aldehyde group, carbonyl group, and amino group can also include groups substituted with aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic rings, and the like.
  • aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, and heterocyclic ring may be unsubstituted or substituted.
  • the silyl group refers to, for example, a silicon compound group such as a trimethylsilyl group, which may be unsubstituted or substituted.
  • the carbon number of the silyl group is not particularly limited, but is usually in the range of 3-20.
  • the number of silicon is usually 1-6.
  • the condensed ring formed between adjacent substituents includes, for example, Ar 1 and R 2 , Ar 1 and R 3 , Ar 2 and R 2 , Ar 2 and R 3 , R 2 and R 3 , Ar 1 and A conjugated or non-conjugated fused ring formed between Ar 2 and the like.
  • n when n is 1, it may be formed conjugated or non-conjugated fused ring with two of R 1 each other.
  • These condensed rings may contain a nitrogen, oxygen, or sulfur atom in the ring structure, or may be further condensed with another ring.
  • phosphine oxide derivative examples include the following compounds.
  • This phosphine oxide derivative can be produced using a known raw material and a known synthesis method.
  • the pyrimidine derivative is, for example, a compound represented by the following formula (ETM-8), and preferably a compound represented by the following formula (ETM-8-1). Details are also described in International Publication No. 2011/021689.
  • Ar is each independently an optionally substituted aryl or an optionally substituted heteroaryl.
  • n is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2 or 3.
  • aryl in “optionally substituted aryl” include aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 24 carbon atoms, more preferably aryl having 6 to 20 carbon atoms, More preferred is aryl having 6 to 12 carbon atoms.
  • aryl include monocyclic aryl phenyl, bicyclic aryl (2-, 3-, 4-) biphenylyl, condensed bicyclic aryl (1-, 2-) naphthyl.
  • Terphenylyl which is a tricyclic aryl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o -Terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, o-terpheny
  • heteroaryl in the “optionally substituted heteroaryl” include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and heteroaryl having 2 to 20 carbon atoms.
  • Aryl is more preferred, heteroaryl having 2 to 15 carbons is more preferred, and heteroaryl having 2 to 10 carbons is particularly preferred.
  • heteroaryl include heterocycles containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring constituent atoms.
  • heteroaryl includes, for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, Isobenzofuranyl, benzo [b] thienyl, indolyl, isoindolyl, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naph
  • the aryl and heteroaryl may be substituted, and may be substituted with, for example, the aryl or heteroaryl.
  • this pyrimidine derivative include the following compounds.
  • This pyrimidine derivative can be produced using a known raw material and a known synthesis method.
  • the carbazole derivative is, for example, a compound represented by the following formula (ETM-9) or a multimer in which a plurality of such carbazole derivatives are bonded by a single bond or the like. Details are described in US Publication No. 2014/0197386.
  • Ar is each independently an optionally substituted aryl or an optionally substituted heteroaryl.
  • n is an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably 0 or 1.
  • aryl in “optionally substituted aryl” include aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 24 carbon atoms, more preferably aryl having 6 to 20 carbon atoms, More preferred is aryl having 6 to 12 carbon atoms.
  • aryl include monocyclic aryl phenyl, bicyclic aryl (2-, 3-, 4-) biphenylyl, condensed bicyclic aryl (1-, 2-) naphthyl.
  • Terphenylyl which is a tricyclic aryl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o -Terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, o-terpheny
  • heteroaryl in the “optionally substituted heteroaryl” include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and heteroaryl having 2 to 20 carbon atoms.
  • Aryl is more preferred, heteroaryl having 2 to 15 carbons is more preferred, and heteroaryl having 2 to 10 carbons is particularly preferred.
  • heteroaryl include heterocycles containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring constituent atoms.
  • heteroaryl includes, for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, Isobenzofuranyl, benzo [b] thienyl, indolyl, isoindolyl, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naph
  • the aryl and heteroaryl may be substituted, and may be substituted with, for example, the aryl or heteroaryl.
  • the carbazole derivative may be a multimer in which a plurality of compounds represented by the above formula (ETM-9) are bonded by a single bond or the like.
  • an aryl ring preferably a polyvalent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring
  • an aryl ring preferably a polyvalent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring
  • carbazole derivative examples include the following compounds.
  • This carbazole derivative can be produced using a known raw material and a known synthesis method.
  • the triazine derivative is, for example, a compound represented by the following formula (ETM-10), and preferably a compound represented by the following formula (ETM-10-1). Details are described in US Publication No. 2011/0156013.
  • Ar is each independently an optionally substituted aryl or an optionally substituted heteroaryl.
  • n is an integer of 1 to 3, preferably 2 or 3.
  • aryl in “optionally substituted aryl” include aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 24 carbon atoms, more preferably aryl having 6 to 20 carbon atoms, More preferred is aryl having 6 to 12 carbon atoms.
  • aryl include monocyclic aryl phenyl, bicyclic aryl (2-, 3-, 4-) biphenylyl, condensed bicyclic aryl (1-, 2-) naphthyl.
  • Terphenylyl which is a tricyclic aryl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o -Terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, o-terpheny
  • heteroaryl in the “optionally substituted heteroaryl” include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and heteroaryl having 2 to 20 carbon atoms.
  • Aryl is more preferred, heteroaryl having 2 to 15 carbons is more preferred, and heteroaryl having 2 to 10 carbons is particularly preferred.
  • heteroaryl include heterocycles containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring constituent atoms.
  • heteroaryl includes, for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, Isobenzofuranyl, benzo [b] thienyl, indolyl, isoindolyl, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naph
  • the aryl and heteroaryl may be substituted, and may be substituted with, for example, the aryl or heteroaryl.
  • triazine derivative examples include the following compounds.
  • This triazine derivative can be produced using a known raw material and a known synthesis method.
  • the benzimidazole derivative is, for example, a compound represented by the following formula (ETM-11).
  • ⁇ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1 to 4
  • the “benzimidazole substituent” means that the pyridyl group in the “pyridine substituent” in the above formula (ETM-2), formula (ETM-2-1) and formula (ETM-2-2) is benzo It is a substituent substituted with an imidazole group, and at least one hydrogen in the benzimidazole derivative may be substituted with deuterium.
  • R 11 in the benzimidazole group is hydrogen, alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 12 carbon atoms or aryl having 6 to 30 carbon atoms, and the above formula (ETM-2-1) and the formula ( The description of R 11 in ETM-2-2) can be cited.
  • ⁇ is preferably an anthracene ring or a fluorene ring, and the structure in this case can be referred to the description in the above formula (ETM-2-1) or formula (ETM-2-2), In the formula, R 11 to R 18 can be referred to the description of the above formula (ETM-2-1) or formula (ETM-2-2). Further, in the above formula (ETM-2-1) or formula (ETM-2-2), it is explained in a form in which two pyridine-based substituents are bonded.
  • this benzimidazole derivative include, for example, 1-phenyl-2- (4- (10-phenylanthracen-9-yl) phenyl) -1H-benzo [d] imidazole, 2- (4- (10- ( Naphthalen-2-yl) anthracen-9-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 2- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 5- (10- (naphthalen-2-yl) anthracen-9-yl) -1,2-diphenyl-1H-benzo [d] imidazole, 1- (4 -(10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -2-phenyl-1H-benzo [d] imidazole, 2- (4- (9,10 Di (naphthalen-2
  • This benzimidazole derivative can be produced using a known raw material and a known synthesis method.
  • the phenanthroline derivative is, for example, a compound represented by the following formula (ETM-12) or formula (ETM-12-1). Details are described in International Publication No. 2006/021982.
  • ⁇ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1 to 4 is there.
  • R 11 to R 18 in each formula are independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms) or aryl (preferably carbon (Aryl of formula 6 to 30).
  • alkyl preferably alkyl having 1 to 24 carbon atoms
  • cycloalkyl preferably cycloalkyl having 3 to 12 carbon atoms
  • aryl preferably carbon (Aryl of formula 6 to 30).
  • any of R 11 to R 18 is bonded to ⁇ which is an aryl ring.
  • At least one hydrogen in each phenanthroline derivative may be replaced with deuterium.
  • Alkyl in R 11 ⁇ R 18, cycloalkyl and aryl may be cited to the description of R 11 ⁇ R 18 in the formula (ETM-2).
  • ⁇ includes the following structural formula, for example.
  • each R is independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenylyl or terphenylyl.
  • this phenanthroline derivative include, for example, 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 9,10-di (1,10- Phenanthroline-2-yl) anthracene, 2,6-di (1,10-phenanthroline-5-yl) pyridine, 1,3,5-tri (1,10-phenanthroline-5-yl) benzene, 9,9 ′ -Difluoro-bi (1,10-phenanthroline-5-yl), bathocuproin, 1,3-bis (2-phenyl-1,10-phenanthroline-9-yl) benzene and compounds represented by the following structural formula can give.
  • This phenanthroline derivative can be produced using a known raw material and a known synthesis method.
  • the quinolinol-based metal complex is, for example, a compound represented by the following general formula (ETM-13).
  • R 1 to R 6 are each independently hydrogen, fluorine, alkyl, cycloalkyl, aralkyl, alkenyl, cyano, alkoxy or aryl
  • M is Li, Al, Ga, Be or Zn
  • n is an integer of 1 to 3.
  • quinolinol metal complexes include 8-quinolinol lithium, tris (8-quinolinolato) aluminum, tris (4-methyl-8-quinolinolato) aluminum, tris (5-methyl-8-quinolinolato) aluminum, tris (3 , 4-dimethyl-8-quinolinolato) aluminum, tris (4,5-dimethyl-8-quinolinolato) aluminum, tris (4,6-dimethyl-8-quinolinolato) aluminum, bis (2-methyl-8-quinolinolato) ( Phenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-methylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3-methylphenolato) aluminum, bis (2-methyl-8- Quinolinolato) (4- Tylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3-phenylphenolate)
  • This quinolinol-based metal complex can be produced using a known raw material and a known synthesis method.
  • the thiazole derivative is, for example, a compound represented by the following formula (ETM-14-1).
  • the benzothiazole derivative is, for example, a compound represented by the following formula (ETM-14-2).
  • ⁇ in each formula is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is 1 to 4
  • the “thiazole-based substituent” and “benzothiazole-based substituent” are “pyridine-based” in the above formula (ETM-2), formula (ETM-2-1) and formula (ETM-2-2).
  • the pyridyl group in the “substituent” is a substituent in which the following thiazole group or benzothiazole group is substituted, and at least one hydrogen in the thiazole derivative and the benzothiazole derivative may be substituted with deuterium.
  • ⁇ is preferably an anthracene ring or a fluorene ring, and the structure in this case can be referred to the description in the above formula (ETM-2-1) or formula (ETM-2-2), In the formula, R 11 to R 18 can be referred to the description of the above formula (ETM-2-1) or formula (ETM-2-2). Further, in the above formula (ETM-2-1) or formula (ETM-2-2), it is described in the form of two pyridine-based substituents bonded to each other, but these are represented by thiazole-based substituents (or benzothiazole-based substituents).
  • at least one of R 11 to R 18 in the above formula (ETM-2-1) is replaced with a thiazole substituent (or benzothiazole substituent) to replace the “pyridine substituent” with R 11 to R 18. May be replaced.
  • thiazole derivatives or benzothiazole derivatives can be produced using known raw materials and known synthesis methods.
  • the electron transport layer or the electron injection layer may further contain a substance capable of reducing the material forming the electron transport layer or the electron injection layer.
  • a substance capable of reducing the material forming the electron transport layer or the electron injection layer various substances can be used as long as they have a certain reducing ability.
  • alkali metals, alkaline earth metals, rare earth metals, alkali metal oxides, alkali metal halides, alkalis From the group consisting of earth metal oxides, alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes At least one selected can be suitably used.
  • Preferred reducing substances include alkali metals such as Na (work function 2.36 eV), K (2.28 eV), Rb (2.16 eV) or Cs (1.95 eV), and Ca (2. 9eV), Sr (2.0 to 2.5 eV) or Ba (2.52 eV), and alkaline earth metals such as those having a work function of 2.9 eV or less are particularly preferable.
  • a more preferable reducing substance is an alkali metal of K, Rb or Cs, more preferably Rb or Cs, and most preferably Cs.
  • alkali metals have particularly high reducing ability, and by adding a relatively small amount to the material forming the electron transport layer or the electron injection layer, the luminance of the organic EL element can be improved and the lifetime can be extended.
  • a reducing substance having a work function of 2.9 eV or less a combination of two or more alkali metals is also preferable.
  • a combination containing Cs such as Cs and Na, Cs and K, Cs and Rb, or A combination of Cs, Na and K is preferred.
  • Cs such as Cs and Na, Cs and K, Cs and Rb, or A combination of Cs, Na and K is preferred.
  • the cathode 108 plays a role of injecting electrons into the light emitting layer 105 through the electron injection layer 107 and the electron transport layer 106.
  • the material for forming the cathode 108 is not particularly limited as long as it can efficiently inject electrons into the organic layer, but the same material as the material for forming the anode 102 can be used.
  • metals such as tin, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, cesium and magnesium or alloys thereof (magnesium-silver alloy, magnesium -Indium alloys, aluminum-lithium alloys such as lithium fluoride / aluminum, etc.) are preferred.
  • Lithium, sodium, potassium, cesium, calcium, magnesium, or alloys containing these low work function metals are effective for increasing the electron injection efficiency and improving device characteristics.
  • metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium, or alloys using these metals, and inorganic materials such as silica, titania and silicon nitride, polyvinyl alcohol, vinyl chloride Lamination of hydrocarbon polymer compounds and the like is a preferred example.
  • the method for producing these electrodes is not particularly limited as long as conduction can be achieved, such as resistance heating, electron beam evaporation, sputtering, ion plating, and coating.
  • the materials used for the hole injection layer, hole transport layer, light emitting layer, electron transport layer and electron injection layer can form each layer alone, but as a polymer binder, polyvinyl chloride, polycarbonate, Polystyrene, poly (N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate resin, ABS resin, polyurethane resin It can also be used by dispersing it in solvent-soluble resins such as phenol resins, xylene resins, petroleum resins, urea resins, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, silicone resins, etc. is there.
  • solvent-soluble resins such as phenol resins, xylene resins, petroleum resins, urea resins, melamine resins,
  • Each layer constituting the organic EL element is a thin film formed by a method such as vapor deposition, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, printing method, spin coat method or cast method, coating method, etc. Thus, it can be formed.
  • the film thickness of each layer thus formed is not particularly limited and can be appropriately set according to the properties of the material, but is usually in the range of 2 nm to 5000 nm. The film thickness can usually be measured with a crystal oscillation type film thickness measuring device or the like.
  • the vapor deposition conditions vary depending on the type of material, the target crystal structure and association structure of the film, and the like.
  • Deposition conditions generally include boat heating temperature +50 to + 400 ° C., vacuum degree 10 ⁇ 6 to 10 ⁇ 3 Pa, deposition rate 0.01 to 50 nm / second, substrate temperature ⁇ 150 to + 300 ° C., film thickness 2 nm to 5 ⁇ m. It is preferable to set appropriately within the range.
  • an organic EL element composed of an anode / hole injection layer / hole transport layer / a light emitting layer composed of a host material and a dopant material / electron transport layer / electron injection layer / cathode
  • a manufacturing method of will be described.
  • a thin film of an anode material is formed on a suitable substrate by vapor deposition or the like to produce an anode, and then a thin film of a hole injection layer and a hole transport layer is formed on the anode.
  • a host material and a dopant material are co-evaporated to form a thin film to form a light emitting layer.
  • An electron transport layer and an electron injection layer are formed on the light emitting layer, and a thin film made of a cathode material is formed by vapor deposition. By forming it as a cathode, a target organic EL element can be obtained.
  • the production order can be reversed, and the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode can be produced in this order. It is.
  • the anode When a DC voltage is applied to the organic EL device thus obtained, the anode may be applied with a positive polarity and the cathode with a negative polarity. When a voltage of about 2 to 40 V is applied, a transparent or translucent electrode is applied. Luminescence can be observed from the side (anode or cathode, and both).
  • the organic EL element also emits light when a pulse current or an alternating current is applied.
  • the alternating current waveform to be applied may be arbitrary.
  • the present invention can also be applied to a display device including an organic EL element or a lighting device including an organic EL element.
  • the display device or lighting device including the organic EL element can be manufactured by a known method such as connecting the organic EL element according to the present embodiment and a known driving device, such as DC driving, pulse driving, or AC driving. It can drive using a well-known drive method suitably.
  • Examples of the display device include a panel display such as a color flat panel display, and a flexible display such as a flexible color organic electroluminescence (EL) display (for example, JP-A-10-335066 and JP-A-2003-321546). Gazette, JP-A-2004-281086, etc.).
  • Examples of the display method of the display include a matrix and / or segment method. Note that the matrix display and the segment display may coexist in the same panel.
  • pixels for display are two-dimensionally arranged such as a grid or mosaic, and characters and images are displayed with a set of pixels.
  • the shape and size of the pixel are determined by the application. For example, a square pixel with a side of 300 ⁇ m or less is usually used for displaying images and characters on a personal computer, monitor, TV, and a pixel with a side of mm order for a large display such as a display panel. become.
  • monochrome display pixels of the same color may be arranged. However, in color display, red, green, and blue pixels are displayed side by side. In this case, there are typically a delta type and a stripe type.
  • the matrix driving method may be either a line sequential driving method or an active matrix.
  • the line-sequential driving has an advantage that the structure is simple. However, the active matrix may be superior in consideration of the operation characteristics, so that it is necessary to properly use it depending on the application.
  • a pattern is formed so as to display predetermined information, and a predetermined region is caused to emit light.
  • a predetermined region is caused to emit light.
  • the time and temperature display in a digital clock or a thermometer the operation state display of an audio device or an electromagnetic cooker, the panel display of an automobile, and the like can be mentioned.
  • the illuminating device examples include an illuminating device such as indoor lighting, a backlight of a liquid crystal display device, and the like (for example, JP 2003-257621 A, JP 2003-277741 A, JP 2004-119211 A). Etc.)
  • the backlight is used mainly for the purpose of improving the visibility of a display device that does not emit light, and is used for a liquid crystal display device, a clock, an audio device, an automobile panel, a display panel, a sign, and the like.
  • this embodiment As a backlight for a liquid crystal display device, especially a personal computer application where thinning is an issue, considering that it is difficult to thin the conventional method because it is made of a fluorescent lamp or a light guide plate, this embodiment
  • the backlight using the light emitting element according to the present invention is thin and lightweight.
  • the polycyclic aromatic compound according to the present invention can be used for producing an organic field effect transistor or an organic thin film solar cell in addition to the above-described organic electroluminescent element.
  • An organic field effect transistor is a transistor that controls current by an electric field generated by voltage input, and includes a gate electrode in addition to a source electrode and a drain electrode. When a voltage is applied to the gate electrode, an electric field is generated, and the current can be controlled by arbitrarily blocking the flow of electrons (or holes) flowing between the source electrode and the drain electrode.
  • Field effect transistors are easier to miniaturize than simple transistors (bipolar transistors), and are often used as elements constituting integrated circuits and the like.
  • the structure of the organic field effect transistor is usually provided with a source electrode and a drain electrode in contact with the organic semiconductor active layer formed using the polycyclic aromatic compound according to the present invention, and further in contact with the organic semiconductor active layer.
  • the gate electrode may be provided with the insulating layer (dielectric layer) interposed therebetween. Examples of the element structure include the following structures.
  • Substrate / gate electrode / insulator layer / source electrode / drain electrode / organic semiconductor active layer (2) Substrate / gate electrode / insulator layer / organic semiconductor active layer / source electrode / drain electrode (3) substrate / organic Semiconductor active layer / source electrode / drain electrode / insulator layer / gate electrode (4) substrate / source electrode / drain electrode / organic semiconductor active layer / insulator layer / gate electrode It can be applied as a pixel driving switching element for an active matrix driving type liquid crystal display or an organic electroluminescence display.
  • Organic thin-film solar cells have a structure in which an anode such as ITO, a hole transport layer, a photoelectric conversion layer, an electron transport layer, and a cathode are laminated on a transparent substrate such as glass.
  • the photoelectric conversion layer has a p-type semiconductor layer on the anode side and an n-type semiconductor layer on the cathode side.
  • the polycyclic aromatic compound according to the present invention can be used as a material for a hole transport layer, a p-type semiconductor layer, an n-type semiconductor layer, and an electron transport layer, depending on its physical properties.
  • the polycyclic aromatic compound according to the present invention can function as a hole transport material or an electron transport material in an organic thin film solar cell.
  • the organic thin film solar cell may appropriately include a hole block layer, an electron block layer, an electron injection layer, a hole injection layer, a smoothing layer, and the like.
  • known materials used for the organic thin film solar cell can be appropriately selected and used in combination.
  • bromobenzene (5.25 ml, 50.0 mmol), 2,6-difluoroaniline (7.59 ml, 75.0 mmol), Pd 2 (dba) 3 (0.687 mg, 0.750 mmol), BINAP ( A flask containing 0.934 g, 1.50 mmol), NaOtBu (7.21 g, 75.0 mmol), and toluene (150 ml) was heated to 110 ° C. and stirred for 4 hours. The reaction solution was cooled to room temperature, poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate.
  • 1,3-dibromo-5-chlorobenzene (4.87 g, 18.0 mmol), 2,6-difluoro-N-phenylaniline (7.39 g, 36.0 mmol), Pd 2 (dba) 3 ( 0.330 g, 0.360 mmol), SPhos (0.296 g, 0.720 mmol), NaOtBu (5.19 g, 54.0 mmol), and toluene (90.0 ml) were heated to 100 ° C. and heated to 3 ° C. Stir for hours. The reaction solution was cooled to room temperature, poured into water, and the aqueous layer was extracted with toluene.
  • N 1 , N 3 -diphenylbenzene-1,3-diamine (0.521 g, 2.00 mmol), 5-chloro-N 1 synthesized according to the method described in International Publication No. WO 2018/212169 under a nitrogen atmosphere , N 3 -bis (2,6-difluorophenyl) -N 1 , N 3 -diphenylbenzene-1,3-diamine (2.28 g, 4.40 mmol), Pd 2 (dba) 3 (0.0916 g , 0.100 mmol), SPhos (0.0821 g, 0.200 mmol), NaOtBu (0.577 g, 6.00 mmol), and toluene (10.0 ml) were heated to 110 ° C.
  • N 1 , N 1 ′-(1,3-phenylene) bis (N 3 , N 5 -bis (2,6-difluorophenyl) -N 1 , N 3 , N 5 -triphenylbenzene- 1 under a nitrogen atmosphere , 3,5-triamine) (1.59 g, 1.30 mmol) and 1,2,4-trichlorobenzene (19.5 ml) in a flask with boron tribromide (0.990 ml, 10.4 mmol). It added at room temperature and stirred at 180 degreeC for 20 hours. After the reaction solution was cooled to room temperature, boron tribromide remaining under reduced pressure and hydrogen bromide in the reaction solution were distilled off.
  • 1,3-dibromobenzene (1.22 ml, 10.0 mmol), 2,4-difluoroaniline (2.54 ml, 25.0 mmol), Pd 2 (dba) 3 (0.183 g, 0.200 mmol) ), SPhos (0.164 g, 0.400 mmol), NaOtBu (2.88 g, 30.0 mmol), and toluene (100 ml) were heated to 40 ° C. and stirred for 6 hours. The reaction solution was cooled to room temperature, poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate.
  • N 1 , N 3 -bis (2,4-difluorophenyl) benzene-1,3-diamine (0.997 mg, 3.00 mmol), described in WO 2018/212169 under a nitrogen atmosphere 5-chloro-N 1 , N 1 , N 3 , N 3 -tetraphenylbenzene-1,3-diamine (2.95 g, 6.60 mmol), Pd 2 (dba) 3 (0.137 g, synthesized according to the procedure) 0.150 mmol), SPhos (0.123 g, 0.300 mmol), NaOtBu (0.865 g, 9.00 mmol), and toluene (15.0 ml) were heated to 110 ° C. and stirred for 24 hours.
  • N 1 , N 1 ′-(1,3-phenylene) bis (N 1- (2,4-difluorophenyl) -N 3 , N 3 , N 5 , N 5 -tetraphenylbenzene-1, 3,5-triamine) (0.173 g, 0.150 mmol) and 1,2,4-trichlorobenzene (3.00 ml) in a flask with boron tribromide (0.114 ml, 1.20 mmol) at room temperature. And stirred at 180 ° C. for 20 hours. After the reaction solution was cooled to room temperature, boron tribromide remaining under reduced pressure and hydrogen bromide in the reaction solution were distilled off.
  • 1,3-dibromobenzene (1.22 ml, 10.0 mmol), 2,6-difluoroaniline (3.04 ml, 30.0 mmol), Pd 2 (dba) 3 (0.183 g, 0.200 mmol) ), SPhos (0.164 g, 0.400 mmol), NaOtBu (2.88 g, 30.0 mmol), and toluene (50.0 ml) were heated to 60 ° C. and stirred for 2 hours. The reaction solution was cooled to room temperature, poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate.
  • N 1 , N 3 -bis (2,6-difluorophenyl) benzene-1,3-diamine (1.16 g, 3.50 mmol), described in International Publication No. WO 2018/212169 under a nitrogen atmosphere 5-chloro-N 1 , N 1 , N 3 , N 3 -tetraphenylbenzene-1,3-diamine (3.44 g, 7.70 mmol), Pd 2 (dba) 3 (0.160 g, synthesized according to the procedure)
  • a flask containing 0.180 mmol), SPhos (0.144 g, 0.350 mmol), NaOtBu (1.01 g, 10.5 mmol), and toluene (17.5 ml) was heated to 110 ° C.
  • N 1 , N 1 ′-(1,3-phenylene) bis (N 1- (2,6-difluorophenyl) -N 3 , N 3 , N 5 , N 5 -tetraphenylbenzene-1, 3,5-triamine) (2.65 g, 2.30 mmol) and 1,2,4-trichlorobenzene (50.0 ml) in a flask containing boron tribromide (1.75 ml, 18.4 mmol) at room temperature. And stirred at 200 ° C. for 20 hours. After the reaction solution was cooled to room temperature, boron tribromide remaining under reduced pressure and hydrogen bromide in the reaction solution were distilled off.
  • 1,3-dibromobenzene (25.0 g, 106 mmol), aniline (20.3 ml, 223 mmol), Pd 2 (dba) 3 (971 mg, 1.06 mmol), BINAP (1.98 g, 3.18 mmol) ), NaOtBu (25.5 g, 265 mmol) and toluene (400 ml) were heated to 110 ° C. and stirred for 18 hours.
  • the reaction solution was cooled to room temperature, filtered through silica gel (eluent: toluene), and the solvent was distilled off under reduced pressure to obtain a crude product.
  • 1,3-dibromo-5-chlorobenzene (8.11 g, 30 mmol), diphenylamine (10.1 g, 60 mmol), Pd 2 (dba) 3 (550 mg, 0.6 mmol), SPhos (0.493 g, 1.2 mmol), NaOtBu (8.60 g, 90 mmol) and toluene (300 ml) were heated to 80 ° C. and stirred for 15 hours.
  • the reaction solution was cooled to room temperature, filtered through silica gel (eluent: toluene), and the solvent was distilled off under reduced pressure to obtain a crude product.
  • N 1 , N 3 -diphenylbenzene-1,3-diamine (1.34 g, 5.1 mmol)
  • 5-chloro-N 1 , N 1 , N 3 , N 3 -tetraphenylbenzene-1, 3-diamine (4.80 g, 11 mmol)
  • Pd 2 (dba) 3 (0.140 g, 0.15 mmol)
  • tri-tert-butylphosphine (60.7 mg, 0.30 mmol
  • toluene 200 ml were heated to 110 ° C. and stirred for 8 hours.
  • the reaction solution was cooled to room temperature, filtered through silica gel (eluent: toluene), and the solvent was distilled off under reduced pressure to obtain a crude product.
  • the obtained crude product was washed with hexane and methanol in this order, so that N 1 , N 1 ′-(1,3-phenylene) bis (N 1 , N 3 , N 3 , N 5 , N 5 -pentaphenyl) (Benzene-1,3,5-triamine) was obtained as a white solid (4.80 g, 87% yield).
  • N 1 , N 1 ′-(1,3-phenylene) bis (N 1 , N 3 , N 3 , N 5 , N 5 -pentaphenylbenzene-1,3,5-triamine) (3.24 g, 3.
  • Boron tribromide (1.13 ml, 12 mmol) was added to a flask containing 0 mmol) and orthodichlorobenzene (400 ml) at room temperature under a nitrogen atmosphere. After completion of dropping, the mixture was heated to 180 ° C. and stirred for 20 hours.
  • polycyclic aromatic compounds of the present invention can be synthesized by a method according to the synthesis example described above by appropriately changing the raw material compound.
  • the quantum efficiency of a light emitting device includes an internal quantum efficiency and an external quantum efficiency.
  • the internal quantum efficiency is that the external energy injected as electrons (or holes) into the light emitting layer of the light emitting device is converted into pure photons. The ratio is shown.
  • the external quantum efficiency is calculated based on the amount of photons emitted to the outside of the light emitting device, and some of the photons generated in the light emitting layer continue to be absorbed or reflected inside the light emitting device. In other words, the external quantum efficiency is lower than the internal quantum efficiency because it is not emitted to the outside of the light emitting element.
  • the external quantum efficiency is measured as follows.
  • a voltage / current generator R6144 manufactured by Advantest Corporation was used to apply a voltage at which the luminance of the element was 1000 cd / m 2 to cause the element to emit light.
  • a spectral radiance meter SR-3AR manufactured by TOPCON the spectral radiance in the visible light region was measured from the direction perpendicular to the light emitting surface. Assuming that the light emitting surface is a completely diffusing surface, the value obtained by dividing the measured spectral radiance value of each wavelength component by the wavelength energy and multiplying by ⁇ is the number of photons at each wavelength.
  • the value obtained by dividing the applied current value by the elementary charge is the number of carriers injected into the device, and the number obtained by dividing the total number of photons emitted from the device by the number of carriers injected into the device is the external quantum efficiency.
  • Table 1A and Table 1B below show the material configuration of each layer and the EL characteristic data in the organic EL element according to Example 1 that was produced.
  • HI means N 4 , N 4 ′ -diphenyl-N 4 , N 4 ′ -bis (9-phenyl-9H-carbazol-3-yl)-[1,1′-biphenyl] -4, 4'-diamine
  • HAT-CN is 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile
  • HT-1 is N-([1,1'-biphenyl ] -4-yl) -9,9-dimethyl-N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) -9H-fluoren-2-amine
  • HT-2 N, N-bis (4- (dibenzo [b, d] furan-4-yl) phenyl)-[1,1 ′: 4 ′, 1 ′′ -terphenyl] -4-amine
  • BH-1 Is 2- (10-phenylanthracen-9-yl) nap
  • Example 1 A glass substrate of 26 mm ⁇ 28 mm ⁇ 0.7 mm (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate.
  • This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and HI, HAT-CN, HT-1, HT-2, BH-1, compound (1-1), ET A molybdenum vapor deposition boat containing -1 and ET-2, and an aluminum nitride vapor deposition boat containing Liq, LiF, and aluminum, respectively, were mounted.
  • a commercially available vapor deposition apparatus manufactured by Showa Vacuum Co., Ltd.
  • the following layers were sequentially formed on the ITO film of the transparent support substrate.
  • the vacuum chamber was depressurized to 5 ⁇ 10 ⁇ 4 Pa, first, HI was heated and evaporated to a film thickness of 40 nm, then HAT-CN was heated and evaporated to a film thickness of 5 nm, Next, HT-1 is heated and evaporated to a film thickness of 45 nm, and then HT-2 is heated and evaporated to a film thickness of 10 nm to form a four-layer hole layer. did. Next, BH-1 and the compound (1-1) were heated at the same time and evaporated to a thickness of 25 nm to form a light emitting layer.
  • the deposition rate was adjusted so that the weight ratio of BH-1 to compound (1-1) was approximately 98 to 2. Further, ET-1 was heated and evaporated to a thickness of 5 nm, and then ET-2 and Liq were simultaneously heated to a thickness of 25 nm to form a two-layer electronic layer. Formed. The deposition rate was adjusted so that the weight ratio of ET-2 to Liq was approximately 50:50. The deposition rate of each layer was 0.01 to 1 nm / second. Thereafter, LiF is heated to deposit at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm, and then aluminum is heated to deposit to a film thickness of 100 nm to form a cathode. Thus, an organic EL element was obtained.
  • Table 2A and Table 2B below show the material configuration of each layer and EL characteristic data in the organic EL elements according to Examples 2-8 and Comparative Examples 1-2.
  • BH-2 is 2- (10-phenylanthracen-9-yl) dibenzo [b, d] furan.
  • the chemical structure is shown below together with compound (C-1) and compound (C-2).
  • Example 2 A glass substrate of 26 mm ⁇ 28 mm ⁇ 0.7 mm (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate.
  • This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and HI, HAT-CN, HT-1, HT-2, BH-2, compound (1-1), ET A molybdenum evaporation boat containing -1 and ET-2, and an aluminum nitride evaporation boat containing Liq, LiF and aluminum, respectively, were mounted.
  • the following layers were sequentially formed on the ITO film of the transparent support substrate.
  • the vacuum chamber was depressurized to 5 ⁇ 10 ⁇ 4 Pa, first, HI was heated and evaporated to a film thickness of 40 nm, then HAT-CN was heated and evaporated to a film thickness of 5 nm, Next, HT-1 is heated and evaporated to a film thickness of 45 nm, and then HT-2 is heated and evaporated to a film thickness of 10 nm to form a four-layer hole layer. did. Next, BH-2 and compound (1-1) were heated at the same time and evaporated to a thickness of 25 nm to form a light emitting layer.
  • the deposition rate was adjusted so that the weight ratio of BH-2 to compound (1-1) was approximately 98 to 2. Further, ET-1 was heated and evaporated to a thickness of 5 nm, and then ET-2 and Liq were simultaneously heated to a thickness of 25 nm to form a two-layer electronic layer. Formed. The deposition rate was adjusted so that the weight ratio of ET-2 to Liq was approximately 50:50. The deposition rate of each layer was 0.01 to 1 nm / second. Thereafter, LiF is heated to deposit at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm, and then aluminum is heated to deposit to a film thickness of 100 nm to form a cathode. Thus, an organic EL element was obtained.
  • a driving voltage was 3.80 V and an external quantum efficiency was 7.50%. Further, the time for maintaining the luminance of 98% or more of the initial luminance when driven at a constant current at a current density of 10 mA / cm 2 was 53 hours.
  • Examples 3 to 8 and Comparative Examples 1 and 2 An organic EL device was produced by a method according to Example 2 (Table 2A), and EL characteristics were measured (Table 2B).
  • the fluorescence spectrum was measured by dissolving a compound of formula (1-1666), formula (1-1674) or formula (1-1668) in toluene at a concentration of 2 ⁇ 10 ⁇ 5 M, and preparing a measurement solution. This was put in a quartz optical cell and excited at an excitation wavelength of 380 nm to measure a fluorescence spectrum. The results are shown in Table 3A below.
  • the choice of materials for organic devices such as materials for organic EL elements can be increased.
  • a novel fluorine-substituted polycyclic aromatic compound as a material for an organic EL element, for example, an organic EL element excellent in luminous efficiency and element lifetime, a display device including the same, a lighting device including the same, and the like Can be provided.

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