JP4979247B2 - Anthracene compound and organic electroluminescence device containing the compound - Google Patents

Description

  The present invention relates to an anthracene compound and an organic electroluminescent device containing the compound, and more specifically, an anthracene compound that can be suitably used for an organic electroluminescent device, has thin film stability and high durability, and uses the compound. The present invention relates to an organic electroluminescent device having high emission luminance and luminous efficiency at a low voltage, and a luminescent material for an organic electroluminescent device realizing high stability and long life.

  In recent years, various organic compounds have been actively researched and developed as materials having various functions such as display materials and recording materials.

  For example, recently Eastman Kodak's C.I. W. Tang et al. Developed an organic electroluminescence device (organic electroluminescence device; organic EL device) using an organic compound as a constituent material [see, for example, Non-Patent Document 1]. The organic electroluminescent element has a structure in which a thin film containing a fluorescent organic compound (light emitting material) is sandwiched between an anode and a cathode. When an electric field is applied to the thin film, excitons are generated by recombination of holes injected from the anode and electrons injected from the cathode, and the excitons are deactivated. It is a self-luminous element that utilizes the principle that a fluorescent organic compound emits light by the energy emitted to the. The organic electroluminescent element is driven at a low direct current voltage of about several volts to several tens of volts, and can emit light of various colors (for example, red, blue, green) by selecting a light emitting material. . The organic electroluminescent element having such characteristics is expected to be applied to various light emitting elements and display elements because of its energy saving, good visibility due to self-emission, and reduction in thickness and weight. . However, organic electroluminescence devices generally have problems such as low emission luminance, poor stability and durability, and insufficient practical use.

These problems will be described in detail below.
As an element structure of the organic electroluminescent element, there are a two-layer type of a hole (injection) transport layer and an electron transport light-emitting layer, or a three-layer type of a hole (injection) transport layer, a light-emitting layer, and an electron (injection) transport layer. well known. In such a stacked structure element, the element structure and the formation method are devised in order to increase the recombination efficiency of injected holes and electrons. Tang et al. Use a triphenyldiamine derivative for the hole transport layer and a tris (8-quinolinolato) aluminum complex for the light emitting layer. The advantages of the stacked structure are that it increases the efficiency of hole injection into the light-emitting layer, blocks the electrons injected from the cathode, increases the generation efficiency of excitons generated by recombination, and generates in the light-emitting layer For example, confining excitons.

  Known light-emitting materials include chelate complexes such as tris (8-quinolinolato) aluminum complex, coumarin derivatives, pyran derivatives, tetraphenylbutadiene derivatives, bisstyrylarylene derivatives, oxadiazole derivatives, and the like [Patent Documents 1 to 3]. See 3 etc.].

  As a method for improving the light emission luminance, an organic electroluminescent device using, for example, a tris (8-quinolinolato) aluminum complex as a host compound and a coumarin derivative or a pyran derivative as a guest compound (dopant) has been proposed [for example, Non-patent document 2]. However, it cannot be said that these light emitting elements also have sufficient durability and light emission luminance. In addition, when a tris (8-quinolinolato) aluminum complex is used as a host compound, it is possible to obtain red light having a longer wavelength than green, which is the emission color of the compound itself, but to obtain light having a shorter wavelength. Is difficult considering the energy state. In view of the above, in recent years, there has been a demand for improvements in light emission luminance, stability, and durability on the shorter wavelength side, particularly in blue light-emitting elements, and new materials are strongly desired.

  As a blue light emitting material, for example, a device using a phenylanthracene derivative [see Patent Document 4] and an anthracene derivative having a naphthyl group at the 9th and 10th positions [see Patent Document 5] has been reported. Such anthracene derivatives are also insufficient in stability and durability of the element, and further life extension of the element is desired.

  Since an organic electroluminescent element emits light by applying an electric field to an organic compound thin film, the organic compound is easily damaged by the load. In order to further stabilize the element, improve the durability, and prolong the life of the element, a material that is difficult to receive such a load is desired. That is, the material is required to have high stability and durability of the thin film. Asymmetry of the compound improves the stability of the thin film.

  Devices using asymmetric anthracene derivatives as blue light-emitting materials have also been reported [see Patent Document 6], but they have a styryl structure that is susceptible to thermal modification. In addition, although there is a report that illustrates an asymmetric type anthracene derivative [see Patent Documents 7 to 9], the implementation is limited to the monoanthracene derivative, and it still lacks sufficient durability.

In addition, there are reports that various anthracene derivatives have been used as hole transport materials, but their synthesis has not actually been performed, and evaluation as a light-emitting material has not been made [see Patent Document 10].
Appl. Phys. Lett., 51, 913 (1987). J. Appl. Phys., 65, 3610 (1989). JP-A-8-239655 JP 7-138561 A JP-A-3-200289 JP-A-8-012600 JP 11-003782 A JP 2003-306454 A International Publication WO2004-018587 JP 2004-59535 A International Publication No. WO2005-121057 JP 2000-182776 A

  An object of the present invention is to provide a novel compound and a long-life organic electroluminescence device containing the compound. More specifically, the compound can be suitably used for an organic electroluminescent device, has a thin film stability and high durability, and an organic material that realizes high stability and long life with improved emission luminance using the compound. The object is to provide an electroluminescent device.

As a result of intensive studies on various compounds and organic electroluminescent devices containing the compounds, the present inventors have found that an asymmetric anthracene having good thin film stability and high durability represented by the following general formula (1): It has been found that by using a compound, an organic electroluminescence device having improved emission luminance and realizing high stability and long life can be obtained, and the present invention has been completed. That is, the present invention
[1] Anthracene compound represented by the following general formula (1) [Chemical Formula 1],

[Wherein, A and B are substituted or unsubstituted aryl groups having 11 to 48 carbon atoms, and A and B do not match. n is an integer of 2-4. ]
[2] The anthracene compound represented by the general formula (1), wherein A is represented by the general formulas (2) to (7) [Chemical Formula 2],

[Wherein R _{21 to} R ₂₉ , R _{31 to} R ₃₉ , R _{41 to} R ₄₉ , R _{51 to} R ₅₇ , R _{61 to} R ₆₉ and R _{71 to} R ₇₉ each independently represents a hydrogen atom or a substituent. , X ₅ represents an oxygen atom or a sulfur atom. ]
[3] In the anthracene compound represented by the general formula (1), A is the general formula (2) to (7) [Chemical Formula 2], and B is the general formula (8) or (9) [Chemical Formula 3] The compound according to [2],

[Wherein Y _{1 to} Y ₅ and Y _{6 to} Y ₁₂ each independently represent a hydrogen atom or a substituted or unsubstituted aryl group having 5 to 36 carbon atoms, and X ₉ represents an oxygen atom or a sulfur atom. . ]
[4] An organic electroluminescence device comprising at least one layer containing at least one anthracene compound represented by the general formula (1) between a pair of electrodes,
[5] The organic electroluminescent element according to [4], wherein the layer containing the anthracene compound represented by the general formula (1) is a light emitting layer.
[6] The organic electroluminescence device according to [4], wherein the layer containing the anthracene compound represented by the general formula (1) is a hole injection transport layer,
[7] The organic electroluminescent element according to [5], wherein the light emitting layer is formed of a host material and a dopant material, and an anthracene compound represented by the general formula (1) is contained as the light emitting layer host material.
[8] The organic electroluminescence device according to [4], [5], [6] or [7], further having a hole injection / transport layer between a pair of electrodes,
[9] The organic electroluminescence device according to any one of [4] to [8], further including an electron injection / transport layer between the pair of electrodes.
It is about.

Hereinafter, the present invention will be described in detail.
The anthracene compound of the present invention is a compound represented by the general formula (1) [Chemical Formula 4].

[Wherein, A and B are substituted or unsubstituted aryl groups having 11 to 48 carbon atoms, and A and B do not match. n is an integer of 2-4. ]
In the present application, the aryl group represents a carbocyclic aromatic group or a heterocyclic aromatic group.
In the anthracene compound represented by the general formula (1), A is a substituted or unsubstituted aryl group having 11 to 48 carbon atoms,
Here, the carbon number means “the carbon number of the aryl group forming A or B” bonded to the anthracene ring, and the aryl group bonded to the anthracene ring is substituted with a substituent other than the aryl group The carbon contained in these substituents is not included in the “carbon number” described above.

  As used herein, substituted or unsubstituted means “straight-chain, branched or cyclic alkyl group, straight-chain, branched or cyclic alkoxy group, straight-chain, branched or cyclic alkyl group, or di-substituted. Substituted with a substituent such as an amino group substituted with an amino group, an aryl group, an amino group monocyclic or disubstituted with an aryl group, or an amino group substituted with a linear, branched or cyclic alkyl group and an aryl group, Or “unsubstituted”, preferably “a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 30 carbon atoms, carbon atom” A mono- or di-substituted amino group having a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, an aryl group having 3 to 20 carbon atoms, or an aryl group having 3 to 20 carbon atoms Amino group Or substituted with a substituent such as an amino group substituted with a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms and an aryl group having 4 to 20 carbon atoms, or unsubstituted " means.

  A represents a substituted or unsubstituted carbocyclic aromatic group having 11 to 48 carbon atoms, or a substituted or unsubstituted heterocyclic aromatic group.

  Specific examples of the carbocyclic aromatic group include a phenyl group substituted with an aryl group having 5 to 42 carbon atoms, a naphthyl group substituted with an aryl group, an azulenyl group substituted with an aryl group, a heptalenyl group, Biphenyl group, biphenylenyl group, as-indacenyl group, s-indacenyl group, acenaphthylenyl group, fluorenyl group, phenalenyl group, phenanthrenyl group, pyrenyl group, fluoranthenyl group, acephenanthrenylenyl group, aceanthrylenyl group, triphenylenyl group , Pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, rubicenyl group, coronenyl group, pyransrenyl group, and oberenyl group.

  Specific examples of the heterocyclic aromatic group include a furanyl group substituted with an aryl group having 7 to 44 carbon atoms, a thiophenyl group substituted with an aryl group having 7 to 44 carbon atoms, and a 7 to 44 carbon atom. A pyrrole group substituted by an aryl group, a benzofuranyl group substituted by an aryl group having 5 to 40 carbon atoms, an isobenzofuranyl group substituted by an aryl group having 5 to 40 carbon atoms, an aryl group having 5 to 40 carbon atoms Substituted with an aryl group having 5 to 40 carbon atoms, an indolyl group substituted with an aryl group having 5 to 40 carbon atoms, and an aryl group having 5 to 40 carbon atoms. Indolizinyl group, carbazolyl group, pyridyl group substituted with aryl group having 6 to 43 carbon atoms, quinolyl group substituted with aryl group having 5 to 39 carbon atoms, 5-39 carbon atoms Isoquinolyl group substituted with aryl group, phenanthridinyl group, acridinyl group, oxazolyl group substituted with aryl group having 8 to 45 carbon atoms, isoxazolyl group substituted with aryl group having 8 to 45 carbon atoms, carbon number A thiazolyl group substituted with an 8-45 aryl group, an isothiazolyl group substituted with an aryl group having 8 to 45 carbon atoms, a furazanyl group substituted with an aryl group having 9 to 46 carbon atoms, an aryl having 8 to 45 carbon atoms Substituted with an imidazolyl group substituted with a group, a pyrazolyl group substituted with an aryl group having 8 to 45 carbon atoms, a benzimidazolyl group substituted with an aryl group having 5 to 41 carbon atoms, or an aryl group with 5 to 40 carbon atoms 1,8-naphthyridinyl group, pyrazinyl group substituted with an aryl group having 7 to 44 carbon atoms, substituted with an aryl group having 7 to 44 carbon atoms Pyrimidinyl group, pyridazinyl group substituted with an aryl group having 7 to 44 carbon atoms, quinoxalinyl group substituted with an aryl group having 5 to 40 carbon atoms, quinazolinyl group substituted with an aryl group having 5 to 40 carbon atoms, carbon A sinolinyl group substituted with an aryl group having 5 to 40 carbon atoms, a phthalazinyl group substituted with an aryl group having 5 to 40 carbon atoms, a purinyl group substituted with an aryl group having 6 to 43 carbon atoms, Examples include a pteridinyl group, a perimidinyl group, a 1,10-phenanthrolinyl group, a thiantenyl group, a phenoxathinyl group, a phenoxazinyl group, a phenothiazinyl group, and a phenazinyl group that are substituted with an aryl group.

  Preferable examples include groups selected from the following general formulas (2) to (7) [Chemical Formula 5].

R _{21 to} R ₂₉ , R _{31 to} R ₃₉ , R _{41 to} R ₄₉ , R _{51 to} R ₅₇ , R _{61 to} R ₆₉ and R _{71 to} R ₇₉ each independently represent a hydrogen atom or a substituent, Hydrogen atom, halogen atom, cyano group, nitro group, substituted or unsubstituted amino group, substituted or unsubstituted ester group, linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, 1 to 10 carbon atoms Linear, branched or cyclic alkoxy group, substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms, substituted or unsubstituted group having 4 to 20 carbon atoms An aryl group or a substituted or unsubstituted aryloxy group having 4 to 20 carbon atoms, more preferably a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted amino group. Group, a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 8 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 16 carbon atoms, carbon A substituted or unsubstituted aralkyloxy group having 7 to 16 carbon atoms, a substituted or unsubstituted aryl group having 4 to 16 carbon atoms, or a substituted or unsubstituted aryloxy group having 4 to 16 carbon atoms is represented.

The adjacent groups of R _{21 to} R ₂₉ , R _{31 to} R ₃₉ , R _{41 to} R ₄₉ , R _{51 to} R ₅₇ , R _{61 to} R _69, and R _{71 to} R ₇₉ each have a ring together with the adjacent group. It may be formed.

  Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and the like.

  Specific examples of the above-mentioned substituted or unsubstituted amino group include amino group, N-methylamino group, N-ethylamino group, Nn-propylamino group, N-iso-propylamino group, Nn- Butylamino group, N-iso-butylamino group, N-sec-butylamino group, N-tert-butylamino group, Nn-pentylamino group, N-cyclopentylamino group, Nn-hexylamino group, N-cyclohexylamino group, N-benzylamino group, N-phenethylamino group, N-phenylamino group, N- (1-naphthyl) amino group, N- (2-naphthyl) amino group, N- (4-phenyl) Phenyl) amino group, N- (3-phenylphenyl) amino group, N- (2-phenylphenyl) amino group, N- (4-methylphenyl) amino group, N- (2-methylphenyl) amino Group, N- (2-anthranyl) amino group, N- (9-anthranyl) amino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-di-n-propylamino group, N , N-di-iso-propylamino group, N, N-di-n-butylamino group, N, N-di-iso-butylamino group, N, N-di-sec-butylamino group, N, N -Di-tert-butylamino group, N, N-di-n-pentylamino group, N, N-dicyclopentylamino group, N, N-dicyclohexylamino group, N, N-dibenzylamino group, N, N -Diphenethylamino group, N-methyl-N-ethylamino group, N-methyl-Nn-propylamino group, N-methyl-N-iso-propylamino group, N-methyl-Nn-butylamino Group, N-methyl-N-tert-butylamino group, N- Tyl-N-cyclopentylamino group, N-methyl-N-cyclohexylamino group, N-methyl-N-benzylamino group, N-methyl-N-phenethylamino group, N-ethyl-N-benzylamino group, N- Ethyl-N-phenethylamino group, N-ethyl-N-tert-butylamino group, N-ethyl-N-cyclopentylamino group, N-ethyl-N-cyclohexylamino group, N-iso-propyl-N-cyclopentylamino Group, N-iso-propyl-N-cyclohexylamino group, N-iso-propyl-N-benzylamino group, N-tert-butyl-N-cyclopentylamino group, N-tert-butyl-N-cyclohexylamino group, N-tert-butyl-N-benzylamino group, N-cyclopentyl-N-benzylamino group, N-cyclohexyl-N-benzyl Mino group, N-methyl-N-phenylamino group, N-ethyl-N-phenylamino group, N-cyclohexyl-N-phenylamino group, N, N-diphenylamino group, N, N-di (1-naphthyl) ) Amino group, N, N-di (2-naphthyl) amino group, N- (1-naphthyl) -N- (2-naphthyl) amino group, N, N- (4-phenylphenyl) amino group, N- (1-naphthyl) -N-phenylamino group, N- (2-naphthyl) -N-phenylamino group, N- (4-phenylphenyl) -N-phenylamino group, N- (4-tert-butylphenyl) ) -N-phenylamino group, N- (3-tert-butylphenyl) -N-phenylamino group, N- (4-methylphenyl) -N-phenylamino group, N- (1-naphthyl) -N- (4'-phenylphenyl) a Amino group, N-(2-naphthyl) such as-N-(4'-phenylphenyl) amino group and the like.

  Specific examples of the above-mentioned substituted or unsubstituted ester group include, for example, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, iso-propoxycarbonyl group, n-butoxycarbonyl group, iso-butoxycarbonyl group, sec -Butoxycarbonyl group, n-pentyloxycarbonyl group, iso-pentyloxycarbonyl group, neopentyloxycarbonyl group, cyclopentyloxycarbonyl group, n-hexyloxycarbonyl group, 2-ethylbutoxycarbonyl group, 3,3-dimethylbutoxy Carbonyl group, cyclohexyloxycarbonyl group, n-heptyloxycarbonyl group, cyclohexylmethyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, n-nonyloxycal Nyl group, n-decyloxycarbonyl group, n-dodecyloxycarbonyl group, n-tetradecyloxycarbonyl group, n-hexadecyloxycarbonyl group, benzyloxycarbonyl group, phenyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, acetyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, iso-propylcarbonyloxy group, n-butylcarbonyloxy group, iso-butylcarbonyloxy group, sec-butylcarbonyloxy group N-pentylcarbonyloxy group, iso-pentylcarbonyloxy group, neopentylcarbonyloxy group, cyclopentylcarbonyloxy group, n-hexylcarbonyloxy group, 2-ethylbutylcarbonyloxy group, 3, 3 Dimethylbutylcarbonyloxy group, cyclohexylcarbonyloxy group, n-heptylcarbonyloxy group, cyclohexylmethylcarbonyloxy group, n-octylcarbonyloxy group, 2-ethylhexylcarbonyloxy group, n-nonylcarbonyloxy group, n-decylcarbonyloxy Group, n-dodecylcarbonyloxy group, ncarbonyl-tetradecyloxy group, n-hexadecylcarbonyloxy group, benzylcarbonyloxy group, phenylcarbonyloxy group, 1-naphthylcarbonyloxy group, 2-naphthylcarbonyloxy group, etc. Can be mentioned.

Specific examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an iso-butyl group. , Sec-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2 -Ethylbutyl group, 2-ethylhexyl group, n-heptyl group, 1-methylhexyl group, n-octyl group, 1-methylheptyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 2,6-dimethyl-4-heptyl group, 3,5,5-trimethylhexyl group, n-decyl group, 1-ethyloctyl group, n-dodecyl group, 1-methyldecyl group, n-tridecyl 1-hexylheptyl group, n-tetradecyl group, n-pentadecyl group, 1-hexyloctyl group, n-hexadecyl group, n-heptadecyl group, 1-octylnonylki, n-octadecyl group, n-nonyldecyl group, 1 -Decylundecyl group, n-eicosyl group, n-docosyl group, n-tetracosyl group, cyclohexyl group, cyclohexylmethyl group, (1-isopropylcyclohexyl) methyl group, (2-isopropylcyclohexyl) ethyl group, cyclopentyl group, 2-ethylbutyl Group, 3,3-dimethylbutyl group, 1,1-dimethylhexyl group, bornel group, isobornel group, 1-norbornyl group, 2-norbornanemethyl group, 1-bicyclo [2.2.2] octyl group, 1- Adamantyl group, 3-noradamantyl group, 1-adamantyl group Til group, cyclobutyl group, 1-methylcyclopentyl group, 4-methylcyclohexyl group, 3-methylcyclohexyl group, 2-methylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,6- Dimethylcyclohexyl group, 3,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,4,6-trimethylcyclohexyl group, 3,3,5-trimethylcyclohexyl group, 2,6-diisopropylcyclohexyl group, 4- tert-butylcyclohexyl group, 3-tert-butylcyclohexyl group, 4-phenylcyclohexyl group, 2-phenylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, cyclotetradecyl group,
Methoxymethyl group, ethoxymethyl group, n-butoxymethyl group, n-hexyloxymethyl group, (2-ethylbutyloxy) methyl group, n-octyloxymethyl group, n-decyloxymethyl group, 2-methoxyethyl group 2-ethoxyethyl group, 2-n-propoxyethyl group, 2-iso-propoxyethyl group, 2-n-butoxyethyl group, 2-n-pentyloxyethyl group, 2-n-hexyloxyethyl group, 2 -(2'-ethylbutyloxy) ethyl group, 2-n-heptyloxyethyl group, 2-n-octyloxyethyl group, 2- (2'-ethylhexyloxy) ethyl group, 2-n-decyloxyethyl group 2-n-dodecyloxyethyl group, 2-n-tetradecyloxyethyl group, 2-cyclohexyloxyethyl group, 2-methoxypropyl 3-methoxypropyl group, 3-ethoxypropyl group, 3-n-propoxypropyl group, 3-iso-propoxypropyl group, 3- (n-butoxy) propyl group, 3- (n-pentyloxy) propyl group, 3- (n-hexyloxy) propyl group, 3- (2'-ethylbutoxy) propyl group, 3- (n-octyloxy) propyl group, 3- (2'-ethylhexyloxy) propyl group, 3- (n- Decyloxy) propyl group, 3- (n-dodecyloxy) propyl group, 3- (n-tetradecyloxy) propyl group, 3-cyclohexyloxypropyl group, 4-methoxybutyl group, 4-ethoxybutyl group, 4-n -Propoxybutyl group, 4-iso-propoxybutyl group, 4-n-butoxybutyl group, 4-n-hexyloxybutyl group, 4-n-octyl Xylbutyl, 4-n-decyloxybutyl, 4-n-dodecyloxybutyl, 5-methoxypentyl, 5-ethoxypentyl, 5-n-ethoxypentyl, 6-ethoxyhexyl, 6-iso Propoxyhexyl group, 6-n-butoxyhexyl group, 6-n-hexyloxyhexyl group, 6-n-decyloxyhexyl group, 4-methoxycyclohexyl group, 7-ethoxyheptyl group, 7-isopropoxyheptyl group, 8 -Methoxyoctyl group, 10-methoxydecyl group, 10-n-butoxydecyl group, 12-ethoxydodecyl group, 12-isopropoxide decyl group, tetrahydrofurfuryl group,
2- (2′-methoxyethoxy) ethyl group, 2- (2′-ethoxyethoxy) ethyl group, 2- (2′-n-butoxyethoxy) ethyl group, 3- (2′-ethoxyethoxy) propyl group, 2-allyloxyethyl group, 2- (4′-pentenyloxy) ethyl group, 3-allyloxypropyl group, 3- (2′-hexenyloxy) propyl group, 3- (2′-heptenyloxy) propyl group, 3 -(1'-cyclohexenyloxy) propyl group, 4-allyloxybutyl group,
Benzyloxymethyl group, 2-benzyloxyethyl group, 2-phenethyloxyethyl group, 2- (4′-methylbenzyloxy) ethyl group, 2- (2′-methylbenzyloxy) ethyl group, 2- (4 ′) -Fluorobenzyloxy) ethyl group, 2- (4'-chlorobenzyloxy) ethyl group, 3-benzyloxypropyl group, 3- (4'-methoxybenzyloxy) propyl group, 4-benzyloxybutyl group, 2- (Benzyloxymethoxy) ethyl group, 2- (4′-methylbenzyloxymethoxy) ethyl group,
Phenyloxymethyl group, 4-methylphenyloxymethyl group, 3-methylphenyloxymethyl group, 2-methylphenyloxymethyl group, 4-methoxyphenyloxymethyl group, 4-fluorophenyloxymethyl group, 4-chlorophenyloxymethyl group Group, 2-chlorophenyloxymethyl group, 2-phenyloxyethyl group, 2- (4′-methylphenyloxy) ethyl group, 2- (4′-ethylphenyloxy) ethyl group, 2- (4′-methoxyphenyl) Oxy) ethyl group, 2- (4′-chlorophenyloxy) ethyl group, 2- (4′-bromophenyloxy) ethyl group, 2- (1′-naphthyloxy) ethyl group, 2- (2′-naphthyloxy) ) Ethyl group, 3-phenyloxypropyl group, 3- (2′-naphthyloxy) propyl group, 4-phenyloxy Sibutyl group, 4- (2′-ethylphenyloxy) butyl group, 5- (4′-tert-butylphenyloxy) pentyl group, 6- (2′-chlorophenyloxy) hexyl group, 8-phenyloxyoctyl group, 10-phenyloxydecyl group, 10- (3′-chlorophenyloxy) decyl group, 2- (2′-phenyloxyethoxy) ethyl group, 3- (2′-phenyloxyethoxy) propyl group, 4- (2 ′ -Phenyloxyethoxy) butyl group,
n-butylthiomethyl group, n-hexylthiomethyl group, 2-methylthioethyl group, 2-ethylthioethyl group, 2-n-butylthioethyl group, 2-n-hexylthioethyl group, 2-n-octyl Thioethyl group, 2-n-decylthioethyl group, 3-methylthiopropyl group, 3-ethylthiopropyl group, 3-n-butylthiopropyl group, 4-ethylthiobutyl group, 4-n-propylthiobutyl group 4-n-butylthiobutyl group, 5-ethylthiopentyl group, 6-methylthiohexyl group, 6-ethylthiohexyl group, 6-n-butylthiohexyl group, 8-methylthiooctyl group, 2- (2 ′ -Methoxyethylthio) ethyl group, 4- (3'-ethoxypropylthio) butyl group, 2- (2'-ethylthioethylthio) ethyl group, 2-allylthioethyl group, 2- N-dithioethyl group, 3- (4′-methylbenzylthio) propyl group, 4-benzylthiobutyl group, 2- (2′-benzyloxyethylthio) ethyl group, 3- (3′-benzylthiopropylthio) propyl group ,
2-phenylthioethyl group, 2- (4′-methoxyphenylthio) ethyl group, 2- (2′-phenyloxyethylthio) ethyl group, 3- (2′-phenylthioethylthio) propyl group,
2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, 6-hydroxyhexyl group, 5-hydroxyheptyl group, 8-hydroxyoctyl group, 10- Examples thereof include a hydroxydecyl group, a 12-hydroxydodecyl group, and a 2-hydroxycyclohexyl group.

  Specific examples of the linear, branched or cyclic alkoxy group having 1 to 10 carbon atoms include a linear, branched or cyclic alkoxy group derived from the linear, branched or cyclic alkyl group. Can do.

Specific examples of the substituted or unsubstituted aralkyl group include benzyl group, α-methylbenzyl group, α-ethylbenzyl group, phenethyl group, α-methylphenethyl group, β-methylphenethyl group, α, α-dimethyl. Benzyl group, α, α-dimethylphenethyl group, 4-methylphenethyl group, 4-methylbenzyl group, 3-methylbenzyl group, 2-methylbenzyl group, 4-ethylbenzyl group, 2-ethylbenzyl group, 4-isopropyl Benzyl group, 4-tert-butylbenzyl group, 2-tert-butylbenzyl group, 4-tert-pentylbenzyl group, 4-cyclohexylbenzyl group, 4-n-octylbenzyl group, 4-tert-octylbenzyl group, 4 -Allylbenzyl group, 4-benzylbenzyl group, 4-phenethylbenzyl group, 4-phenylbenzyl group, 4- (4'-methyl) Phenyl) benzyl, 4-methoxybenzyl group, 2-methoxybenzyl group, 2-ethoxy benzyl group, 4-n-butoxybenzyl group, 4-n-heptyloxy benzyl group,
4-n-decyloxybenzyl group, 4-n-tetradecyloxybenzyl group, 4-n-heptadecyloxybenzyl group,
3,4-dimethoxybenzyl group, 4-methoxymethylbenzyl group, 4-isobutoxymethylbenzyl group, 4-allyloxybenzyl group, 4-vinyloxymethylbenzyl group, 4-benzyloxybenzyl group, 4-phenethyloxybenzyl Group, 4-phenyloxybenzyl group, 3-phenyloxybenzyl group,
4-hydroxybenzyl group, 3-hydroxybenzyl group, 2-hydroxybenzyl group, 4-hydroxy-3-methoxybenzyl group, 4-fluorobenzyl group, 2-fluorobenzyl group, 4-chlorobenzyl group, 3-chlorobenzyl Group, 2-chlorobenzyl group, 3,4-dichlorobenzyl group, 2-furfuryl group, diphenylmethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group and the like.

  Specific examples of the above substituted or unsubstituted aralkyloxy group include a substituted or unsubstituted aralkyloxy group derived from the above substituted or unsubstituted aralkyl group.

Specific examples of the above-mentioned substituted or unsubstituted aryl group include, for example, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 1-phenanthryl group, 2 -Phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-biphenyleneyl group, 2-biphenyleneyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-fluorenyl group 5-acenaphthylenyl group, 3-fluoranthenyl group, 1-triphenylenyl group, 2-triphenylenyl group, 1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group, 3-perylenyl group,
4-quinolyl group, 5-pyridyl group, 4-pyridyl group, 3-pyridyl group, 2-pyridyl group, 2-pyrimidyl group, 4-pyrimidine group, 5-pyrimidyl group, 2-pyridazinyl group, 2-pyrazinyl group, 3-furyl group, 2-furyl group, 3-thienyl group, 2-thienyl group, 2-oxazolyl group, 2-thiazolyl group, 2-benzothiophenyl group, 2-benzofuryl group, 2-benzoxazolyl group, 2-benzothiazolyl group, 2-benzimidazolyl group, 3-carbazolyl group, 9-carbazolyl group o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, p-terphenyl-4-yl group, p -Terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group,
4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 3-ethylphenyl group, 2-ethylphenyl group, 4-n-propylphenyl group, 4-isopropylphenyl group, 2-isopropylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-sec-butylphenyl group, 2-sec-butylphenyl group, 4-tert-butylphenyl group, 3-tert-butylphenyl Group, 2-tert-butylphenyl group, 4-n-pentylphenyl group, 4-isopentylphenyl group, 4-tert-pentylphenyl group, 4-n-hexylphenyl group, 4-n-heptylphenyl group, 4 -N-octylphenyl group, 4- (2'-ethylhexyl) phenyl group, 4-tert-octylphenyl group, 4-n-nonylphenyl group, 4- -Decylphenyl group, 4-n-dodecylphenyl group, 4-n-tetradecylphenyl group, 4-n-hexadecylphenyl group, 4-n-octadecylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group 4- (4′-tert-butylcyclohexyl) phenyl group, 4- (4′-methylcyclohexyl) phenyl group, 3-cyclohexylphenyl group, 2-cyclohexylphenyl group,
4-ethyl-1-naphthyl group, 6-n-butyl-2-naphthyl group,
2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,6-dimethylphenyl group, 2, 3,5-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,4-diethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 2,6- Diethylphenyl group, 2,6-diisopropylphenyl group, 2,6-diisobutylphenyl group, 2,4-di-tert-butylphenyl group, 2,5-di-tert-butylphenyl group, 3,5-di- tert-butylphenyl group, 2,4-dineopentylphenyl group, 2,5-di-tert-pentylphenyl group, 4,6-di-tert-butyl-2-methylphenyl group, 5-tert-butyl- 2 Methylphenyl group, 4-tert-butyl-2,6-dimethylphenyl group, 2,3,5,6-tetramethyl-phenyl group,
5-indanyl group, 1,2,3,4-tetrahydro-5-naphthyl group, 1,2,3,4-tetrahydro-6-naphthyl group,

4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl group, 2-ethoxyphenyl group, 3-n-propoxyphenyl group, 4-isopropoxyphenyl group, 2-isopropoxyphenyl Group, 4-n-butoxyphenyl group, 4-isobutoxyphenyl group, 2-isobutoxyphenyl group, 2-sec-butoxyphenyl group, 4-n-pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2 -Isopentyloxyphenyl group, 2-neopentyloxyphenyl group, 4-n-hexyloxyphenyl group, 2- (2'-ethylbutyl) oxyphenyl group, 4-n-octyloxyphenyl group, 4-n-decyl Oxyphenyl group, 4-n-dodecyloxyphenyl group, 4-n-tetradecyloxypheny Group, 4-n-hexadecyloxyphenyl group, 4-n-octadecyloxyphenyl group, 4-cyclohexyloxyphenyl group, 2-cyclohexyloxyphenyl group,
2-methoxy-1-naphthyl group, 4-methoxy-1-naphthyl group, 4-n-butoxy-1-naphthyl group, 5-ethoxy-1-naphthyl group, 6-ethoxy-2-naphthyl group, 6-n -Butoxy-2-naphthyl group, 6-n-hexyloxy-2-naphthyl group, 7-methoxy-2-naphthyl group, 7-n-butoxy-2-naphthyl group,
2,3-dimethoxyphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3, 5-diethoxyphenyl group, 3,5-di-n-butoxyphenyl group, 2-methoxy-4-methylphenyl group, 2-methoxy-5-methylphenyl group, 2-methyl-4-methoxyphenyl group, 3 -Methyl-4-methoxyphenyl group, 3-methyl-5-methoxyphenyl group, 3-ethyl-5-methoxyphenyl group, 2-methoxy-4-ethoxyphenyl group, 2-methoxy-6-ethoxyphenyl group, 3 , 4,5-trimethoxyphenyl group,
4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 4-chlorophenyl group, 3-chlorophenyl group, 2-chlorophenyl group, 4-bromophenyl group, 2-bromophenyl group, 4-chloro-1 -Naphthyl group, 4-chloro-2-naphthyl group, 6-bromo-2-naphthyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6- Difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 3, 4-dichlorophenyl group, 3,5-dichlorophenyl group, 2,5-dibromophenyl group, 2,4,6-trichloroph Group, 2,3,6-bromophenyl group, 3,4,5-trifluorophenyl group, 2,4-dichloro-1-naphthyl group, 1,6-dichloro-2-naphthyl group,
2-fluoro-4-methylphenyl group, 2-fluoro-5-methylphenyl group, 3-fluoro-2-methylphenyl group, 3-fluoro-4-methylphenyl group, 4-fluoro-2-methylphenyl group, 5-fluoro-2-methylphenyl group, 2-chloro-4-methylphenyl group, 2-chloro-5-methylphenyl group, 2-chloro-6-methylphenyl group, 3-chloro-2-methylphenyl group, 4-chloro-2-methylphenyl group, 4-chloro-3-methylphenyl group, 2-chloro-4,6-dimethylphenyl group, 2-fluoro-4-methoxyphenyl group, 2-fluoro-6-methoxyphenyl Group, 3-fluoro-4-ethoxyphenyl group, 5-chloro-2-methoxyphenyl group, 6-chloro-3-methoxyphenyl group, 5-chloro-2,4- Methoxyphenyl group, 2-chloro-4-nitrophenyl group, 4-chloro-2-nitrophenyl group,
4-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 2-trifluoromethylphenyl group, 3,5-bis (trifluoromethyl) phenyl group,
4-trifluoromethyloxyphenyl group,
4-allylphenyl group, 2-allylphenyl group, 2-isopropenylphenyl group, 4-benzylphenyl group, 2-benzylphenyl group, 4- (4′-methylbenzyl) phenyl group, 4-cumylphenyl group, 4- (4′-methoxycumyl) phenyl group,
4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 4- (4′-methylphenyl) phenyl group, 4- (4′-ethylphenyl) phenyl group, 4- (4′-isopropylphenyl) ) Phenyl group, 4- (4′-tert-butylphenyl) phenyl group, 4- (4′-n-hexylphenyl) phenyl group, 4- (4′-n-octylphenyl) phenyl group,

4- (4′-methoxyphenyl) phenyl group, 4- (4′-ethoxyphenyl) phenyl group, 4- (4′-n-butoxyphenyl) phenyl group, 2- (2′-methoxyphenyl) phenyl group, 4- (4′-fluorophenyl) phenyl group, 4- (4′-chlorophenyl) phenyl group, 3-methyl-4-phenyl group, 2-methoxy-5-phenylphenyl group, 3-methoxy-4-phenylphenyl Group,
4-methoxymethylphenyl group, 4-ethoxymethylphenyl group, 4-n-butoxymethylphenyl group, 3-methoxymethylphenyl group, 4- (2′-methoxyethyl) phenyl group, 4- (2′-ethoxyethyl) Oxy) phenyl group, 4- (2′-n-butoxyethyloxy) phenyl group, 4- (3′-ethoxypropyloxy) phenyl group, 4-vinyloxyphenyl group, 4-allyloxyphenyl group, 3-allyl Oxyphenyl group, 4- (4′-pentenyloxy) phenyl group, 4-allyloxy-1-naphthyl group,
4-allyloxymethylphenyl group, 4- (2′-allyloxyethyloxy) phenyl group,
4-benzyloxyphenyl group, 2-benzyloxyphenyl group, 4-phenethyloxyphenyl group, 4- (4′-chlorobenzyloxy) phenyl group, 4- (4′-methylbenzyloxy) phenyl group, 4- ( 4′-methoxybenzyloxy) phenyl group, 4- (3′-ethoxybenzyloxy) phenyl group, 4-benzyloxy-1-naphthyl group, 5- (4′-methylbenzyloxy) -1-naphthyl group, 6 -Benzyloxy-2-naphthyl group, 6- (4'-methylbenzyloxy) -2-naphthyl group, 7-benzyloxy-2-naphthyl group, 4- (benzyloxymethyl) phenyl group, 4- (2 ' -Benzyloxyethyloxy) phenyl group,
4-phenyloxyphenyl group, 3-phenyloxyphenyl group, 2-phenyloxyphenyl group, 4- (4′-methylphenyloxy) phenyl group, 4- (4′-methoxyphenyloxy) phenyl group, 4- ( 4′-chlorophenyloxy) phenyl group, 4-phenyloxy-1-naphthyl group, 6-phenyloxy-2-naphthyl group, 7-phenyloxy-2-naphthyl group, 4-phenyloxymethylphenyl group, 4- ( 2′-phenyloxyethyloxy) phenyl group, 4- [2 ′-(4′-methylphenyloxy) ethyloxy] phenyl group, 4- [2 ′-(4′-methoxyphenyloxy) ethyloxy] phenyl group, 4 -[2 '-(4'-chlorophenyloxy) ethyloxy] phenyl group,
4-acetylphenyl group, 3-acetylphenyl group, 2-acetylphenyl group, 4-ethylcarbonylphenyl group, 2-ethylcarbonylphenyl group, 4-n-butylcarbonylphenyl group, 4-n-hexylcarbonylphenyl group, 4-n-octylcarbonylphenyl group, 4-cyclohexylcarbonylphenyl group, 4-acetyl-1-naphthyl group, 6-acetyl-2-naphthyl group, 6-n-butylcarbonyl-2-naphthyl group, 4-allylcarbonyl Phenyl group, 4-benzylcarbonylphenyl group, 4- (4′-methylbenzyl) carbonylphenyl group, 4-phenylcarbonylphenyl group, 4- (4′-methylphenyl) carbonylphenyl group, 4- (4′-chlorophenyl) ) Carbonylphenyl group, 4-phenylcarbonyl-1-na Methyl group,

4-methoxycarbonylphenyl group, 2-methoxycarbonylphenyl group, 4-ethoxycarbonylphenyl group, 3-ethoxycarbonylphenyl group, 4-n-propoxycarbonylphenyl group, 4-n-butoxycarbonylphenyl group, 4-n- Hexyloxycarbonylphenyl group, 4-n-decyloxycarbonylphenyl group, 4-cyclohexyloxycarbonylphenyl group, 4-ethoxycarbonyl-1-naphthyl group, 6-methoxycarbonyl-2-naphthyl group, 6-n-butoxycarbonyl 2-naphthyl group, 4-allyloxycarbonylphenyl group, 4-benzyloxycarbonylphenyl group, 4- (4′-chlorobenzyl) oxycarbonylphenyl group, 4-phenethyloxycarbonylphenyl group, 6-benzyloxycal Bonyl-2-naphthyl group, 4-phenyloxycarbonylphenyl group, 4- (4′-ethylphenyl) oxycarbonylphenyl group, 4- (4′-chlorophenyl) oxycarbonylphenyl group, 4- (4′-ethoxyphenyl) ) Oxycarbonylphenyl group, 6-phenyloxycarbonyl-2-naphthyl group,
4-acetyloxyphenyl group, 3-acetyloxyphenyl group, 2-acetyloxyphenyl group, 4-ethylcarbonyloxyphenyl group, 2-ethylcarbonyloxyphenyl group, 4-n-propylcarbonyloxyphenyl group, 4-n -Pentylcarbonyloxyphenyl group, 4-n-octylcarbonyloxyphenyl group, 4-cyclohexylcarbonyloxyphenyl group, 3-cyclohexylcarbonyloxyphenyl group, 4-acetyloxy-1-naphthyl group, 4-n-butylcarbonyloxy -1-naphthyl group, 5-acetyloxy-1-naphthyl group, 6-ethylcarbonyloxy-2-naphthyl group, 7-acetyloxy-2-naphthyl group, 4-allylcarbonyloxyphenyl group, 4-benzylcarbonyloxy Phenyl group 4- phenethyl carbonyloxy phenyl group, 6-benzyloxy carbonyloxy-2-naphthyl group,
4-phenylcarbonyloxyphenyl group, 4- (4′-methylphenyl) carbonyloxyphenyl group, 4- (2′-methylphenyl) carbonyloxyphenyl group, 4- (4′-chlorophenyl) carbonyloxyphenyl group, 4 -(2'-chlorophenyl) carbonyloxyphenyl group, 4-phenylcarbonyloxy-1-naphthyl group, 6-phenylcarbonyloxy-2-naphthyl group, 7-phenylcarbonyloxy-2-naphthyl group,
4-methylthiophenyl group, 2-methylthiophenyl group, 2-ethylthiophenyl group, 3-ethylthiophenyl group, 4-n-propylthiophenyl group, 2-isopropylthiophenyl group, 4-n-butylthiophenyl group 2-isobutylthiophenyl group, 2-neopentylphenyl group, 4-n-hexylthiophenyl group, 4-n-octylthiophenyl group, 4-cyclohexylthiophenyl group,
4-benzylthiophenyl group, 3-benzylthiophenyl group, 2-benzylthiophenyl group, 4- (4′-chlorobenzylthio) phenyl group, 4-phenylthiophenyl group, 3-phenylthiophenyl group, 2- Phenylthiophenyl group, 4- (4'-methylphenylthio) phenyl group, 4- (3'-methylphenylthio) phenyl group, 4- (4'-methoxyphenylthio) phenyl group, 4- (4'- Chlorophenylthio) phenyl group, 2-ethylthio-1-naphthyl group, 4-methylthio-1-naphthyl group, 6-ethylthio-2-naphthyl group, 6-phenylthio-2-naphthyl group,
4-nitrophenyl group, 3-nitrophenyl group, 2-nitrophenyl group, 3,5-dinitrophenyl group, 4-nitro-1-naphthyl group, 4-formylphenyl group, 3-formylphenyl group, 2-formyl Phenyl group, 4-formyl-1-naphthyl group, 1-formyl-2-naphthyl group,

4-pyrrolidinophenyl group, 4-piperidinophenyl group, 4-morpholinophenyl group, 4- (N-ethylpiperazino) phenyl group, 4-pyrrolidino-1-naphthyl group,
4-aminophenyl group, 3-aminophenyl group, 2-aminophenyl group,
4- (N-methylamino) phenyl group, 3- (N-methylamino) phenyl group, 4- (N-ethylamino) phenyl group, 2- (N-isopropylamino) phenyl group, 4- (Nn) -Butylamino) phenyl group, 2- (Nn-butylamino) phenyl group, 4- (Nn-octylamino) phenyl group, 4- (Nn-dodecylamino) phenyl group, 4- (N -Benzylamino) phenyl group, 4- (N-phenylamino) phenyl group, 2- (N-phenylamino) phenyl group,
4- (N, N-dimethylamino) phenyl group, 3- (N, N-dimethylamino) phenyl group, 4- (N, N-diethylamino) phenyl group, 2- (N, N-dimethylamino) phenyl group 2- (N, N-diethylamino) phenyl group, 4- (N, N-di-n-butylamino) phenyl group, 4- (N, N-di-n-hexylamino) phenyl group, 4- (N N-cyclohexyl-N-methylamino) phenyl group, 4- (N, N-diethylamino) -1-naphthyl group, 4- (N-benzyl-N-phenylamino) phenyl group, 4- (N, N-diphenyl) Amino) phenyl group, 4- [N-phenyl-N- (4-methylphenyl) amino] phenyl group, 4- [N, N-di (3′-methylphenyl) amino] phenyl group, 4- [N, N-di (4′-methylphenol ) Amino] phenyl group, 4- [N, N-di (4'-methoxyphenyl) amino] phenyl group, 2-(N, N-diphenylamino) phenyl group,
4-hydroxyphenyl group, 3-hydroxyphenyl group, 2-hydroxyphenyl group, 4-methyl-3-hydroxyphenyl group, 6-methyl-3-hydroxyphenyl group, 2-hydroxy-1-naphthyl group, 8-hydroxy -1-naphthyl group, 4-hydroxy-1-naphthyl group, 1-hydroxy-2-naphthyl group, 6-hydroxy-2-naphthyl group, 4-cyanophenyl group, 2-cyanophenyl group, 4-cyano-1 -A naphthyl group, 6-cyano- 2-naphthyl group, etc. can be mentioned.

  Specific examples of the above-mentioned substituted or unsubstituted aryloxy group include a substituted or unsubstituted aryloxy group derived from the above aryl group.

In the general formula (5), X ₅ represents an oxygen atom or a sulfur atom, preferably an oxygen atom.

  B represents a substituted or unsubstituted carbocyclic aromatic group having 11 to 48 carbon atoms, or a substituted or unsubstituted heterocyclic aromatic group.

  Specific examples of B include, for example, the substituted or unsubstituted substituted or unsubstituted carbocyclic aromatic group described above in A, or a substituted or unsubstituted heterocyclic aromatic group. Specific examples include a substituted or unsubstituted aryl group having 11 or more carbon atoms, and a group represented by the following general formula (8) or (9) [Chem. 6]. be able to.

[Wherein Y _{1 to} Y ₅ and Y _{6 to} Y ₁₂ each independently represent a hydrogen atom or a substituted or unsubstituted aryl group having 5 to 36 carbon atoms, and X ₉ represents an oxygen atom or a sulfur atom. . ]
Y _{1 to} Y ₅ and Y _{6 to} Y ₁₂ are each independently a hydrogen atom or a substituted or unsubstituted aryl group having 5 to 36 carbon atoms, preferably a hydrogen atom or a substituted or unsubstituted group having 5 to 30 carbon atoms. It is a substituted aryl group, and more preferably represents a hydrogen atom or a substituted or unsubstituted aryl group having 5 to 24 carbon atoms.

Specific examples of the substituted or unsubstituted aryl group represented by Y _{1 to} Y ₅ and Y _{6 to} Y ₁₂ include, for example, R _{21 to} R ₂₉ , R _{31 to} R ₃₉ , R _{41 to} R ₄₉ , and R _{51 to} R _57. , R _{61 to} R ₆₉ and R _{71 to} R ₇₉ substituted or unsubstituted aryl having 5 or more carbon atoms as specific examples.

In the general formula (9), X ₉ represents an oxygen atom or a sulfur atom, preferably an oxygen atom.

In the anthracene compound represented by the general formula (1), n represents an integer of 2 to 4, preferably 2 to 3.
In the anthracene compound represented by the general formula (1), A is preferably a group represented by the general formulas (2) to (7), and more preferably the general formulas (2), (3), ( 4), (5) and (6).

  In the anthracene compound represented by the general formula (1), B is preferably a group represented by the general formulas (8) and (9).

  In the anthracene compound represented by the general formula (1), A and B do not match.

The fact that A and B do not match means that it is asymmetric around n anthracenes in the general formula (1). Therefore, A and B are not represented by the same general formula at the same time. For example, when A consists of the general formula (2), (3), or (4) and B is represented by the general formula (8), Y ₁ = R ₂₁ and Y ₂ = R ₂₂ and Y ₃ = R ₂₃ and Y ₄ = R ₂₄ and Y ₅ is a phenyl group substituted with R _{25 to} R ₂₉ , or Y ₁ = R ₃₂ and Y ₂ = R ₃₃ and Y ₃ = R ₃₄ and Y ₅ = R ₃₁ and Y ₄ is a phenyl group substituted with R _{35 to} R ₃₉ , or Y ₁ = R ₄₃ and Y ₂ = R ₄₄ and Y ₄ = R ₄₁ and Y ₅ = R ₄₂ and Y ₃ is R _{45 to} R ₄₉ It is not represented by a substituted phenyl group. Further, when A consists of the general formula (5) and B is represented by the general formula (9), Y ₆ = R ₅₁ and Y ₇ = R ₅₂ and Y ₈ = R ₅₃ and Y ₉ = R ₅₄ and Y ₁₀ = _{R 55} and _Y 11 _{= R 56} and _Y 12 _{= R 57} and _X 9 = is not represented by _{X 5.}

Specific examples of the anthracene compound represented by the general formula (1) of the present invention are illustrated below, but the present invention is not limited to these specific examples. Formulas (10) to (36) represent general formulas, and in Tables 1 to 27, specific examples corresponding to R _{21 to} R ₂₉ , R _{31 to} R ₃₉ , R ₄₁ to R ₄₉ , R _{51 to} R ₅₇ , X ₅ , R _{61 to} R ₆₉ and R _{71 to} R ₇₉ and Y ₁ to Y ₅ , R _{51 to} R ₅₇ , X ₅ and R _{61 to} R ₆₉ and Y ₆ to Y ₁₂ , X ₉ . In the table, Ph represents a phenyl group.

  The anthracene compound represented by the general formula (1) of the present invention can be produced by, for example, the following steps.

  Production of anthracene compound represented by general formula (1)

[Wherein, A, B, and n have the same meaning as in general formula (1), L ₁ and L ₂ represent a leaving group such as a halogen atom or a trifluoromethanesulfonyloxy group, or a boronic acid group or boronic acid. Represents an ester group, and _one of L ₁ and L ₂ is a leaving group such as a halogen atom or trifluoromethanesulfonyloxy, and the other is a boronic acid group or a boronic ester group]
That is, a compound represented by general formula (B) is converted into a compound represented by general formula (A) using a palladium catalyst [eg, tetrakis (triphenylphosphine) palladium, tritert-butylphosphine / palladium acetate] and a base (eg, And an anthracene compound represented by the general formula (1) can be produced by the reaction in the presence of an inorganic base such as sodium carbonate, potassium carbonate or potassium phosphate, or an organic base such as triethylamine or pyridine.

  Moreover, the anthracene compound represented by General formula (1) can also be manufactured according to the following processes [Chemical 35], for example.

[Wherein A, B, and n represent the same meaning as in general formula (1), and L ₃ and L ₄ represent Li, MgI, or MgBr]
That is, the organometallic reagent represented by the general formula (D) is allowed to act on the anthraquinone derivative represented by the general formula (C) to obtain the compound represented by the general formula (E). Then, the organometallic reagent represented by the general formula (F) is allowed to act on the compound represented by the general formula (E) to produce the compound represented by the general formula (G). The anthracene compound represented by the general formula (1) can be produced by treating the compound represented by the general formula (G) with hydrogen iodide or hydrogen bromide and dehydroaromatizing it.

  Next, the organic electroluminescent element of the present invention will be described. The organic electroluminescent element of the present invention comprises at least one layer containing at least one anthracene compound represented by the general formula (1) between a pair of electrodes. An organic electroluminescent element is usually formed by sandwiching at least one light emitting layer containing at least one light emitting component between a pair of electrodes. A hole injection / transport layer and / or an electron injection containing a hole injection component as desired, considering the functional level of the hole injection and hole transport, electron injection and electron transport of the compound used in the light emitting layer. An electron injecting and transporting layer containing a transporting component can also be provided.

  For example, when the hole injection function, the hole transport function and / or the electron injection function, and the electron transport function of the compound used in the light emitting layer are good, the light emitting layer is a hole injection transport layer and / or an electron injection transport layer. As a type of element configuration that also serves as a single layer type element configuration. Further, when the light emitting layer is poor in the hole injection function and / or the hole transport function, a two-layer device configuration in which a hole injection transport layer is provided on the anode side of the light emitting layer, the light emitting layer has an electron injection function and / or Alternatively, when the electron transport function is poor, a two-layer device structure in which an electron injection transport layer is provided on the cathode side of the light emitting layer can be obtained. Furthermore, a three-layer device structure in which the light-emitting layer is sandwiched between a hole injection transport layer and an electron injection transport layer can be used.

  In addition, each of the hole injecting and transporting layer, the electron injecting and transporting layer, and the light emitting layer may have a single layer structure or a multilayer structure, and the hole injecting and transporting layer and the electron injecting and transporting layer The layer having an injection function and the layer having a transport function can be separately provided.

  In the organic electroluminescent element of the present invention, the anthracene compound represented by the general formula (1) is preferably used as a component of the hole injection transport layer and / or the light emitting layer, and is used as a component of the light emitting layer. It is more preferable.

  In the organic electroluminescent element of the present invention, the anthracene compound represented by the general formula (1) may be used alone or in combination.

  The configuration of the organic electroluminescent device of the present invention is not particularly limited. For example, (EL-1) anode / hole injection transport layer / light emitting layer / electron injection transport layer / cathode type device (FIG. 1). ), (EL-2) anode / hole injection transport layer / light emitting layer / cathode type device (FIG. 2), (EL-3) anode / light emitting layer / electron injection transport layer / cathode type device (FIG. 3), EL-4) Anode / light emitting layer / cathode type element (FIG. 4), and the like. Further, an EL (EL-5) anode / hole injection / transport layer / electron injection / transport layer / light-emitting layer / electron injection / transport layer / cathode-type device (FIG. 5) in which the light-emitting layer is sandwiched between electron injection / transport layers. You can also. The (EL-4) type element structure includes an element of a type in which a light emitting component is sandwiched between a pair of electrodes as a light emitting layer, (EL-6) a hole injection transport component as a light emitting layer, A device of a type sandwiched between a pair of electrodes in a single layer form in which a light emitting component and an electron injecting and transporting component are mixed (FIG. 6), (EL-7) A hole injecting and transporting component and a light emitting component are mixed as a light emitting layer. A device of a type sandwiched between a pair of electrodes in a single layer form (FIG. 7), (EL-8) A type sandwiched between a pair of electrodes in a single layer form in which a light emitting component and an electron injection / transport component are mixed as a light emitting layer Any of these elements (FIG. 8) may be used.

  The organic electroluminescent device of the present invention is not limited to these device configurations, and each type of device can be provided with a plurality of hole injection / transport layers, light emitting layers, and electron injection / transport layers. Further, in each type of device, the hole injection / transport layer is disposed between the light emitting layer, the hole injection / transport component and the light emitting component mixed layer and / or the light emitting layer and the electron injection / transport layer between the light emitting component and the light emitting component. And a mixed layer of electron injecting and transporting components can be provided.

  A preferred organic electroluminescent element is an (EL-1) type element, an (EL-2) type element, an (EL-5) type element, an (EL-6) type element or an (EL-7) type element. More preferably, it is an (EL-1) type element, an (EL-2) type element or an (EL-7) type element.

  Hereinafter, the components of the organic electroluminescence device of the present invention will be described in detail. As an example, (EL-1) anode / hole injection / transport layer / light emitting layer / electron injection / transport layer / cathode type device shown in FIG. 1 will be described.

  In FIG. 1, 1 is a substrate, 2 is an anode, 3 is a hole injecting and transporting layer, 4 is a light emitting layer, 5 is an electron injecting and transporting layer, 6 is a cathode, and 7 is a power source.

  The organic electroluminescent element of the present invention is preferably supported by the substrate 1, and the substrate is not particularly limited, but a transparent or translucent substrate is preferable, and the material is soda lime glass, Examples thereof include glass such as borosilicate glass and transparent polymers such as polyester, polycarbonate, polysulfone, polyethersulfone, polyacrylate, polymethyl methacrylate, polypropylene, and polyethylene. Further, a substrate made of a translucent plastic sheet, quartz, transparent ceramics, or a composite sheet in which these are combined can also be used. Furthermore, for example, a color filter film, a color conversion film, and a dielectric reflection film can be combined with the substrate to control the emission color.

As the anode 2, it is preferable to use a metal, an alloy or a conductive compound having a relatively large work function as an electrode material. Examples of the electrode material used for the anode include gold, platinum, silver, copper, cobalt, nickel, palladium, vanadium, tungsten, indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), zinc oxide, ITO ( Indium tin oxide (Indium Tin Oxide), polythiophene, polypyrrole, etc. can be mentioned. These electrode materials may be used alone or in combination.

  For the anode, these electrode materials can be formed on the substrate by a method such as vapor deposition or sputtering.

  Further, the anode may have a single layer structure or a multilayer structure. The sheet electrical resistance of the anode is preferably set to several hundred Ω / □ or less, more preferably about 5 to 50 Ω / □.

  The thickness of the anode is generally about 5 to 1000 nm, more preferably about 10 to 500 nm, although it depends on the material of the electrode material used.

  The hole injection transport layer 3 is a layer containing a compound having a function of facilitating the injection of holes from the anode and a function of transporting the injected holes.

  The hole injecting and transporting layer is formed of an anthracene compound represented by the general formula (1) or other compounds having a hole injecting and transporting function (for example, phthalocyanine derivatives, triarylamine derivatives, triarylmethane derivatives, oxazole derivatives, hydrazones). Derivatives, stilbene derivatives, pyrazoline derivatives, polysilane derivatives, polyphenylene vinylene and derivatives thereof, polythiophene and derivatives thereof, poly-N-vinylcarbazole, and the like).

  The compounds having a hole injecting and transporting function may be used alone or in combination.

  The organic electroluminescent element of the present invention preferably contains an anthracene compound represented by the general formula (1) in the hole injection transport layer. Examples of the compound having a hole injecting and transporting function other than the anthracene compound represented by the general formula (1) of the present invention that can be used in the organic electroluminescent device of the present invention include triarylamine derivatives (for example, 4,4 '-Bis [N-phenyl-N- (4 "-methylphenyl) amino] biphenyl, 4,4'-bis [N-phenyl-N- (3" -methylphenyl) amino] biphenyl, 4,4'- Bis [N-phenyl-N- (3 ″ -methoxyphenyl) amino] biphenyl, 4,4′-bis [N-phenyl-N- (1 ″ -naphthyl) amino] biphenyl, 3,3′-dimethyl-4 , 4′-bis [N-phenyl-N- (3 ″ -methylphenyl) amino] biphenyl, 1,1-bis [4 ′-[N, N-di (4 ″ -methylphenyl) amino] phenyl] cyclo Xanthine, 9,10-bis [N- (4′-methylphenyl) -N- (4 ″ -n-butylphenyl) amino] phenanthrene, 3,8-bis (N, N-diphenylamino) -6-phenyl Phenanthridine, 4-methyl-N, N-bis [4 ", 4" '-bis [N', N'-di (4-methylphenyl) amino] biphenyl-4-yl] aniline, N, N ' -Bis [4- (diphenylamino) phenyl] -N, N'-diphenyl-1,3-diaminobenzene, N, N'-bis [4- (diphenylamino) phenyl] -N, N'-diphenyl-1 , 4-diaminobenzene, 5,5 "-bis [4- (bis [4-methylphenyl] amino] phenyl-2,2 ': 5', 2" -terthiophene, 1,3,5-tris (diphenyl Amino) benzene, 4,4 ' 4 "-tris (N-carbazolyl) triphenylamine, 4,4 ', 4" -tris [N, N-bis (4 "'-tert-butylbiphenyl-4" "-yl) amino] triphenylamine 1,3,5-tris [N- (4′-diphenylamino] benzene and the like, polythiophene and its derivatives, and poly-N-vinylcarbazole and its derivatives are more preferable.

  When the anthracene compound represented by the general formula (1) and another compound having a hole injection function are used in combination, the content of the anthracene compound represented by the general formula (1) in the hole injection transport layer is as follows: Preferably, it is 0.1% by weight or more, more preferably 0.5 to 99.9% by weight, still more preferably 3 to 97% by weight.

  The light emitting layer 4 is a layer containing a compound having a function of injecting holes and electrons, a function of transporting them, and a function of generating excitons by recombination of holes and electrons.

  The light emitting layer is formed using an anthracene compound represented by the general formula (1) as a host material and at least one compound having a light emitting function other than the anthracene compound represented by the general formula (1) as a guest material. In addition, a compound having a light emitting function other than the anthracene compound represented by the general formula (1) is used as at least one host material, and the anthracene compound represented by the general formula (1) is used as a guest material. It can also be formed.

  As a compound (guest material / host material) having a light emitting function other than the anthracene compound represented by the general formula (1), for example, an acridone derivative, a quinacridone derivative, a diketopyrrolopyrrole derivative, a polycyclic aromatic compound [for example, Rubrene, anthracene, tetracene, pyrene, perylene, chrysene, decacyclene, coronene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, 9,10-diphenylanthracene, 9,10-bis (phenylethynyl) anthracene, 1,4-bis ( 9'-ethynylanthcenyl) benzene, 4,4'-bis (9 "-ethynylanthracenyl) biphenyl, dibenzo [f, f] diindeno [1,2,3-cd: 1 ', 2', 3 '-lm] perylene derivatives], triarylamine derivatives (eg, hole injection and transport functions) Examples of the compound having the above-mentioned compounds), organometallic complexes [for example, tris (8-quinolinolato) aluminum, bis (10-benzo [h] quinolinolato) beryllium, 2- (2′-hydroxyphenyl) benzothiazole Zinc salt, zinc salt of 4-hydroxyacridine, zinc salt of 3-hydroxyflavone, beryllium salt of 5-hydroxyflavone, aluminum salt of 5-hydroxyflavone], phosphorescent organometallic complex [for example, phenylpyridine iridium complex , Fluorine-substituted phenylpyridine iridium complexes, tetraazaporphyrin platinum complexes] stilbene derivatives [eg 1,1,4,4-tetraphenyl-1,3-butadiene, 4,4′-bis (2,2-diphenyl) Vinyl) biphenyl, 4,4′-bis [( , 1,2-triphenyl) ethenyl] biphenyl], coumarin derivatives (eg, coumarin 1, coumarin 6, coumarin 7, coumarin 30, coumarin 106, coumarin 138, coumarin 151, coumarin 152, coumarin 153, coumarin 307, coumarin 311. , Coumarin 314, Coumarin 334, Coumarin 338, Coumarin 343, Coumarin 500), pyran derivatives (eg DCM1, DCM2), oxazone derivatives (eg Nile Red), benzothiazole derivatives, benzoxazole derivatives, benzimidazole derivatives, pyrazine derivatives Cinnamate derivatives, poly-N-vinylcarbazole and derivatives thereof, polythiophene and derivatives thereof, polyphenylene and derivatives thereof, polyfluorene and derivatives thereof, poly Enirenbiniren and its derivatives, poly-biphenylene vinylene and derivatives thereof, poly terpolymers phenylene vinylene and derivatives thereof, poly naphthylene vinylene and its derivatives, and polythienylenevinylene and derivatives thereof. Compounds having a light emitting function other than the anthracene compound represented by the general formula (1) (guest material / host material) include acridone derivatives, quinacridone derivatives, polycyclic aromatic compounds, triarylamine derivatives, organometallic complexes, and stilbenes. Derivatives are preferred, and polycyclic aromatic compounds and organometallic complexes are more preferred.

  The organic electroluminescent element of the present invention preferably contains an anthracene compound represented by the general formula (1) as a host material in the light emitting layer.

  When the anthracene compound represented by the general formula (1) is used as a host material in combination with another compound having a light emitting function (guest material), the inclusion of the anthracene compound represented by the general formula (1) in the light emitting layer The rate is preferably 99.9-80% by weight, more preferably 99.9-90% by weight.

  A host material may be used independently and may be used together.

  Moreover, a guest material may be used independently and may be used together.

  When a plurality of host materials are used in combination, the ratio of the anthracene compound represented by the general formula (1) of the present invention to the entire host material is preferably 99 to 10% by weight, more preferably 90 to 20% by weight. It is.

  The electron injection / transport layer 5 is a layer containing a compound having a function of facilitating injection of electrons from the cathode and / or a function of transporting injected electrons.

  Examples of the compound having an electron injecting and transporting function used in the electron injecting and transporting layer include, for example, organometallic complexes, oxadiazole derivatives, triazole derivatives, triazine derivatives, perylene derivatives, quinoline derivatives, quinoxaline derivatives, diphenylquinone derivatives, phenanthroline derivatives. Nitro-substituted fluorenone derivatives, thiopyrandioxide derivatives, and the like. Examples of the organometallic complex include an organoaluminum complex such as tris (8-quinolinolato) aluminum, an organic beryllium complex such as bis (10-benzo [h] quinolinolato) beryllium, a beryllium salt of 5-hydroxyflavone, 5- Examples thereof include an aluminum salt of hydroxyflavone. An organoaluminum complex is preferable, and an organoaluminum complex having a substituted or unsubstituted 8-quinolinolato ligand is more preferable. Examples of the organoaluminum complex having a substituted or unsubstituted 8-quinolylate ligand include compounds represented by general formula (a) to general formula (c).

(Q) ₃ -Al (a)
(Wherein Q represents a substituted or unsubstituted 8-quinolinolate ligand)

(Q) ₂ -Al-OL '(b)
(In the formula, Q represents a substituted or unsubstituted 8-quinolinolate ligand, OL ′ represents a phenolate ligand, and L ′ represents a hydrocarbon group having 6 to 24 carbon atoms having a phenyl group. )

(Q) _2- Al-O-Al- (Q) ₂ (c)
(Wherein Q represents a substituted or unsubstituted 8-quinolinolate ligand)
Specific examples of the organoaluminum complex having a substituted or unsubstituted 8-quinolinolato ligand include, for example, 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-methylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (3-methylphenolate) ) Aluminum, bis (2-methyl-8-quinolinolato) (4-methylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-phenylphenolato) aluminum, bis (2-methyl-8-quinolinolato) ) (3-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (4-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,3-dimethylphenolate) aluminum, Bis (2-methyl-8-quinolinolate) ( , 6-Dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3,4-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3,5-dimethylphenolate) aluminum Bis (2-methyl-8-quinolinolato) (3,5-di-tert-butylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,6-diphenylphenolato) aluminum, bis (2 -Methyl-8-quinolinolato) (2,4,6-triphenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,6-trimethylphenolato) aluminum, bis (2-methyl- 8-quinolinolato) (2,4,5,6-tetramethylphenolate) aluminum, bi (2-methyl-8-quinolinolato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinolato) (2-naphtholato) aluminum, bis (2,4-dimethyl-8-quinolinolato) (2-phenyl) Phenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (4-phenylphenolate) aluminum, bis (2 , 4-dimethyl-8-quinolinolato) (3,5-dimethylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3,5-di-tert-butylphenolate) aluminum,
Bis (2-methyl-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-8-quinolinolato) aluminum, bis (2,4-dimethyl-8-quinolinolato) aluminum-μ-oxo-bis (2, 4-dimethyl-8-quinolinolato) aluminum, bis (2-methyl-4-ethyl-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-4-ethyl-8-quinolinolato) aluminum, bis (2- Methyl-4-methoxy-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-4-methoxy-8-quinolinolato) aluminum, bis (2-methyl-5-cyano-8-quinolinolato) aluminum-μ- Oxo-bis (2-methyl-5-cyano-8-quinolinolato) aluminum, bi (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum.

  A compound having an electron injecting and transporting function may be used alone or in combination.

  As the cathode 6, it is preferable to use a metal, an alloy or a conductive compound having a relatively small work function as an electrode material. Examples of the electrode material used for the cathode include lithium, lithium-indium alloy, sodium, sodium-potassium alloy, calcium, magnesium, magnesium-silver alloy, magnesium-indium alloy, indium, ruthenium, titanium, manganese, yttrium, and aluminum. , Aluminum-lithium alloys, aluminum-calcium alloys, aluminum-magnesium alloys, and graphite thin films. These electrode materials may be used alone or in combination.

  It is also possible to insert an insulating thin film layer between the cathode and the electron injecting and transporting layer for the purpose of improving the electron injection efficiency or preventing defects due to leakage or short circuit.

  Examples of the material used for the insulating layer material include lithium fluoride, lithium oxide, cesium fluoride, cesium oxide, magnesium fluoride, calcium fluoride, calcium oxide, aluminum oxide, aluminum nitride, titanium oxide, silicon oxide, and oxide. Examples thereof include germanium, silicon nitride, boron nitride, molybdenum oxide, ruthenium oxide, vanadium oxide and the like. These may be used alone, or may be used in a mixed system or a stacked system.

  For the cathode, these electrode materials can be formed on the electron injecting and transporting layer by, for example, vapor deposition, sputtering, ion vapor deposition, ion plating, or cluster ion beam.

  The cathode may have a single layer structure or a multilayer structure. The sheet electrical resistance of the cathode is preferably several hundred Ω / □ or less. The thickness of the cathode is usually 5 to 1000 nm, preferably 10 to 500 nm, although it depends on the electrode material used. In order to take out light emitted from the organic electroluminescence device of the present invention with high efficiency, at least one of the anode and the cathode is preferably transparent or translucent, and generally has a transmittance of emitted light of 70% or more. Thus, it is preferable to set the material and thickness of the anode or cathode.

  The organic electroluminescent device of the present invention may contain a singlet oxygen quencher in at least one of the hole injection transport layer, the light emitting layer, and the electron injection transport layer. Although it does not specifically limit as a singlet oxygen quencher, For example, rubrene, a nickel complex, diphenylisobenzofuran is mentioned, Preferably it is rubrene.

  The layer containing the singlet oxygen quencher is not particularly limited, but is preferably a light emitting layer or a hole injection transport layer, and more preferably a hole injection transport layer. When a singlet oxygen quencher is contained in the hole injecting and transporting layer, it may be uniformly contained in the hole injecting and transporting layer, and a layer adjacent to the hole injecting and transporting layer (for example, a light emitting layer, a light emitting function). May be contained in the vicinity of the electron injecting and transporting layer).

  The content of the singlet oxygen quencher is 0.01 to 50% by weight, preferably 0.05 to 30% by weight, based on the total amount constituting the layer to be contained (for example, hole injection transport layer). Preferably, it is 0.1 to 20% by weight.

The formation method of the hole injection transport layer, the light emitting layer, and the electron injection transport layer is not particularly limited. For example, a vacuum deposition method, an ionization deposition method, a solution coating method (for example, a spin coating method, a casting method, A dip coat method, a bar coat method, a roll coat method, a Langmuir-Blodget method, an ink jet method) can be used. When forming each layer such as a hole injecting and transporting layer, a light emitting layer, and an electron injecting and transporting layer by a vacuum deposition method, the conditions for vacuum deposition are not particularly limited, but a vacuum of about 10 ⁻⁴ Pa or less is usually used. Below, it is preferable to carry out at a boating temperature (deposition source temperature) of about 50 to 500 ° C. and a substrate temperature of about −50 to 300 ° C. at a deposition rate of about 0.005 to 50 nm / sec. In this case, each layer such as a hole injecting and transporting layer, a light emitting layer, and an electron injecting and transporting layer is preferably formed continuously under vacuum. It becomes possible to manufacture an organic electroluminescent element excellent in various characteristics by forming continuously. When each layer such as hole injection transport layer, light emitting layer, electron injection transport layer, etc. is formed using a plurality of compounds by vacuum deposition, the temperature of each boat containing the compounds is individually controlled and co-evaporated. It is preferable to do.

  When each layer is formed by a solution coating method, the component forming each layer or the component and a binder resin are dissolved or dispersed in a solvent to obtain a coating solution. Examples of the solvent include organic solvents (hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, ethylbenzene, 1-methylnaphthalene, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dichloromethane, chloroform, and the like. , Halogenated hydrocarbon solvents such as tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, ester solvents such as ethyl acetate, butyl acetate, amyl acetate, ethyl lactate, methanol, propanol, butanol Alcohol solvents such as pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol, dibutyl ether, tetrahydro Ether solvents such as ethylene, dioxane, dimethoxyethane, anisole, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide And polar solvents) and water. A solvent may be used independently and may be used together. When the components of the hole injecting and transporting layer, the light emitting layer, and the electron injecting and transporting layer are dispersed in a solvent, for example, a ball mill, a sand mill, a paint shaker, an attritor, a homogenizer or the like is used as a dispersion method. Can be used.

Examples of binder resins that can be used in each layer such as a hole injecting and transporting layer, a light emitting layer, and an electron injecting and transporting layer include poly-N-vinylcarbazole, polyarylate, polystyrene, polyester, polysiloxane, polymethyl methacrylate, poly Methyl acrylate, polyether, polycarbonate, polyamide, polyimide, polyamideimide, polyparaxylene, polyethylene, polyphenylene oxide, polyethersulfone, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polyphenylene vinylene and derivatives thereof, polyfluorene and derivatives thereof, Examples thereof include polymer compounds such as polythienylene vinylene and its derivatives. Binder resins may be used alone or in combination. The concentration of the coating solution is not particularly limited, but can be set to a concentration range suitable for producing a desired thickness by the coating method to be carried out, usually 0.1 to 50% by weight, preferably 1 to 30% by weight. When a binder resin is used, the amount used is not particularly limited, but it is usually based on the total amount of components and binder resin that form each layer such as a hole injection transport layer, a light emitting layer, and an electron injection transport layer. It is used such that the content of the binder resin is 5 to 99.9% by weight, preferably 10 to 99% by weight (relative to the total amount of each component in the case of forming a single-layer element).
The film pressure of each layer such as the hole injecting and transporting layer, the light emitting layer, and the electron injecting and transporting layer is not particularly limited, but is usually 5 nm to 5 μm.

  The organic electroluminescent device of the present invention produced under the above conditions is provided with a protective layer (sealing layer) for the purpose of preventing contact with oxygen, moisture, etc. For example, it can be protected by enclosing it in paraffin, liquid paraffin, silicon oil, fluorocarbon oil, zeolite-containing fluorocarbon oil). Examples of the material used for the protective layer include organic polymer materials (for example, fluorine resin, epoxy resin, silicone resin, epoxy silicone resin, polystyrene, polyester, polycarbonate, polyamide, polyimide, polyamideimide, polyparaxylene, polyethylene, Polyphenylene oxide), inorganic materials (for example, diamond thin film, amorphous silica, electrically insulating glass, metal oxide, metal nitride, metal carbide, metal sulfide), and photocurable resin. The material used for the protective layer may be used alone or in combination. The protective layer may have a single layer structure or a multilayer structure.

  The organic electroluminescent element of the present invention can also be provided with an interface layer (intermediate layer) on the surface of the anode. Examples of the material for the interface layer include organic phosphorus compounds, polysilanes, aromatic amine derivatives, phthalocyanine derivatives, fluorocarbon polymers, and the like.

Furthermore, the surface of an electrode, for example, an anode, can be used by treating the surface with acid, ammonia / hydrogen peroxide, UV ozone, or plasma.
The organic electroluminescent element of the present invention can be usually used as a DC drive type element, but can also be used as an AC drive type element. Further, the organic electroluminescence device of the present invention may be a segment type, a passive drive type such as a simple matrix drive type, or an active drive type such as a TFT (thin film transistor) type or an MIM (metal-insulator-metal) type. It may be. The driving voltage is usually 2 to 30V. The organic electroluminescent element of the present invention includes a panel-type light source (for example, a backlight for a clock, a liquid crystal panel, etc.), various light-emitting elements (for example, an alternative to a light-emitting element such as an LED), and various display elements [for example, information display Element (PC monitor, mobile phone / mobile terminal display element)], various signs, various sensors, and the like.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to a following example.

Production of Exemplary Compound BA (5) (8) -2 9-Bromo-anthracene 18.7 g (72.7 mmol), 3-biphenylboronic acid 14.4 g (72.7 mmol), Sodium carbonate 8.0 g (75.0 mmol) ), 0.6 g of tetrakis (triphenylphosphine) palladium was added to a mixture of 60 g of toluene and 45 g of water under a nitrogen atmosphere, and the mixture was heated and stirred at 83 ° C. for 6 hours. The reaction mixture was cooled to room temperature and extracted with toluene. The extract was washed with water and saturated brine, and then dried over anhydrous magnesium sulfate. This was concentrated, and the resulting solid was washed with a small amount of toluene, 200 ml of isopropanol was added, and the mixture was heated to reflux. The precipitated solid was collected by filtration and heated sludge with methanol to obtain 21.5 g of 9- (biphenyl-3-yl) -anthracene.

  21.2 g (64.2 mmol) of 9- (biphenyl-3-yl) -anthracene was dissolved in 250 ml of tetrahydrofuran, charged with 11.4 g (64.2 mmol) of N-bromosuccinimide, and reacted at room temperature for 6 hours. . The reaction solution was concentrated, charged with 250 ml of methanol and heated to reflux. After cooling, the residue was collected by filtration to obtain 24.4 g of 9- (biphenyl-3-yl) -10-bromo-anthracene.

  Next, 12.3 g (30 mmol) of 9- (biphenyl-3-yl) -10-bromo-anthracene, 6.6 g (30 mmol) of anthracene-9-boronic acid, 4.1 g (37.5 mmol) of sodium carbonate, 100 ml of toluene Under a nitrogen atmosphere, 0.5 g of tetrakis (triphenylphosphine) palladium was added to a mixture of 5 ml of dimethyl sulfoxide and 33 ml of water, and the mixture was heated and stirred at 83 ° C. for 12 hours. Thereafter, the reaction mixture was cooled to room temperature, and the generated solid was collected by filtration and washed with water, methanol, isopropanol, and toluene in this order to obtain 10- (biphenyl-3-yl) -bianthracene.

  Further, 12.3 g (22.6 mmol) of 10- (biphenyl-3-yl) -bianthracene was suspended in 225 ml of methylene chloride and reacted with 3.98 g (22.6 mmol) of N-bromosuccinimide. After concentration of the reaction solution, 150 ml of methanol was charged, and the residue was collected by filtration to obtain 13.5 g of 9-bromo-10- (biphenyl-3-yl) -bianthracene.

9-bromo-10- (biphenyl-3-yl) bianthracene 11.0 g (18 mmol), 4-dibenzofuranboronic acid 3.9 g (18 mmol), sodium carbonate 2.4 g (22 mmol), toluene 100 ml, dimethyl sulfoxide 5 ml and Under a nitrogen atmosphere, 0.5 g of tetrakis (triphenylphosphine) palladium was added to a mixture consisting of 60 ml of water, and the mixture was heated and stirred at 83 ° C. for 12 hours. The produced solid was collected by filtration, washed with water, methanol, and toluene, and then recrystallized twice from tetralin to obtain 4.1 g of the target compound of the exemplified compound BA (5) (8) -2. Further, this compound was purified by sublimation at 450 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 672 (M ⁺ )
Elemental analysis: calculated (%); C, 92.83; H, 4.79
Analytical value (%); C, 92.4; H, 4.8

Production of Exemplified Compound BA (5) (8) -1 In Example 1, instead of using 14.4 g (72.7 mmol) of 3-biphenylboronic acid, 14.4 g (72.7 mmol) of 2-biphenylboronic acid Except that was used, 3.6 g of the compound of the exemplified compound BA (5) (8) -1 was obtained according to the procedure described in Example 1. Further, this compound was purified by sublimation under conditions of 430 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 672 (M ⁺ )
Elemental analysis: calculated (%); C, 92.83; H, 4.79
Analytical value (%); C, 92.7; H, 4.7

Production of Exemplified Compound BA (6) (9) -1 In 800 ml of tetrahydrofuran, under nitrogen atmosphere, at −60 ° C. or lower, 50 g (194 mmol) of 9-bromophenanthrene and 76.1 ml of 2.55N n-butyllithium hexane solution ( 194 mmol). Next, 45.1 g (388 mmol) of tetramethylethylenediamine (TMEDA) was added and aged. This was transferred into 40.4 g (194 mmol) of anthraquinone suspended in 360 ml of tetrahydrofuran at −40 ° C. or lower, and the temperature was naturally raised to room temperature. 2N hydrochloric acid aqueous solution was added to the reaction solution to stop the reaction, and the organic phase was concentrated. This was washed with water, methanol, isopropanol, and hexane in this order to obtain a pale yellow solid. Furthermore, it wash | cleaned with methyl isobutyl ketone (MIBK), the obtained solid was dissolved in methyl cellosolve, and the insoluble matter was removed. The filtrate was concentrated, and the precipitated pale yellow solid was washed with toluene to obtain 10-hydroxy-10- (9-phenanthryl) anthrone.

  In a nitrogen atmosphere, 30.4 ml (77.5 mmol) of 2.55N n-butyllithium hexane solution was added dropwise to 21.1 g (73.8 mmol) of 9-bromoanthracene in 250 ml of tetrahydrofuran at −60 ° C. or less, and the lithiated form. Was generated. This was transferred to a suspension of 10.00 g (24.6 mmol) of 10-hydroxy-10- (9-phenanthryl) anthrone in 125 ml of tetrahydrofuran at −40 ° C., and the temperature was naturally raised to room temperature. The reaction solution was charged with 67 ml of 2N aqueous hydrochloric acid to stop the reaction, and the precipitated solid was collected by filtration. The residue was washed with water, tetrahydrofuran, methanol, isopropanol, and hexane in this order, and then heated twice with toluene. Washing gave 9,10-bishydroxy-9-anthryl-10-phenanthrylanthracene.

  14.0 g (22.8 mmol) of this anthracene derivative was charged with 300 ml of acetic acid and purged with nitrogen, and then 21 g (94 mmol) of hydroiodic acid was inserted. Subsequently, it was heated and refluxed gently for 1 hour. The reaction solution was cooled and then discharged into 1.5 L of water. The mixture was stirred for 6 hours, and the precipitated solid was collected by filtration. Washing with water, methanol, isopropanol, and hexane in this order yielded 13.5 g of 9-phenanthryl bianthracene.

  Further, 12.0 g (22.6 mmol) of 9-phenanthrylbianthracene was suspended in 225 ml of methylene chloride and reacted with 3.98 g (22.6 mmol) of N-bromosuccinimide. After concentration of the reaction solution, 150 ml of methanol was charged, and the residue was collected by filtration to obtain 12.5 g of 9-bromo-10-phenanthryl-bianthracene.

Dissolved in 13 g of water in a mixed solution of 5.00 g (7.95 mmol) of 9-bromo-10-phenanthrylbianthracene, 3.37 g (15.9 mmol) of 4-dibenzofuranboronic acid, 200 ml of toluene and 10 ml of dimethyl sulfoxide. 2.3 g of sodium carbonate was inserted. After replacing the system with nitrogen, 0.5 g of tetrakistriphenylphosphine palladium complex was inserted, and the mixture was heated to reflux for 4 hours. The organic phase was washed with water, and the organic phase was filtered hot to remove insolubles. This was concentrated and washed with isopropanol. This was recrystallized with tetralin and washed with methyl cellosolve and cyclooctane in this order to obtain 2.8 g of the target compound of the exemplified compound BA (6) (9) -1. Further, this compound was purified by sublimation at 450 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 696 (M ⁺ )
Elemental analysis: calculated value (%); C, 93.08; H, 4.63
Analytical value (%); C, 93.1; H, 4.6

Preparation of Exemplified Compound BA (7) (8) -5 2-iodopyridine 10 g (49 mmol), m-bromophenylboronic acid 9.8 g (49 mmol), sodium hydroxide 2.2 g (54 mmol), toluene 60 g and water 45 g In a nitrogen atmosphere, 0.5 g of tetrakis (triphenylphosphine) palladium was added to the resulting mixture, and the mixture was heated and stirred at 83 ° C. for 6 hours. After cooling, the precipitated solid was collected by filtration and washed with water, isopropanol and toluene to obtain 9.1 g of 1-bromo-3- (2-pyridyl) benzene.

  A sufficiently dried reaction vessel was charged with a small amount of iodine and 1,2-dibromoethane in 0.8 g of magnesium (shaved) and 20 ml of tetrahydrofuran under a nitrogen atmosphere. Next, 9.1 g (39 mmol) of 3- (2-pyridyl) bromobenzene dissolved in 50 ml of tetrahydrofuran was added dropwise, and the mixture was heated to reflux for 3 hours. Next, the reaction solution was cooled to −60 ° C. or lower, and 6 g (104 mmol) of trimethyl boronate dissolved in 50 ml of tetrahydrofuran was added dropwise. Furthermore, after reacting at room temperature for 3 hours, 80 ml of 0.5 N hydrochloric acid aqueous solution was dropped. The reaction was further allowed to proceed at room temperature for 2 hours, and then the organic phase and the aqueous phase were separated. The aqueous phase was extracted with ethyl acetate and combined with the previous organic phase. This was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated. The remaining mass was charged with 5% aqueous sodium hydroxide solution, stirred at room temperature, and insolubles were removed by filtration. The filtrate was adjusted to pH 7-8, and the precipitated solid was collected by filtration. This was dried to obtain 6.0 g of 3- (2-pyridyl) phenylboronic acid.

In Example 1, instead of using 4.3 g (18.5 mmol) of 3-bromobiphenyl, 5.2 g (18.5 mmol) of 1-bromopyrene and 3.9 g (18 mmol) of 4-dibenzofuranboronic acid are used. Instead of the compound of Exemplified Compound BA (7) (8) -5 according to the procedure described in Example 1, except that 3.58 g (18 mmol) of 3- (2-pyridyl) phenylboronic acid was used. 3 g was obtained. Further, this compound was purified by sublimation at 490 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 699 (M ⁺ )
Elemental analysis: calculated value (%); C, 92.67; H, 5.33
Analytical value (%); C, 92.7; H, 5.3

Production of Exemplified Compound BA (7) (9) -1 In 800 ml of tetrahydrofuran, at −60 ° C. or lower in a nitrogen atmosphere, 52.0 g (185 mmol) of 1-bromopyrene and 76.2 ml of 2.55N n-butyllithium hexane solution Reacted with (194 mmol). Next, 25. 1 g (243 mmol) of trimethyl boronate was added, and the temperature was naturally raised to room temperature with stirring. A mixed solution of 22 ml of water and 220 ml of concentrated sulfuric acid was added dropwise thereto to hydrolyze the ester, followed by liquid separation. The organic phase was washed with saturated brine and dried over anhydrous magnesium sulfate. The aqueous phase was extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous magnesium sulfate. All organic phases were combined and concentrated. This was sludged with 50 ml of toluene to obtain 31.9 g of 1-pyrenylboronic acid.

In Example 1, instead of using 14.4 g (72.7 mmol) of 3-biphenylboronic acid, 17.9 g (72.7 mmol) of 1-pyrenylboronic acid was used, and the procedure described in Example 1 was followed. 3.9 g of the compound of Exemplified Compound BA (7) (9) -1 was obtained. Further, this compound was purified by sublimation under conditions of 430 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 720 (M ⁺ )
Elemental analysis: calculated value (%); C, 93.31; H, 4.47
Analytical value (%); C, 93.3; H, 4.5

Production of Exemplified Compound BA (2) (8) -9 1-Bromo-3-iodobenzene 28 g (98 mmol), 1-naphthaleneboronic acid 16.8 g (98 mmol), sodium carbonate 10.2 g (108 mmol), toluene 120 g and Under a nitrogen atmosphere, 0.8 g of tetrakis (triphenylphosphine) palladium was added to a mixture of 90 g of water, and the mixture was heated and stirred at 83 ° C. for 6 hours. After cooling, the precipitated solid was collected by filtration and washed with water, isopropanol, and toluene to obtain 22.2 g of 1-bromo-3- (1-naphthyl) benzene.
A sufficiently dried reaction vessel was charged with a small amount of iodine and 1,2-dibromoethane in 0.8 g of magnesium (shaved) and 20 ml of tetrahydrofuran under a nitrogen atmosphere. Next, 11.0 g (39 mmol) of 1-bromo-3- (1-naphthyl) benzene dissolved in 50 ml of tetrahydrofuran was added dropwise, and the mixture was heated to reflux for 3 hours. Next, the reaction solution was cooled to −60 ° C. or lower, and 6 g (104 mmol) of trimethyl boronate dissolved in 50 ml of tetrahydrofuran was added dropwise. Furthermore, after reacting at room temperature for 3 hours, 80 ml of 0.5 N hydrochloric acid aqueous solution was dropped. The reaction was further allowed to proceed at room temperature for 2 hours, and then the organic phase and the aqueous phase were separated. The aqueous phase was extracted with ethyl acetate and combined with the previous organic phase. This was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated. The remaining mass was charged with 5% aqueous sodium hydroxide solution, stirred at room temperature, and insolubles were removed by filtration. The filtrate was adjusted to pH 7-8, and the precipitated solid was collected by filtration. This was dried to obtain 6.0 g of 3- (1-naphthyl) phenylboronic acid.

In Example 1, instead of using 4.3 g (18.5 mmol) of 3-bromobiphenyl, 4.3 g (18.5 mmol) of 2-bromobiphenyl and 3.9 g (18 mmol) of 4-dibenzofuranboronic acid were used. Instead of using 4- (1-naphthyl) phenylboronic acid 4.46 g (18 mmol), the compound of Exemplified Compound BA (2) (8) -9 was prepared according to the procedure described in Example 1. .5 g was obtained. Further, this compound was purified by sublimation at 490 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 708 (M ⁺ )
Elemental analysis: calculated value (%); C, 94.88; H, 5.12
Analytical value (%); C, 94.9; H, 5.1

Preparation of Exemplified Compound BA (3) (8) -17 In Example 6, instead of using 14 g (49 mmol) of 1-bromo-3-iodobenzene, 14 g (49 mmol) of 1-bromo-2-iodobenzene was used. Instead of using 8.4 g (49 mmol) of 1-naphthaleneboronic acid, according to the procedure described in Example 6 except that 11 g (49 mmol) of 4-dibenzofuranboronic acid was used, 2- (4-dibenzofuranyl) 6.9 g of phenylboronic acid was obtained.

In Example 1, instead of using 3.9 g (18 mmol) of 4-dibenzofuranboronic acid, Example 1 was used except that 5.18 g (18 mmol) of 2- (4-dibenzofuranyl) phenylboronic acid was used. According to the operation described, 4.2 g of the compound of Exemplified Compound BA (3) (8) -17 was obtained. Further, this compound was purified by sublimation at 490 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 748 (M ⁺ )
Elemental analysis: calculated value (%); C, 93.02; H, 4.85
Analytical value (%); C, 93.0; H, 4.8

Production of Exemplified Compound BA (6) (8) -1 Under a nitrogen atmosphere, 24.2 g (57.6 mmol) of 9-bromo-10- (2-biphenyl) anthracene was added in 600 ml of tetrahydrofuran at −50 ° C. or lower. Reaction with 23.7 ml (60.5 mmol) of 55N n-butyllithium hexane solution to form a lithiate, and 6.00 g (15) of 10-hydroxy-10- (9-phenanthryl) anthrone suspended in 150 ml of tetrahydrofuran .4 mmol) at -40 ° C. or lower.

  2N hydrochloric acid aqueous solution was added to the reaction solution to stop the reaction, and the organic phase was concentrated. It was dissolved in toluene and washed with water and saturated saline in this order. The extract was dried over anhydrous magnesium sulfate and treated with activated carbon (ADP), celite, and silica gel. Concentrated and sonicated with hexane and tetrahydrofuran. The precipitated solid was collected by filtration to obtain 9,10-bishydroxy-9- (9 '-(2-biphenyl) anthryl-10'-yl) -10-phenanthryl anthracene.

9.50 g (8.17 mmol) of 9,10-bishydroxy-9- (9 ′-(2-biphenyl) anthryl-10′-yl) -10-phenanthrylanthracene and 150 ml of acetic acid were charged and the atmosphere was replaced with nitrogen. Thereafter, 10 g (40 mmol) of hydroiodic acid was inserted. Next, the mixture was gently heated to reflux for 1 hour, and the reaction solution was cooled and then poured into 750 ml of water. The mixture was stirred for 6 hours, and the precipitated solid was collected by filtration. After washing with water, methanol and isopropanol in this order, the residue was completely dissolved in toluene. This was treated with activated carbon (ADP) and washed with heat in the order of isopropanol and toluene to obtain 3.0 g of the target compound of exemplified compound BA (6) (8) -1. Further, this compound was purified by sublimation at 490 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 682 (M ⁺ )
Elemental analysis: calculated value (%); C, 94.98; H, 5.02
Analytical value (%); C, 94.7; H, 5.0

Production of Exemplified Compound BA (5) (8) -17 In Example 1, instead of using 4.3 g (18.5 mmol) of 3-bromobiphenyl, 4.3 g (18.5 mmol) of 2-bromobiphenyl was used. Exemplified compound BA (5) according to the procedure described in Example 1, except that 4.20 g (18 mmol) of 4-dibenzothiopheneboronic acid was used instead of using 3.9 g (18 mmol) of 4-dibenzofuranboronic acid. 3.9 g of compound (8) -17 was obtained. Further, this compound was purified by sublimation at 450 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 688 (M ⁺ )
Elemental analysis: calculated value (%); C, 90.66; H, 4.68
Analytical value (%); C, 90.6; H, 4.7

Production of Exemplified Compound BA (2) (8) -2 In Example 3, instead of using 50 g (194 mmol) of 9-bromophenanthrene, 45 g (194 mmol) of 4-bromobiphenyl was replaced with 3.37 g of 4-dibenzofuranboronic acid. Instead of using (15.9 mmol), Exemplified Compound BA (2) (8) -2 according to the procedure described in Example 3 except that 3.50 g (15.9 mmol) of 2-biphenylboronic acid was used. 2.4 g of this compound was obtained. Further, this compound was purified by sublimation under conditions of 480 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 658 (M ⁺ )
Elemental analysis: calculated value (%); C, 94.80; H, 5.20
Analytical value (%); C, 94.8; H, 5.2

Production of Exemplified Compound BA (3) (8) -2 In Example 3, instead of using 50 g (194 mmol) of 9-bromophenanthrene, 45 g (194 mmol) of 4-bromobiphenyl was replaced with 3.37 g of 4-dibenzofuranboronic acid. Instead of using (15.9 mmol), according to the procedure described in Example 3, except that 3.50 g (15.9 mmol) of 3-biphenylboronic acid was used, Exemplified Compound BA (3) (8) -2 2.9 g of this compound was obtained. Further, this compound was purified by sublimation under conditions of 480 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 658 (M ⁺ )
Elemental analysis: calculated value (%); C, 94.80; H, 5.20
Analytical value (%); C, 94.8; H, 5.2

Production of Exemplified Compound BA (6) (8) -2 In Example 3, instead of using 3.37 g (15.9 mmol) of 4-dibenzofuranboronic acid, 3.50 g (15.9 mmol) of 3-biphenylboronic acid 2.9 g of Compound of Example Compound BA (6) (8) -2 was obtained according to the procedure described in Example 3 except that was used. Further, this compound was purified by sublimation at 490 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 682 (M ⁺ )
Elemental analysis: calculated value (%); C, 90.98; H, 4.52
Analytical value (%); C, 91.0; H, 4.5

Production of Exemplified Compound BA (6) (8) -3 In Example 3, instead of using 3.37 g (15.9 mmol) of 4-dibenzofuranboronic acid, 3.50 g (15.9 mmol) of 4-biphenylboronic acid The compound of Exemplified Compound BA (6) (8) -3 was obtained in an amount of 3.0 g according to the procedure described in Example 3 except that was used. Further, this compound was purified by sublimation at 490 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 682 (M ⁺ )
Elemental analysis: calculated value (%); C, 90.98; H, 4.52
Analytical value (%); C, 91.0; H, 4.5

Production of Exemplified Compound BA (4) (8) -14 In Example 3, instead of using 50 g (194 mmol) of 9-bromophenanthrene, 45 g (194 mmol) of 4-bromobiphenyl was replaced with 3.37 g of 4-dibenzofuranboronic acid. Example 3 except that instead of using (15.9 mmol), 4.36 g (15.9 mmol) of (1,1 ′: 3 ′, 1 ″ -terphenyl) -3-boronic acid was used. Then, 3.6 g of the compound of Exemplified Compound BA (4) (8) -14 was obtained and further purified by sublimation at 490 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 734 (M ⁺ )
Elemental analysis: calculated value (%); C, 94.79; H, 5.21
Analytical value (%); C, 94.8; H, 5.2

Preparation of Exemplified Compound BA (6) (8) -15 In Example 3, instead of using 3.37 g (15.9 mmol) of 4-dibenzofuranboronic acid, (1,1 ′: 3 ′, 1 ″ -ter Except that 4.36 g (15.9 mmol) of phenyl) -3-boronic acid was used, 4.0 g of the compound of Exemplified Compound BA (6) (8) -15 was obtained according to the procedure described in Example 3. Further, this compound was purified by sublimation at 490 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 758 (M ⁺ )
Elemental analysis: calculated value (%); C, 94.95; H, 5.05
Analytical value (%); C, 94.9; H, 5.1

Production of Exemplified Compound BA (7) (8) -15 In Example 1, instead of using 4.3 g (18.5 mmol) of 3-bromobiphenyl, 5.2 g (18.5 mmol) of 1-bromopyrene was used. -Examples except that instead of using 3.9 g (18 mmol) of dibenzofuranboronic acid, 4.93 g (18 mmol) of (1,1 ': 3', 1 "-terphenyl) -3-boronic acid were used. 4.5 g of the compound of Exemplified Compound BA (7) (8) -15 was obtained according to the operation described in 1. This compound was further purified by sublimation under conditions of 490 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 782 (M ⁺ )
Elemental analysis: calculated (%); C, 95.11; H, 4.89
Analytical value (%); C, 95.1; H, 4.9

Production of Exemplary Compound BA (7) (9) -4 2,8-dibromodibenzothiophene 10.3 g (30 mmol), phenylboronic acid 7.4 g (60 mmol), sodium carbonate 3.7 g (35 mmol), toluene 60 g and water Under a nitrogen atmosphere, 0.5 g of tetrakis (triphenylphosphine) palladium was added to the mixture consisting of 45 g, and the mixture was heated and stirred at 83 ° C. for 6 hours. The reaction mixture was cooled to room temperature and extracted with toluene. The extract was washed with water and saturated brine, and then dried over anhydrous magnesium sulfate. This was concentrated, and the resulting solid was washed with a small amount of toluene, 100 ml of isopropanol was added, and the mixture was heated to reflux. The precipitated solid was collected by filtration and heated and sludged with methanol to obtain 7.5 g of 2,8-diphenyldibenzothiophene.

  7.3 g (21.7 mmol) of 2,8-diphenyldibenzofuran and 200 ml of tetrahydrofuran were charged, and 10 ml (25.5 mmol) of 2.55N n-butyllithium hexane solution was added dropwise at −55 ° C. or lower under a nitrogen atmosphere. Then, the temperature was naturally raised to room temperature. Next, 3.1 g (29 mmol) of trimethyl boronate dissolved in 10 ml of tetrahydrofuran was dropped at −60 ° C. or lower, and the temperature was naturally raised to room temperature.

  To the reaction solution, 2.5 ml of concentrated sulfuric acid diluted with 25 ml of water was added dropwise and reacted for 3 hours. The organic phase was recovered, the aqueous phase was extracted with ethyl acetate, combined with the previous organic phase, and the organic phase was washed with saturated brine three times. After drying over anhydrous magnesium sulfate and concentrating, it was sludged with 100 ml of toluene. The residue was collected by filtration and then rinsed with hexane to obtain 6.8 g of 2,8-diphenyl-4-dibenzothiopheneboronic acid.

In Example 1, instead of using 4.3 g (18.5 mmol) of 3-bromobiphenyl, 5.2 g (18.5 mmol) of 1-bromopyrene and 3.9 g (18 mmol) of 4-dibenzofuranboronic acid are used. Instead of the compound of Exemplified Compound BA (7) (9) -4 according to the procedure described in Example 1, except that 6.8 g (18 mmol) of 2,8-diphenyl-4-dibenzothiopheneboronic acid was used. 3.3 g was obtained. Further, this compound was purified by sublimation at 490 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 889 (M ⁺ )
Elemental analysis: calculated value (%); C, 91.86; H, 4.53
Analytical value (%); C, 91.9; H, 4.5

Production of Exemplified Compound BA (6) (9) -4 In Example 3, instead of using 3.37 g (15.9 mmol) of 4-dibenzofuranboronic acid, 2,8-diphenyl-4-dibenzothiopheneboronic acid 6 Except for using 0.0 g (15.9 mmol), 3.5 g of the compound of Exemplified Compound BA (6) (9) -4 was obtained according to the procedure described in Example 3. Further, this compound was purified by sublimation at 490 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 865 (M ⁺ )
Elemental analysis: calculated value (%); C, 91.63; H, 4.66
Analytical value (%); C, 91.6; H, 4.7

Production of Exemplified Compound BA (7) (9) -10 2,8-dibromodibenzofuran 11.4 g (35 mmol), 9,9-dimethylfluorenyl-2-boronic acid 19.5 g (70 mmol), sodium carbonate 4. Under a nitrogen atmosphere, 0.5 g of tetrakis (triphenylphosphine) palladium was added to a mixture of 3 g (41 mmol), 60 g of toluene and 45 g of water, and the mixture was heated and stirred at 83 ° C. for 6 hours. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration. Washing with water, toluene and methanol gave 14.0 g of 2,8-bis (9,9-dimethylfluoren-2-yl) dibenzofuran.

  2,8-bis (9,9-dimethylfluoren-2-yl) dibenzofuran (14.0 g, 25.4 mmol) and tetrahydrofuran (200 ml) were charged, and the temperature was −55 ° C. or lower, under a nitrogen atmosphere, and 2.55 N 12 ml (29.8 mmol) of butyllithium hexane solution was added dropwise, and the temperature was naturally raised to room temperature. Subsequently, 3.6 g (34 mmol) of trimethyl boronate dissolved in 10 ml of tetrahydrofuran was dropped at −60 ° C. or lower, and the temperature was naturally raised to room temperature.

  To the reaction solution, 2.5 ml of concentrated sulfuric acid diluted with 25 ml of water was added dropwise and reacted for 3 hours. The organic phase was recovered, the aqueous phase was extracted with ethyl acetate, combined with the previous organic phase, and the organic phase was washed with saturated brine three times. After drying over anhydrous magnesium sulfate and concentrating, it was sludged with 100 ml of toluene. The residue was collected by filtration and then rinsed with hexane to obtain 11.8 g of 2,8-bis (9,9-dimethylfluoren-2-yl) -4-dibenzofuranboronic acid.

In Example 1, instead of using 4.3 g (18.5 mmol) of 3-bromobiphenyl, 5.2 g (18.5 mmol) of 1-bromopyrene and 3.9 g (18 mmol) of 4-dibenzofuranboronic acid are used. Instead of the exemplified compound BA according to the procedure described in Example 1, except that 10.7 g (18 mmol) of 2,8-bis (9,9-dimethylfluoren-2-yl) -4-dibenzofuranboronic acid was used. (7) 4.0g of the compound of (9) -10 was obtained. Further, this compound was purified by sublimation at 490 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 1105 (M ⁺ )
Elemental analysis: calculated value (%); C, 93.45; H, 5.11
Analytical value (%); C, 93.4; H, 5.1

Production of Exemplary Compound BA (6) (9) -2 In Example 3, instead of using 3.37 g (15.9 mmol) of 4-dibenzofuranboronic acid, 3.63 g (15.9 mmol) of 4-dibenzothiopheneboronic acid ) Was used according to the procedure described in Example 3 to obtain 2.9 g of the compound of Exemplified Compound BA (6) (9) -2. Further, this compound was purified by sublimation at 450 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 712 (M ⁺ )
Elemental analysis: calculated value (%); C, 94.98; H, 5.02
Analytical value (%); C, 94.8; H, 5.0

Production of Exemplary Compound BA (6) (9) -3 2,8-Dibromodibenzofuran 9.8 g (30 mmol), phenylboronic acid 7.4 g (60 mmol), sodium carbonate 3.7 g (35 mmol), toluene 60 g and water 45 g In a nitrogen atmosphere, 0.5 g of tetrakis (triphenylphosphine) palladium was added to the resulting mixture, and the mixture was heated and stirred at 83 ° C. for 6 hours. The reaction mixture was cooled to room temperature and extracted with toluene. The extract was washed with water and saturated brine, and then dried over anhydrous magnesium sulfate. This was concentrated, and the resulting solid was washed with a small amount of toluene, 100 ml of isopropanol was added, and the mixture was heated to reflux. The precipitated solid was collected by filtration and heated with sludge with methanol to obtain 7.0 g of 2,8-diphenyldibenzofuran.

  7.0 g (21.7 mmol) of 2,8-diphenyldibenzofuran and 200 ml of tetrahydrofuran were charged, and 10 ml (25.5 mmol) of 2.55N n-butyllithium hexane solution was added dropwise at −55 ° C. or lower under a nitrogen atmosphere. Then, the temperature was naturally raised to room temperature. Next, 3.1 g (29 mmol) of trimethyl boronate dissolved in 10 ml of tetrahydrofuran was dropped at −60 ° C. or lower, and the temperature was naturally raised to room temperature.

  To the reaction solution, 2.5 ml of concentrated sulfuric acid diluted with 25 ml of water was added dropwise and reacted for 3 hours. The organic phase was recovered, the aqueous phase was extracted with ethyl acetate, combined with the previous organic phase, and the organic phase was washed with saturated brine three times. After drying over anhydrous magnesium sulfate and concentrating, it was sludged with 100 ml of toluene. The residue was collected by filtration and then rinsed with hexane to obtain 5.8 g of 2,8-diphenyl-4-dibenzofuranboronic acid.

In Example 3, instead of using 3.37 g (15.9 mmol) of 4-dibenzofuranboronic acid, Example 1 was used except that 5.8 g (15.9 mmol) of 2,6,8-triphenyldibenzofuran was used. 5.1 g of the compound of Exemplified Compound BA (6) (9) -3 was obtained. Further, this compound was purified by sublimation under conditions of 470 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 851 (M ⁺ )
Elemental analysis: calculated value (%); C, 93.15; H, 4.97
Analytical value (%); C, 93.2; H, 5.0

Production of Exemplified Compound TA (2) (8) -1 9-bromo-10- (biphenyl-2-yl) bianthracene 18 g (30 mmol), anthracene-9-boronic acid 6.6 g (30 mmol), sodium carbonate 4. Under a nitrogen atmosphere, 0.7 g of tetrakis (triphenylphosphine) palladium was added to a mixture of 1 g (37.5 mmol), 200 ml of toluene, 10 ml of dimethyl sulfoxide and 33 ml of water, and the mixture was heated and stirred at 83 ° C. for 12 hours. Thereafter, the reaction mixture was cooled to room temperature, and the produced solid was collected by filtration and washed with water, methanol, isopropanol, and toluene in this order to obtain 15.4 g of 10- (biphenyl-2-yl) -trianthracene.

  Further, 15.4 g (22.6 mmol) of 10- (biphenyl-2-yl) -trianthracene was suspended in 500 ml of methylene chloride and reacted with 3.98 g (22.6 mmol) of N-bromosuccinimide. After concentration of the reaction solution, 200 ml of methanol was charged, and the residue was collected by filtration to obtain 16.4 g of 9-bromo- (10,9 ': 10', 9 "-trianthryl) -2-biphenyl.

In Example 1, instead of using 11.0 g (18 mmol) of 9-bromo-10- (biphenyl-3-yl) bianthracene, 9-bromo- (10,9 ′: 10 ′, 9 ″ -trianthryl Example 1 except that 13.7 g (18 mmol) of 2-biphenyl was used instead of 3.5 g (18 mmol) of 3-biphenylboronic acid instead of using 3.9 g (18 mmol) of 4-dibenzofuranboronic acid. Then, 3.0 g of the compound of Exemplified Compound TA (2) (8) -1 was obtained by sublimation purification under conditions of 500 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 835 (M ⁺ )
Elemental analysis: calculated value (%); C, 94.93; H, 5.07
Analytical value (%); C, 94.9; H, 5.1

Production of Exemplified Compound TA (3) (8) -18 In Example 22, instead of using 18 g (30 mmol) of 9-bromo-10- (biphenyl-2-yl) bianthracene, 9-bromo-10- ( Biphenyl-2-yl) bianthracene was replaced with 18 g (30 mmol) of (2,6-diphenylpyridin-4-yl) -3-phenylboronic acid 6 instead of using 3.5 g (18 mmol) of 3-biphenylboronic acid. Except that 0.3 g (18 mmol) was used, 5.1 g of the compound of Exemplified Compound TA (3) (8) -18 was obtained according to the procedure described in Example 1. Further, this compound was purified by sublimation at 490 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 988 (M ⁺ )
Elemental analysis: calculated value (%); C, 93.58; H, 5.00
Analytical value (%); C, 93.6; H, 5.0

Production of Exemplified Compound QA (5) (8) -3 In Example 22, instead of using 18 g (30 mmol) of 9-bromo-10- (biphenyl-2-yl) bianthracene, 9-bromo- (10, 9 ′: 10 ′, 9 ″ -trianthryl) -2-biphenyl 22.8 g (30 mmol) instead of using 3.5 g (18 mmol) of 3-biphenylboronic acid 3.5 g of 4-biphenylboronic acid ( 1.9 g of the compound of Exemplified Compound QA (5) (8) -3 was obtained according to the procedure described in Example 1, except that 18 mmol) was used, and this compound was further obtained at 530 ° C. and 1 × 10 ⁻⁴ Pa. Sublimation purification was performed under the conditions of
FD-MS: 1025 (M ⁺ )
Elemental analysis: calculated value (%); C, 93.72; H, 4.72
Analytical value (%); C, 93.7; H, 4.7

Production of Organic Electroluminescent Device A glass substrate having an ITO transparent electrode (anode) having a thickness of 150 nm was washed with a neutral detergent, Semico Clean (manufactured by Furuuchi Chemical), ultrapure water, acetone, and isopropanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, and then fixed to the substrate holder of the vapor deposition apparatus, and the vapor deposition tank was depressurized to 1 × 10 ⁻⁵ Pa. First, on the ITO transparent electrode, copper phthalocyanine was evaporated at a deposition rate of 0.3 nm / sec to a thickness of 20 nm to form a hole injection layer. Next, 4,4′-bis (N-phenyl-N-1 ″ -naphthylamino) -1,1′-biphenyl was deposited to a thickness of 20 nm at a deposition rate of 0.3 nm / sec, and a hole transport layer was formed. Next, as a light emitting layer on the hole injecting and transporting layer, the compound of the exemplified compound BA (5) (8) -2 and the following compound D1 [Chemical Formula 39] were deposited at a deposition rate of 0.3 nm / sec. A light emitting layer was formed by co-evaporation at a thickness of 30 nm from different evaporation sources at 0.03 nm / sec. Further, tris (8-quinolinolato) aluminum was deposited on the light emitting layer at a thickness of 15 nm at a deposition rate of 0.2 nm / sec. Then, an electron injecting and transporting layer was formed, on which lithium fluoride was deposited at a deposition rate of 0.2 nm / sec to a thickness of 0.5 nm, and finally aluminum was deposited as a cathode at a deposition rate of 2.0 nm. 100n at / sec The organic electroluminescence device was fabricated by vapor deposition to a thickness of 1. The deposition was carried out while maintaining the reduced pressure state of the deposition tank, and a DC voltage was applied to the fabricated organic electroluminescence device at room temperature in a dry atmosphere. The device was continuously driven at a constant current density of 50 mA / cm ^2. Initially, the voltage value was 5.4 V, and blue light emission with a luminance of 6300 cd / m ² was confirmed, and the half-life of the luminance was 1980 hours. there were.

Preparation of organic electroluminescent element In Example 19, instead of using the compound of exemplary compound BA (5) (8) -2 in forming the light emitting layer, the compound of exemplary compound BA (5) (8) -1 was used. Except that, an organic electroluminescent element was prepared according to the operation described in Example 19. A DC voltage was applied to the prepared organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 50 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 5.2 V, and blue light emission with a luminance of 6700 cd / m ² was confirmed. The half life of luminance was 2180 hours.

Preparation of organic electroluminescent element In Example 19, the compound of exemplary compound BA (6) (9) -1 was used instead of using the compound of exemplary compound BA (5) (8) -2 at the time of formation of a light emitting layer. Except that, an organic electroluminescent element was prepared according to the operation described in Example 19. A DC voltage was applied to the prepared organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 50 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 5.2 V, and blue light emission with a luminance of 6700 cd / m ² was confirmed. The half life of luminance was 1990 hours.

Preparation of Organic Electroluminescent Device In Example 19, the compound of Exemplified Compound BA (5) (8) -17 was used instead of the compound of Exemplified Compound BA (5) (8) -2 in forming the light emitting layer. Except that, an organic electroluminescent element was prepared according to the operation described in Example 19. A DC voltage was applied to the prepared organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 50 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 5.3 V, and blue light emission with a luminance of 5900 cd / m ² was confirmed. The half life of luminance was 2150 hours.

Preparation of Organic Electroluminescent Device In Example 19, the compound of Exemplified Compound BA (6) (9) -2 was used instead of the compound of Exemplified Compound BA (5) (8) -2 in forming the light emitting layer. Except that, an organic electroluminescent element was prepared according to the operation described in Example 19. A DC voltage was applied to the prepared organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 50 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 4.8 V, and blue light emission with a luminance of 5600 cd / m ² was confirmed. The half life of luminance was 2020 hours.

Preparation of organic electroluminescent device In Example 19, the compound of Exemplified Compound BA (2) (8) -2 was used instead of the compound of Illustrated Compound BA (5) (8) -2 in forming the light emitting layer. Except that, an organic electroluminescent element was prepared according to the operation described in Example 19. A DC voltage was applied to the prepared organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 50 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 5.0 V, and blue light emission with a luminance of 5500 cd / m ² was confirmed. The luminance half-life was 2360 hours.

Preparation of organic electroluminescent device In Example 19, instead of using the compound of exemplary compound BA (5) (8) -2 in forming the light emitting layer, the compound of exemplary compound BA (6) (8) -1 was used. Except that, an organic electroluminescent element was prepared according to the operation described in Example 19. A DC voltage was applied to the prepared organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 50 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 5.2V, and blue light emission with a luminance of 5300 cd / m ² was confirmed. The luminance half-life was 2060 hours.

Preparation of organic electroluminescent element In Example 19, instead of using the compound of the exemplified compound BA (5) (8) -2 in forming the light emitting layer, the compound of the exemplified compound BA (3) (8) -2 was used. Except that, an organic electroluminescent element was prepared according to the operation described in Example 19. A DC voltage was applied to the prepared organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 50 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 4.9 V, and blue light emission with a luminance of 5300 cd / m ² was confirmed. The half life of luminance was 2480 hours.

Preparation of Organic Electroluminescent Device In Example 19, the compound of Exemplified Compound BA (6) (8) -2 was used instead of the compound of Illustrated Compound BA (5) (8) -2 in forming the light emitting layer. Except that, an organic electroluminescent element was prepared according to the operation described in Example 19. A DC voltage was applied to the prepared organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 50 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 5.1 V, and blue light emission with a luminance of 5600 cd / m ² was confirmed. The half life of luminance was 2300 hours.

Preparation of Organic Electroluminescent Device In Example 19, the compound of Exemplified Compound BA (6) (8) -3 was used instead of the compound of Exemplified Compound BA (5) (8) -2 in forming the light emitting layer. Except that, an organic electroluminescent element was prepared according to the operation described in Example 19. A DC voltage was applied to the prepared organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 50 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 5.0 V, and blue light emission with a luminance of 5500 cd / m ² was confirmed. The half life of luminance was 2650 hours.

Preparation of organic electroluminescent element In Example 19, instead of using the compound of exemplary compound BA (5) (8) -2 in forming the light emitting layer, the compound of exemplary compound BA (4) (8) -14 was used. Except that, an organic electroluminescent element was prepared according to the operation described in Example 19. A DC voltage was applied to the prepared organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 50 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 5.3 V, and blue light emission with a luminance of 5600 cd / m ² was confirmed. The half life of luminance was 2500 hours.

Preparation of organic electroluminescent element In Example 19, instead of using the compound of exemplary compound BA (5) (8) -2 in forming the light emitting layer, the compound of exemplary compound BA (6) (8) -15 was used. Except that, an organic electroluminescent element was prepared according to the operation described in Example 19. A DC voltage was applied to the prepared organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 50 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 5.0 V, and blue light emission with a luminance of 5300 cd / m ² was confirmed. The luminance half-life was 2380 hours.

Preparation of organic electroluminescent device In Example 19, the compound of Exemplified Compound BA (3) (8) -17 was used instead of the compound of Illustrated Compound BA (5) (8) -2 in the formation of the light emitting layer. Except that, an organic electroluminescent element was prepared according to the operation described in Example 19. A DC voltage was applied to the prepared organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 50 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 4.9 V, and blue light emission with a luminance of 5600 cd / m ² was confirmed. The half life of luminance was 2080 hours.

Preparation of Organic Electroluminescent Device In Example 19, the compound of Exemplified Compound BA (7) (8) -15 was used instead of the compound of Exemplified Compound BA (5) (8) -2 in forming the light emitting layer. Except that, an organic electroluminescent element was prepared according to the operation described in Example 19. A DC voltage was applied to the prepared organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 50 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 5.1 V, and blue light emission with a luminance of 5600 cd / m ² was confirmed. The half life of luminance was 2460 hours.

Preparation of organic electroluminescent device In Example 19, the compound of Exemplified Compound BA (7) (9) -4 was used instead of the compound of Illustrated Compound BA (5) (8) -2 in forming the light emitting layer. Except that, an organic electroluminescent element was prepared according to the operation described in Example 19. A DC voltage was applied to the prepared organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 50 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 5.0 V, and blue light emission with a luminance of 5600 cd / m ² was confirmed. The luminance half-life was 2280 hours.

Preparation of Organic Electroluminescent Device In Example 19, the compound of Exemplified Compound BA (6) (9) -4 was used instead of the compound of Exemplified Compound BA (5) (8) -2 in forming the light emitting layer. Except that, an organic electroluminescent element was prepared according to the operation described in Example 19. A DC voltage was applied to the prepared organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 50 mA / cm ^{2 in} a dry atmosphere at room temperature. In the initial stage, the voltage value was 5.4 V, and blue light emission with a luminance of 5200 cd / m ² was confirmed. The half life of luminance was 2000 hours.

Preparation of Organic Electroluminescent Device In Example 19, the compound of Exemplified Compound BA (6) (9) -3 was used in place of the compound of Exemplified Compound BA (5) (8) -2 in forming the light emitting layer. Except that, an organic electroluminescent element was prepared according to the operation described in Example 19. A DC voltage was applied to the prepared organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 50 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 5.1 V, and blue light emission with a luminance of 5600 cd / m ² was confirmed. The luminance half-life was 2350 hours.

Preparation of organic electroluminescent element In Example 19, instead of using the compound of exemplary compound BA (5) (8) -2 in forming the light emitting layer, the compound of exemplary compound TA (2) (8) -1 was used. Except that, an organic electroluminescent element was prepared according to the operation described in Example 19. A DC voltage was applied to the prepared organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 50 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 5.1 V, and blue light emission with a luminance of 5500 cd / m ² was confirmed. The half life of luminance was 2230 hours.

Comparative Example 1:
Preparation of Organic Electroluminescent Device For comparison, in Example 19, instead of using the compound of the exemplified compound BA (5) (8) -2 in forming the light emitting layer, the following compound (H1) [Chemical Formula 37] was used. An organic electroluminescent element was prepared according to the procedure described in Example 19 except that it was used. A DC voltage was applied to the prepared organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 50 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 5.4 V and light emission with a luminance of 1800 cd / m ² was observed, but the light emission color was green. In addition, a short circuit occurred in 12 hours during continuous driving, and it was impossible to measure the half-value of luminance.

Comparative Example 2:
For comparison, in Example 19, except that the following compound (H2) [Chem. 38] was used instead of the compound of Exemplified Compound BA (5) (8) -2 in the formation of the light emitting layer. An organic electroluminescent device was prepared according to the procedure described in Example 19. A DC voltage was applied to the prepared organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 50 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 5.6 V, and blue light emission with a luminance of 3600 cd / m ² was observed. The half value of luminance was as short as 310 hours.

Comparative Example 3:
For comparison, in Example 19, except that the following compound (H3) [Chemical Formula 39] was used instead of the compound of the exemplified compound BA (5) (8) -2 in forming the light emitting layer. An organic electroluminescent device was prepared according to the procedure described in Example 19. A DC voltage was applied to the prepared organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 50 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 5.6 V, and blue-green light emission with a luminance of 4500 cd / m ² was observed. The half value of luminance was as short as 42 hours.

Comparative Example 4:
For comparison, in Example 19, except that the following compound (H4) [Chemical Formula 40] was used instead of the compound of Exemplary Compound BA (5) (8) -2 in the formation of the light emitting layer. An organic electroluminescent device was prepared according to the procedure described in Example 19. A DC voltage was applied to the prepared organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 50 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 5.6 V, and blue-green light emission with a luminance of 3400 cd / m ² was observed. The half value of luminance was as short as 112 hours.

Comparative Example 5:
For comparison, in Example 19, except that the following compound (H5) [Chem. 41] was used instead of the compound of the exemplified compound BA (5) (8) -2 in the formation of the light emitting layer. An organic electroluminescent device was prepared according to the procedure described in Example 19. A DC voltage was applied to the prepared organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 50 mA / cm ^{2 in} a dry atmosphere at room temperature. The voltage value was 5.3 V, and blue light emission with a luminance of 4800 cd / m ² was observed. The half value of luminance was as short as 1000 hours.

Production of Organic Electroluminescent Device A glass substrate having an ITO transparent electrode (anode) having a thickness of 150 nm was washed with a neutral detergent, Semico Clean (manufactured by Furuuchi Chemical), ultrapure water, acetone, and isopropanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, and then fixed to the substrate holder of the vapor deposition apparatus, and the vapor deposition tank was depressurized to 1 × 10 ⁻⁵ Pa. First, 4,4 ′, 4 ″ -tris [N- (3 ″ -methylphenyl) -N-phenylamino] triphenylamine is deposited on an ITO transparent electrode at a deposition rate of 0.1 nm / sec and a thickness of 50 nm. To form a hole injection layer. Next, 4,4′-bis [N-phenyl-N- (1-naphthyl) amino] was deposited to a thickness of 20 nm at a deposition rate of 0.2 nm / sec to form a hole transport layer. Furthermore, the compound represented by the exemplified compound BA (2) (8) -2 and the compound represented by the exemplified compound BA (3) (8) -2 are further converted to 0.2 nm / sec and 0.2 nm / sec. A light emitting layer was formed by co-evaporation to a thickness of 40 nm from different evaporation sources. Next, tris (8-quinolinolato) aluminum was vapor-deposited thereon to a thickness of 50 nm at a vapor deposition rate of 0.2 nm / sec to form an electron injecting and transporting layer. Further, magnesium and silver were co-deposited as a cathode at a deposition rate of 0.2 nm / sec to a thickness of 200 nm (weight ratio 10: 1) to form an organic electroluminescent device. A DC voltage was applied to the produced organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 50 mA / cm ² in a dry atmosphere. Initially, blue light emission of 5.4 V and luminance of 2450 cd / m ² was confirmed. The half life of luminance was 950 hours.

Production of Organic Electroluminescent Device A glass substrate having an ITO transparent electrode (anode) having a thickness of 150 nm was washed with a neutral detergent, Semico Clean (manufactured by Furuuchi Chemical), ultrapure water, acetone, and isopropanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, and then fixed to the substrate holder of the vapor deposition apparatus, and the vapor deposition tank was depressurized to 1 × 10 ⁻⁵ Pa. First, poly (thiophene-2,5-diyl) was deposited on the ITO transparent electrode at a deposition rate of 0.1 nm / sec to a thickness of 20 nm to form a first hole injection transport layer. After returning a vapor deposition tank to atmospheric pressure, the vapor deposition tank was pressure-reduced to 1 * 10 < ^-5 > Pa again. Next, the compound of Exemplified Compound BA (6) (9) -1 and rubrene were co-evaporated from different vapor deposition sources to a thickness of 55 nm at a vapor deposition rate of 0.2 nm / sec (weight ratio 10: 1). A light emitting layer having a hole injecting and transporting layer was formed. Next, while maintaining the reduced pressure state, tris (8-quinolinolato) aluminum was deposited thereon to a thickness of 50 nm at a deposition rate of 0.2 nm / sec to form an electron injecting and transporting layer. While maintaining the reduced pressure state, magnesium and silver were further co-deposited as a cathode to a thickness of 200 nm at a deposition rate of 0.2 nm / sec (weight ratio 10: 1) to form a cathode, and an organic electroluminescent device Was made. A DC voltage was applied to the produced organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 50 mA / cm ² in a dry atmosphere. Initially, yellow light emission of 5.5 V and luminance of 5800 cd / m ² was confirmed. This element had a luminance decrease of 10% or less even after 1000 hours.

Preparation of organic electroluminescent element In Example 38, instead of using the compound of the exemplified compound BA (5) (8) -2 in forming the light emitting layer, the compound of the exemplified compound BA (5) (8) -1 was used. Except that, an organic electroluminescent element was produced according to the operation described in Example 38. A DC voltage was applied to the produced organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 50 mA / cm ² in a dry atmosphere. Initially, yellow light emission of 5.4 V and luminance of 5600 cd / m ² was confirmed. This element had a luminance decrease of 10% or less even after 1000 hours.

Preparation of organic electroluminescence device In Example 38, instead of using the compound of the exemplified compound BA (5) (8) -2 in forming the light emitting layer, the compound of the exemplified compound BA (6) (8) -2 was used. Except that, an organic electroluminescent element was produced according to the operation described in Example 38. A DC voltage was applied to the produced organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 50 mA / cm ² in a dry atmosphere. Initially, yellow light emission of 5.8 V and luminance of 5700 cd / m ² was confirmed. This element had a luminance decrease of 10% or less even after 1000 hours.

According to the present invention, it has become possible to provide a novel anthracene compound and an organic electroluminescence device having a long emission lifetime, excellent durability, and high emission efficiency.

It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element.

Explanation of symbols

1: substrate 2: anode 3: hole injection transport layer 3a: hole injection transport component 4: light emitting layer 4a: light emission component 5: electron injection transport layer 5 ": electron injection transport layer 5a: electron injection transport component 6: cathode 7: Power supply

Claims (7)

An anthracene compound represented by the following general formula (1 ) .

[In the formula, A is a group represented by the following general formulas (2) to (7), B is a group represented by the following general formula (8) or (9), and A and B are the same. do not do. n is 2 .

(In the formulas (2) to (7),
R _{21 to} R ₂₉ , R ₃₁ , R ₃₂ , R _{34 to} R ₃₉ , R _{41 to} R ₄₉ , R _{51 to} R ₅₇ , R _{61 to} R ₆₉ and R _{71 to} R ₇₉ are each independently a hydrogen atom or a halogen atom , A cyano group, a nitro group, a substituted or unsubstituted amino group, a substituted or unsubstituted ester group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear or branched chain having 1 to 10 carbon atoms, Cyclic alkoxy group, substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms, substituted or unsubstituted aryl group having 4 to 20 carbon atoms, or carbon number 4 to 20 substituted or unsubstituted aryloxy groups,
R ₃₃ is a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted amino group, a substituted or unsubstituted ester group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or a carbon number 1-10 linear, branched or cyclic alkoxy groups, C7-20 substituted or unsubstituted aralkyl groups, C7-20 substituted or unsubstituted aralkyloxy groups, or C4-20 carbon atoms A substituted or unsubstituted aryloxy group,
X ₅ represents an oxygen atom or a sulfur atom.
However, R ₄₄ and R ₄₅ or R ₄₁ and R ₄₉ are not connected to form a ring. )

_{(Wherein, Y 1 ~Y 5, Y 6} ~Y 12 are each independently a hydrogen atom, a substituted (excluding a vinyl group) or unsubstituted aryl group consisting of 5 to 36 carbon atoms, _{X 9} is oxygen Represents an atom or sulfur atom.)] An organic electroluminescence device comprising at least one layer containing at least one anthracene compound represented by the general formula (1) according to claim 1 between a pair of electrodes. The organic electroluminescent element according to claim 2 , wherein the layer containing the anthracene compound represented by the general formula (1) is a light emitting layer. The organic electroluminescence device according to claim 2 , wherein the layer containing the anthracene compound represented by the general formula (1) is a hole injection transport layer. The organic electroluminescent element according to claim 3, wherein the light emitting layer is formed of a host material and a dopant material, and an anthracene compound represented by the general formula (1) is contained as the light emitting layer host material. The organic electroluminescent element according to any one of claims 2 to 5 , further comprising a hole injecting and transporting layer between the pair of electrodes. The organic electroluminescent element according to any one of claims 2 to 6 , further comprising an electron injecting and transporting layer between the pair of electrodes.

Images