JP5927875B2 - Amine compounds and uses thereof - Google Patents

Description

  The present invention relates to a novel amine compound and an organic EL device using the same.

An organic EL element is a surface-emitting element in which an organic thin film is held between a pair of electrodes, and has features such as a thin and light weight, a high viewing angle, and a high-speed response, and is expected to be applied to various display elements. . Recently, some practical applications such as mobile phone displays have begun. An organic EL element is an element that utilizes light emitted when holes injected from an anode and electrons injected from a cathode are recombined in a light emitting layer, and has a structure of a hole transport layer, a light emitting layer A multi-layer laminate type in which an electron transport layer and the like are laminated is the mainstream. Here, the charge transport layer such as the hole transport layer and the electron transport layer does not emit light by itself, but facilitates the injection of charges into the light emitting layer, and the charge injected into the light emitting layer or the light emitting layer. It plays the role of confining the energy of the generated excitons.
Therefore, the charge transport layer is very important for lowering the driving voltage and improving the light emission efficiency of the organic EL element.

  As the hole transport material, an amine compound having an appropriate ionization potential and hole transport ability is used. For example, 4,4′-bis [N- (1-naphthyl) -N-phenyl] biphenyl (hereinafter referred to as NPD). Is abbreviated). However, the driving voltage, light emission efficiency and durability of an element using NPD for the hole transport layer are not sufficient, and development of new materials is required. Furthermore, in recent years, an organic EL element using a phosphorescent material for a light emitting layer has been developed, and a hole transport material having a high triplet level is required for an element using phosphorescent light emission. NPD is not sufficient from the point of triplet level, and for example, it has been reported that the organic EL element in which a phosphorescent material having green light emission and NPD are combined reduces the luminous efficiency (for example, non-patent Reference 1).

Against this background, recently, amine compounds having a carbazole ring introduced in the molecule have been reported. An amine compound having a carbazole ring introduced is a useful molecular skeleton because it has a higher triplet level than NPD and is excellent in hole transportability, but many of the compounds reported so far are A 3-aminocarbazole compound in which an amino group is introduced at the 3-position of the carbazole ring (see, for example, Patent Documents 1 and 2). Since the 3-position of the carbazole ring is the para-position of the nitrogen atom that is an electron donor property, the amino group substituted at the 3-position is activated by the nitrogen atom of the carbazole ring. That is, the ionization potential of the 3-aminocarbazole compound is lower than that of a normal amine compound. Therefore, when the 3-aminocarbazole compounds reported so far are used for the hole transport layer, there is a problem that the hole injection barrier to the light emitting layer is increased and the driving voltage of the organic EL element is increased. .

From the above background, there is a possibility that the amino group has an appropriate ionization potential when bonded to the 2-position of the carbazole ring. With respect to compounds in which the 2-position of the carbazole ring is substituted with an amino group, 2-ditolylaminocarbazoles are exemplified as charge transport materials in electrophotographic photoreceptors (see, for example, Patent Document 3). However, the exemplified compounds have a low glass transition temperature, and when used in an organic EL device, there is a problem in durability at high temperature driving. In addition, 7-phenyl-2-aminocarbazole compounds are also disclosed as materials for organic electronic devices (see, for example, Patent Document 4). However, the compound described in Patent Document 4 in which the phenyl group is substituted at the 7-position of the carbazole ring, which is the para-position of the amino group, has a small molecular energy gap due to the wide conjugation of pi electrons, and the triplet level Is also low. Therefore, sufficient luminous efficiency cannot be obtained with an element combined with a phosphorescent material having green emission.

  Further, it has been reported that the durability of the element is improved by doping the hole transport layer with a dopant capable of accepting electrons (see, for example, Non-Patent Document 2). When driving an organic EL device, a phenomenon occurs in which electrons that have not recombined with holes in the light-emitting layer are injected into the hole transport layer, so that the irreversible amine compound accompanying the injection of electrons into the hole transport layer Reduction is considered as one of the deterioration factors of the element.

JP 2006-28176 A JP 2006-298898 A JP 2003-316035 A International Publication 2006/108497 Pamphlet

Journal of Applied Physics, 2004, 95, 7798. Japan Journal of Applied Physics, 1995, 34, L824

  An object of the present invention is to provide an amine compound suitable for a hole transport material of an organic EL device, and further an organic EL device having high luminous efficiency and excellent durability.

  As a result of intensive studies, the present inventors have found that an amine compound represented by the following general formula (1) is excellent in hole transport properties and has an electron-accepting stability in an organic EL device using the compound in a hole transport layer. Has found that the driving voltage is low, and that the luminous efficiency and durability are excellent, and the present invention has been completed. That is, the present invention relates to general formula (1)

(In the formula, Ar represents a substituent having 1 to 36 carbon atoms or an aryl group having 6 to 30 carbon atoms which may have a halogen atom. A and B are each independently substituted having 1 to 36 carbon atoms. Represents a heteroaryl group having 3 to 20 carbon atoms and having at least one C═N bond which may have a group or a halogen atom, and X ¹ and X ² each independently represent a carbon atom or a nitrogen atom. R ¹ , R ² and R ^{4 to} R ⁷ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic group having 1 to 18 carbon atoms. An alkoxy group having 1 to 36 carbon atoms, an aryl group having 6 to 30 carbon atoms which may have a halogen atom, or a substituent having 1 to 36 carbon atoms or a halogen atom. Represents a heteroaryl group having 4 to 20 carbon atoms R ³ is a hydrogen atom, a halogen atom, a straight chain of 1 to 18 carbon atoms, branched or cyclic alkyl group, or a straight-chain having 1 to 18 carbon atoms, .R ⁸ and ^{R 9} represents a branched or cyclic alkoxy group Each independently a halogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or a substituent or halogen having 1 to 36 carbon atoms Represents an aryl group having 6 to 30 carbon atoms which may have an atom, and m and n each independently represents an integer of 0 or 1 [provided that m + n is 1 or 2]; Each independently represents an integer of 0-4.)
It is related with the amine compound represented by these, and its use.

  Hereinafter, the present invention will be described in detail.

  In the amine compound represented by the general formula (1) of the present invention, Ar represents a substituent having 1 to 36 carbon atoms or an aryl group having 6 to 30 carbon atoms which may have a halogen atom.

  In the aryl group having 6 to 30 carbon atoms which may have a substituent having 1 to 36 carbon atoms or a halogen atom represented by Ar, the aryl group having 6 to 30 carbon atoms is not particularly limited. Phenyl group, biphenylyl group, terphenyl group, naphthyl group, fluorenyl group, phenanthryl group, benzofluorenyl group, dibenzofluorenyl group, fluoranthenyl group, pyrenyl group, chrysenyl group, perylenyl group, picenyl group, etc. Examples of the substituent or halogen atom having 1 to 36 carbon atoms include linear, branched or cyclic alkyl groups, linear, branched or cyclic alkoxy groups, aryloxy groups, trialkylsilyl groups, and triaryls. Examples include silyl group, 9-carbazolyl group, fluorine, chlorine, bromine, and iodine. There is no particular limitation on the number.

  Examples of linear, branched or cyclic alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl and stearyl. Examples thereof include, but are not limited to, a group, a trichloromethyl group, a trifluoromethyl group, a cyclopropyl group, and a cyclohexyl group.

  Linear, branched or cyclic alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, stearyloxy Examples of the group include, but are not limited to, groups.

  Examples of the aryloxy group include a phenoxy group, a 4-methylphenyloxy group, a 3-methylphenyloxy group, a 4-biphenyloxy group, a 3-biphenyloxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group. However, it is not limited to these.

  Examples of the trialkylsilyl group include, but are not limited to, a trimethylsilyl group, a triethylsilyl group, and a tributylsilyl group.

  As triarylsilyl group, triphenylsilyl group, tri (4-methylphenyl) silyl group, tri (3-methylphenyl) silyl group, tri (4-methylphenyl) silyl group, tri (4-biphenyl) silyl group However, the present invention is not limited to these examples.

  Specific examples of Ar include phenyl 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, 4-tert-butylphenyl group, 4-n- Pentylphenyl group, 4-isopentylphenyl group, 4-neopentylphenyl group, 4-n-hexylphenyl group, 4-n-octylphenyl group, 4-n-decylphenyl group, 4-n-dodecylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 4-tritylphenyl group, 3-tritylphenyl group, -Triphenylsilylphenyl group, 3-triphenylsilylphenyl 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, 2,3,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxy Phenyl group, 4-ethoxyphenyl group, 3-ethoxyphenyl group, 2-ethoxyphenyl group, 4-n-propoxyphenyl group, 3-n-propoxyphenyl group, 4-isopropoxyphenyl group, 2-isopropoxyphenyl group 4-n-butoxyphenyl group, 4-isobutoxyphenyl group, 2-sec-butoxyphenyl group, 4- -Pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2-isopentyloxyphenyl group, 4-neopentyloxyphenyl group, 2-neopentyloxyphenyl group, 4-n-hexyloxyphenyl group, 2- ( 2-ethylbutyl) oxyphenyl group, 4-n-octyloxyphenyl group, 4-n-decyloxyphenyl group, 4-n-dodecyloxyphenyl group, 4-n-tetradecyloxyphenyl group, 4-cyclohexyloxyphenyl Group, 2-cyclohexyloxyphenyl group, 4-phenoxyphenyl group, 2-methyl-4-methoxyphenyl group, 2-methyl-5-methoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3-methyl-5 -Methoxyphenyl group, 3-ethyl-5-methoxyphenyl group, 2-methoxy Ci-4-methylphenyl group, 3-methoxy-4-methylphenyl 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-ethoxyphenyl group, 2-methoxy-6-ethoxyphenyl group, 3 , 4,5-trimethoxyphenyl group, 4- (9-carbazolyl) phenyl group, 3- (9-carbazolyl) phenyl group, 4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 2, 3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 3,4-diph Orophenyl group, 3,5-difluorophenyl group, 4- (1-naphthyl) phenyl group, 4- (2-naphthyl) phenyl group, 3- (1-naphthyl) phenyl group, 3- (2-naphthyl) phenyl group 1-naphthyl group, 2-naphthyl group, 4-methyl-1-naphthyl group, 6-methyl-2-naphthyl group, 4-phenyl-1-naphthyl group, 6-phenyl-2-naphthyl group, 2-anthryl Group, 9-anthryl group, 10-phenyl-9-anthryl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, 9,9-diethyl-2-fluorenyl group, 9,9-di-n -Propyl-2-fluorenyl group, 9,9-di-n-octyl-2-fluorenyl group, 9,9-diphenyl-2-fluorenyl group, 9,9'-spirobifluorenyl group, 9-phena Tolyl group, 2-phenanthryl group, benzofluorenyl group, dibenzofluorenyl group, fluoranthenyl group, pyrenyl group, chrysenyl group, perylenyl group, picenyl group, 4-biphenylyl group, 3-biphenylyl group, 2-biphenylyl group Group, p-terphenyl group, m-terphenyl group, o-terphenyl group and the like can be exemplified, but are not limited thereto.

  In the amine compound represented by the general formula (1), Ar has a high glass transition temperature and preferably has a triplet level higher than that of a phosphorescent material having green emission, and therefore Ar has 1 to 36 carbon atoms. Or a 4-biphenylyl group, a 3-biphenylyl group, an m-terphenyl group, a 4- (9-carbazolyl) phenyl group, or a 2-fluorenyl group, which may have a substituent or a halogen atom.

  In the amine compound represented by the general formula (1), A and B are each independently a substituent having 1 to 36 carbon atoms or a carbon number having at least one C═N bond optionally having a halogen atom. Represents 3-20 heteroaryl groups.

  In the heteroaryl group having 3 to 20 carbon atoms having at least one C═N bond which may have a substituent having 1 to 36 carbon atoms or a halogen atom represented by A and B, at least one C═N The heteroaryl group having 3 to 20 carbon atoms having a bond is not particularly limited as long as it has an electron accepting property and is stable to reduction. For example, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group Group, isoxazolyl group, pyridyl group, pyrimidyl group, pyrazyl group, 1,3,5-triazyl group, benzoimidazolyl group, indazolyl group, benzothiazolyl group, benzoisothiazolyl group, 2,1,3-benzothiadiazolyl group, Benzoxazolyl group, benzoisoxazolyl group, 2,1,3-benzooxadiazolyl group, quinolyl , An isoquinolyl group, a quinoxalyl group, a quinazolyl group, an acridinyl group, a 1,10-phenanthroyl group, and the like. The substituent or halogen atom having 1 to 36 carbon atoms is not particularly limited, but the Ar And a substituent having 1 to 36 carbon atoms or a halogen atom exemplified in the above.

  Specific examples of A and B include 1-imidazolyl group, 2-phenyl-1-imidazolyl group, 2-phenyl-3,4-dimethyl-1-imidazolyl group, 2,3,4-triphenyl-1-imidazolyl. Group, 2- (2-naphthyl) -3,4-dimethyl-1-imidazolyl group, 2- (2-naphthyl) -3,4-diphenyl-1-imidazolyl group, 1-methyl-2-imidazolyl group, 1 -Ethyl-2-imidazolyl group, 1-phenyl-2-imidazolyl group, 1-methyl-4-phenyl-2-imidazolyl group, 1-methyl-4,5-dimethyl-2-imidazolyl group, 1-methyl-4 , 5-diphenyl-2-imidazolyl group, 1-phenyl-4,5-dimethyl-2-imidazolyl group, 1-phenyl-4,5-diphenyl-2-imidazolyl group, 1-phenyl- , 5-Dibiphenylyl-2-imidazolyl group, 1-methyl-3-pyrazolyl group, 1-phenyl-3-pyrazolyl group, 1-methyl-4-pyrazolyl group, 1-phenyl-4-pyrazolyl group, 1-methyl- 5-pyrazolyl group, 1-phenyl-5-pyrazolyl group, 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, 2-oxazolyl group, 4 -Oxazolyl group, 5-oxazolyl group, 3-isoxazolyl group, 4-isoxazolyl group, 5-isoxazolyl group, 2-pyridyl group, 3-methyl-2-pyridyl group, 4-methyl-2-pyridyl group, 5-methyl 2-pyridyl group, 6-methyl-2-pyridyl group, 3-pyridyl group, 4-methyl-3-pyridyl group, 4-pyridyl group 2-pyrimidyl group, 5-pyrimidyl group, pyrazyl group, 1,3,5-triazyl group, 4,6-diphenyl-1,3,5-triazin-2-yl group, 1-benzimidazolyl group, 2-methyl -1-Benzimidazolyl group, 2-phenyl-1-benzimidazolyl group, 1-methyl-2-benzoimidazolyl group, 1-phenyl-2-benzimidazolyl group, 1-methyl-5-benzimidazolyl group, 1,2-dimethyl-5 Benzimidazolyl group, 1-methyl-2-phenyl-5-benzimidazolyl group, 1-phenyl-5-benzoimidazolyl group, 1,2-diphenyl-5-benzimidazolyl group, 1-methyl-6-benzimidazolyl group, 1,2-dimethyl -6-Benzimidazolyl group, 1-methyl-2-phenyl-6-benzimidazolyl group 1-phenyl-6-benzimidazolyl group, 1,2-diphenyl-6-benzimidazolyl group, 1-methyl-3-indazolyl group, 1-phenyl-3-indazolyl group, 2-benzothiazolyl group, 4-benzothiazolyl group, 5 -Benzothiazolyl group, 6-benzothiazolyl group, 7-benzothiazolyl group, 3-benzoisothiazolyl group, 4-benzoisothiazolyl group, 5-benzisothiazolyl group, 6-benzoisothiazolyl group, 7-benzoisothialyl group Azolyl group, 2,1,3-benzothiadiazolyl-4-yl group, 2,1,3-benzothiadiazolyl-5-yl group, 2-benzoxazolyl group, 4-benzoxazolyl group Group, 5-benzoxazolyl group, 6-benzoxazolyl group, 7-benzoxazolyl group, 3-benzisoxazolyl group, -Benzoisoxazolyl group, 5-benzoisoxazolyl group, 6-benzoisoxazolyl group, 7-benzisoxazolyl group, 2,1,3-benzoxoxadiazolyl-4-yl group 2,1,3-benzooxadiazolyl-5-yl group, 2-quinolyl group, 3-quinolyl group, 5-quinolyl group, 6-quinolyl group, 1-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group Group, 2-quinoxalyl group, 3-phenyl-2-quinoxalyl group, 6-quinoxalyl group, 2,3-dimethyl-6-quinoxalyl group, 2,3-diphenyl-6-quinoxalyl group, 2-quinazolyl group, 4- Examples thereof include quinazolyl group, 2-acridinyl group, 9-acridinyl group, 1,10-phenanthroline-3-yl group, 1,10-phenanthroline-5-yl group and the like. That, without being limited thereto.

  In the amine compound represented by the general formula (1), A and B each independently have a substituent having 1 to 36 carbon atoms or a halogen atom from the viewpoint of high stability against reduction and high heat resistance. It may preferably be a substituent selected from an imidazolyl group, a thiazolyl group, a pyridyl group, a pyrimidyl group, a pyrazyl group, a 1,3,5-triazyl group, a benzoimidazolyl group, a benzothiazolyl group, or a quinoxalyl group.

In the amine compound represented by the general formula (1), X ¹ and X ² each independently represent a carbon atom or a nitrogen atom.

In the amine compound represented by the general formula (1), R ¹ , R ² and R ^{4 to} R ⁷ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. , A C1-C18 linear, branched or cyclic alkoxy group, a C1-C36 substituent, or a C6-C30 aryl group optionally having a halogen atom, or C1-C36 Or a heteroaryl group having 4 to 20 carbon atoms which may have a substituent or a halogen atom.

Examples of the halogen atom represented by R ¹ , R ² and R ^{4 to} R ⁷ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Specific examples of the linear, branched or cyclic alkyl group having 1 to 18 carbon atoms represented by R ¹ , R ² and R ^{4 to} R ⁷ include a methyl group, an ethyl group, a propyl group, an isopropyl group, and butyl. Group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, stearyl group, trichloromethyl group, trifluoromethyl group, cyclopropyl group, cyclohexyl group and the like. However, it is not limited to these.

Specific examples of the linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms represented by R ¹ , R ² and R ^{4 to} R ⁷ include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, Examples thereof include, but are not limited to, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, and a stearyloxy group.

The substituent having 1 to 36 carbon atoms represented by R ¹ , R ² and R ^{4 to} R ⁷ or the aryl group having 6 to 30 carbon atoms which may have a halogen atom is not particularly limited. And C1-C36 aryl groups optionally having a substituent having 1 to 36 carbon atoms or a halogen atom exemplified for Ar.

In the heteroaryl group having 4 to 20 carbon atoms which may have a substituent having 1 to 36 carbon atoms or a halogen atom represented by R ¹ , R ² and R ^{4 to} R ⁷ , hetero atoms having 4 to 20 carbon atoms The aryl group is an aromatic group containing at least one hetero atom among an oxygen atom, a nitrogen atom, and a sulfur atom, and is not particularly limited. For example, a 2-pyridyl group, a 3-pyridyl group, 4 -Pyridyl group, 3-quinolyl group, 4-quinolyl group, 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 2-oxazolyl group, 2-thiazolyl group, 2-benzoxazolyl Group, 2-benzothiazolyl group, 2-benzothiophenyl group, 3-benzothiophenyl group, 2-benzimidazolyl group, 2-dibenzothiophenyl group, 3-dibenzothiophenyl group, 2 A dibenzofuranyl group, a 3-dibenzofuranyl group, and the like can be exemplified, and the substituent or halogen atom having 1 to 36 carbon atoms is not particularly limited. There may be mentioned 36 substituents or halogen atoms.

In the amine compound represented by the general formula (1), R ³ is a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a linear, branched or cyclic group having 1 to 18 carbon atoms. Represents a cyclic alkoxy group.

Examples of the halogen atom represented by R ³ , a straight-chain, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a straight-chain, branched or cyclic alkoxy group having 1 to 18 carbon atoms are the above R ¹ and R ² , respectively. And a halogen atom exemplified as R ^{4 to} R ⁷ , a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms.

In the amine compound represented by the general formula (1), R ⁸ and R ⁹ are each independently a halogen atom, a straight chain having 1 to 18 carbon atoms, a branched or cyclic alkyl group, or a straight chain having 1 to 18 carbon atoms. Represents a branched or cyclic alkoxy group, or a substituent having 1 to 36 carbon atoms or an aryl group having 6 to 30 carbon atoms which may have a halogen atom.

As the halogen atom represented by R ⁸ and R ⁹ , a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, respectively, R ¹ , R ² and the halogen atoms exemplified for R ^{4 to} R ⁷ , a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms. .

The aryl group having 6 to 30 carbon atoms which may have a substituent having 1 to 36 carbon atoms or a halogen atom represented by R ⁸ and R ⁹ is not particularly limited, but is exemplified by Ar. Examples thereof include a substituent having 1 to 36 carbon atoms or an aryl group having 6 to 30 carbon atoms which may have a halogen atom.

  In the amine compound represented by the general formula (1), m and n each independently represents an integer of 0 or 1. However, m + n is 1 or 2.

  In the amine compound represented by the general formula (1), p and q each independently represents an integer of 0 to 4.

  Preferred compounds are illustrated below, but are not limited to these compounds.

  The amine compound represented by the general formula (1) can be synthesized, for example, by a known method (Tetrahedron Letters, 1998, Vol. 39, page 2367). Specifically, it can be synthesized by the following route.

  (Route a) 9H-carbazole compound halogenated at 2-position and a halogenated aromatic compound in the presence of a base using a copper catalyst or a palladium catalyst (2-halogenated-9-substituted) Carbazole) is reacted with a secondary amine compound in the presence of a base using a copper catalyst or a palladium catalyst.

  (Route b) Product obtained by reacting 9H-carbazole compound halogenated at the 2-position with a halogenated aromatic compound using a copper catalyst or a palladium catalyst in the presence of a base (2-halogenated-9-substituted) Carbazole) is reacted with a primary amine compound in the presence of a base using a copper catalyst or a palladium catalyst to obtain a secondary amine. Further, the obtained secondary amine is reacted with a halogenated aromatic compound in the presence of a base using a copper catalyst or a palladium catalyst.

  The amine compound represented by the general formula (1) of the present invention can be used as a light emitting layer, a hole transport layer or a hole injection layer of an organic EL device.

In particular, since the amine compound represented by the general formula (1) is excellent in hole transport ability, when used as a hole transport layer and / or a hole injection layer, the driving voltage of the organic EL device is reduced. Thus, it is possible to achieve high luminous efficiency and improved durability. In addition, the amine compound represented by the general formula (1) has a high triplet level as compared with a conventional material, so that it is high not only in a fluorescent material but also in an element using a phosphorescent material in a light emitting layer. Luminous efficiency can be obtained.

  In the light emitting layer when the amine compound represented by the general formula (1) is used as a hole injection layer and / or a hole transport layer of an organic EL device, a known fluorescent or phosphorescent light emitting material that has been conventionally used is used. Material can be used. The light emitting layer may be formed of only one kind of light emitting material, or one or more kinds of light emitting materials may be doped in the host material.

  When forming the hole injection layer and / or hole transport layer made of the amine compound represented by the general formula (1), two or more kinds of materials may be contained or laminated as necessary. For example, oxides such as molybdenum oxide, 7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, hexacyanohexahexa A known electron-accepting material such as azatriphenylene may be contained or laminated.

  When the amine compound represented by the general formula (1) is used as the light emitting layer of the organic EL device, the amine compound is used alone, used by doping a known light emitting host material, or a known light emitting dopant. Can be used by doping.

  As a method for forming a hole injection layer, a hole transport layer, or a light emitting layer containing the amine compound represented by the general formula (1), for example, a known method such as a vacuum deposition method, a spin coating method, or a casting method is used. The method can be applied.

  The amine compound represented by the general formula (1) according to the present invention has a higher hole transport capability than conventional materials and has an electron accepting stability. Durability can be improved.

The cyclic voltammetry measurement result of the compound (A59) obtained in Example 15 is shown.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited by these Examples.

¹ H-NMR and ¹³ C-NMR measurements were performed using Gemini 200 manufactured by Varian.

  The FDMS measurement was performed using Hitachi M-80B.

  The reduction characteristics were evaluated by cyclic voltammetry using HA-501 and HB-104 manufactured by Hokuto Denko.

  The light emission characteristics of the organic EL element were evaluated by applying a direct current to the produced element and using a luminance meter of LUMINANCEMETER (BM-9) manufactured by TOPCON.

Synthesis Example 1 (Synthesis of 2- (4-chlorophenyl) nitrobenzene [see the following formula (2)])
In a 500 mL three-neck flask under a nitrogen stream, o-bromonitrobenzene 25.0 g (123.0 mmol), p-chlorophenylboronic acid 21.1 g (135.3 mmol), tetrakis (triphenylphosphine) palladium 0.71 g (0. 61 mmol), 100 mL of tetrahydrofuran, 162 g of a 20 wt% aqueous sodium carbonate solution (307.5 mmol as sodium carbonate) were added, and the mixture was heated to reflux for 8 hours. After cooling to room temperature, the aqueous layer and the organic layer were separated, and the organic layer was washed with a saturated aqueous ammonium chloride solution and further washed with a saturated aqueous sodium chloride solution. The organic phase was dried over anhydrous magnesium sulfate, the solution from which insolubles were removed by filtration was concentrated under reduced pressure, the residue was purified by silica gel column chromatography (toluene), and 27.2 g of 2- (4-chlorophenyl) nitrobenzene was obtained. Isolated (94% yield).

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.

¹ H-NMR (CDCl ₃ ) δ (ppm); 7.87 (d, 1H), 7.36-7.66 (m, 5H), 7.21-7.27 (m, 2H)
¹³ C-NMR (CDCl ₃ ) δ (ppm); 148.98, 135.85, 135.12, 134.37, 132.45, 131.79, 129.23, 128.84, 128.53, 124 .21
Synthesis Example 2 (Synthesis of 2-chlorocarbazole [see the following formula (2)])
Under a nitrogen stream, a 200 mL eggplant-shaped flask was charged with 10.0 g (42.7 mmol) of 2- (4-chlorophenyl) nitrobenzene obtained in Synthesis Example 1, 50 mL of triethyl phosphite was added, and then the mixture was heated at 150 ° C. for 24 hours. Stir for hours. Triethyl phosphite was distilled off under reduced pressure, and 5.1 g (25.6 mmol) of 2-chlorocarbazole white powder was isolated by adding o-xylene to the residue and recrystallizing (yield 60%). ).

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.

¹ H-NMR (Acetone-d ₆ ) δ (ppm); 10.46 (br-s, 1H), 8.10 (d, 2H), 7.37-7.55 (m, 3H), 7. 15-7.24 (m, 2H)
¹³ C-NMR (acetone-d ₆ ) δ (ppm); 141.35, 141.15, 131.33, 126.70, 123.17, 122.64, 121.92, 120.84, 120.09 119.78, 111.811, 111.43

Synthesis Example 3 (Synthesis of 2-chloro-N- (4-biphenylyl) carbazole)
In a 50 mL three-necked flask under a nitrogen stream, 4.0 g (19.8 mmol) of 2-chlorocarbazole obtained in Synthesis Example 2, 5.5 g (23.7 mmol) of 4-bromobiphenyl, 3.83 g of potassium carbonate (27. 7 mmol) and 20 mL of o-xylene were added, and 44 mg (0.19 mmol) of palladium acetate and 0.14 g (0.69 mmol) of tri (tert-butyl) phosphine were added to the slurry reaction solution, followed by stirring at 130 ° C. for 24 hours. did. After cooling to room temperature, the deposited precipitate was collected by filtration, and the resulting solid was washed with water and further washed with methanol. After drying under reduced pressure, recrystallization from n-butanol isolated 4.9 g (13.8 mmol) of white powder of 2-chloro-N- (4-biphenylyl) carbazole (yield 69%).

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.

¹ H-NMR (CDCl ₃ ) δ (ppm); 8.07 (d, 1H), 8.00 (d, 1H), 7.77 (d, 2H), 7.65 (d, 2H), 7 .54 (d, 2H), 7.21-7.41 (m, 8H)
¹³ C-NMR (CDCl ₃ ) δ (ppm); 141.38, 141.18, 140.72, 140.08, 136.17, 131.75, 128.99, 128.66, 127.74, 127 .27, 127.16, 126.23, 122.82, 121.99, 121.19, 120.47, 120.29, 110.05, 109.98
Synthesis Example 4 (Synthesis of N-phenyl-N- (2- (N- (4-biphenylyl)) carbazolyl) amine)
In a 100 mL three-necked flask under a nitrogen stream, 9.5 g (26.8 mmol) of 2-chloro-N- (4-biphenylyl) carbazole obtained in Synthesis Example 3; 3.7 g (40.2 mmol) of aniline, sodium-tert -Butoxide 3.6 g (37.5 mmol) and o-xylene 60 mL were added, and palladium acetate 60 mg (0.26 mmol) and tri (tert-butyl) phosphine 189 mg (0.93 mmol) were added to the slurry reaction solution. Stir at 130 ° C. for 10 hours. After cooling to room temperature, 35 mL of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the organic layer was washed with pure water and then washed with a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate, and the solution from which insolubles were removed by filtration was concentrated under reduced pressure to obtain a brown solid. Recrystallized from o-xylene, 8.0 g (19.4 mmol) of white powder of N-phenyl-N- (2- (N- (4-biphenylyl)) carbazolyl) amine was isolated (yield 72%) .

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.

¹ H-NMR (CDCl ₃ ) δ (ppm); 7.95-8.04 (m, 2H), 7.74 (d, 2H), 7.18-7.66 (m, 12H), 6. 99-7.12 (m, 4H), 6.87 (t, 1H), 5.77 (br, 1H)
¹³ C-NMR (CDCl ₃ ) δ (ppm); 143.62, 142.19, 141.73, 141.02, 140.21, 136.79, 129.37, 128.95, 128.49, 127 63, 127.23, 127.14, 124.79, 123.77, 121.11, 120.71, 120.12, 119.45, 118.00, 117.27, 112.38, 109.63 , 99.03
Synthesis Example 5 (Synthesis of 2- (4-bromophenyl) -4,5-diphenyl-1H-imidazole)
To a 200 mL three-necked flask, 10 g (54.0 mmol) of 4-bromobenzaldehyde, 11.3 g (54.0 mmol) of diphenylethanedione, 20.8 g (270.2 mmol) of ammonium acetate, and 100 mL of acetic acid were added, and 110 ° C. for 12 hours. Stir. After cooling to room temperature, the reaction solution was added to 200 mL of water. The precipitated white powder was collected by filtration, washed with water, and further washed with methanol, whereby 20.0 g (53.53 g) of white powder of 2- (4-bromophenyl) -4,5-diphenyl-1H-imidazole was obtained. 4 mmol) (yield 98%).

  The compound was identified by FDMS.

FDMS (m / z); 374 (M +)
Synthesis Example 6 (Synthesis of 1-methyl-2- (4-bromophenyl) -4,5-diphenyl-imidazole)
In a 100 mL three-necked flask, 10 g (26.7 mmol) of 2- (4-bromophenyl) -4,5-diphenyl-1H-imidazole obtained in Synthesis Example 5, 4.1 g (29.3 mmol) of iodomethane, benzyltriethylammonium 8.1 g (29.3 mmol) of chloride, 2.4 g of 48% strength sodium hydroxide aqueous solution (1.15 g as a sodium hydroxide solid) and 40 mL of dimethyl sulfoxide were added and stirred at 70 ° C. for 3 hours. After cooling to room temperature, 40 mL of water was added to the reaction solution. The precipitated white powder was collected by filtration, washed with water, and further washed with methanol, whereby 8.2 g of 1-methyl-2- (4-bromophenyl) -4,5-diphenyl-imidazole white powder ( 21.9 mmol) (yield 81%).

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.

¹ H-NMR (CDCl ₃ ) δ (ppm); 7.61 (s, 4H), 7.13-7.54 (m, 10 H), 3.47 (s, 3H) ¹³ C-NMR (CDCl ₃ ) Δ (ppm); 146.66, 137.94, 134.39, 131.73, 130.89, 130.78, 130.43, 129.79, 129.04, 128.66, 128.09, 126.88, 126.41, 123.02, 33.29
Synthesis Example 7 (Synthesis of 1-methyl-2- (4-bromophenyl) benzimidazole)
In a 50 mL three-neck flask, 2 g (7.3 mmol) of 2- (4-bromophenyl) -1H-benzimidazole, 1.1 g (8.0 mmol) of iodomethane, 2.2 g (8.0 mmol) of benzyltriethylammonium chloride, 48 A 0.6% aqueous sodium hydroxide solution (0.29 g as a sodium hydroxide solid) and 10 mL of dimethyl sulfoxide were added, and the mixture was stirred at 70 ° C. for 5 hours. After cooling to room temperature, 10 mL of water was added to the reaction solution. The precipitated white powder was collected by filtration, washed with water, and further washed with methanol to obtain 1.4 g (5.1 mmol) of white powder of 1-methyl-2- (4-bromophenyl) benzimidazole. (Yield 70%).

  The compound was identified by FDMS.

FDMS (m / z); 286 (M +)
Synthesis Example 8 (Synthesis of 1- (4-bromophenyl) -2-phenylbenzimidazole)
Under a nitrogen stream, in a 100 mL three-necked flask, 3.0 g (15.4 mmol) of 2-phenyl-1H-benzimidazole, 8.6 g (30.8 mmol) of p-bromoiodobenzene, 0.58 g of copper iodide (3. 0 mmol), 10.0 g (30.8 mmol) of cesium carbonate, and 30 mL of dimethylformamide were added, and the mixture was stirred at room temperature for 30 minutes. Then, it stirred at 120 degreeC for 36 hours. After cooling to room temperature, 50 mL of ethyl acetate was added, and insoluble matters were filtered. The filtrate was washed with water and further washed with saturated brine, and then concentrated under reduced pressure to obtain a residue. The residue was purified by silica gel column chromatography, and 1.7 g (4.9 mmol) of white powder of 1- (4-bromophenyl) -2-phenylbenzimidazole was isolated (yield 32%).

  The compound was identified by FDMS.

FDMS (m / z); 348 (M +)
Example 1 (Synthesis of Compound (A2))
In a 200 mL three-necked flask under a nitrogen stream, 7.8 g (39.0 mmol) of 2-chlorocarbazole obtained in Synthesis Example 2, 9.0 g (39.0 mmol) of 4- (2-pyridyl) bromobenzene, potassium carbonate 7 0.5 g (54.6 mmol) and 75 mL of o-xylene were added, and 87 mg (0.39 mmol) of palladium acetate and 275 mg (1.3 mmol) of tri (tert-butyl) phosphine were added to the slurry reaction solution at 130 ° C. Stir for 15 hours. After cooling to room temperature, 30 mL of water was added and the organic layer was separated. The organic layer was washed with water and further washed with saturated brine, dried over anhydrous magnesium sulfate, and filtered to remove insolubles. The solution obtained by filtration was charged into a 200 mL three-necked flask. To the solution, 12.5 g (39.0 mmol) of N, N-bis (4-biphenylyl) amine, 5.2 g (54.6 mmol) of sodium-tert-butoxide, 87 mg (0.39 mmol) of palladium acetate, tri (tert- (Butyl) phosphine (275 mg, 1.36 mmol) was added and the mixture was stirred at 130 ° C. for 8 hours. After cooling to room temperature, 30 mL of water was added. The deposited precipitate was collected by filtration, and the obtained precipitate was washed with water and further washed with ethanol. After drying under reduced pressure, it was recrystallized from o-xylene to isolate 17.9 g (28.0 mmol) of white powder of compound (A2) (yield 72%).

The compound was identified by FDMS, ¹ H-NMR measurement, and ¹³ C-NMR measurement.

FDMS (m / z); 639 (M +)
¹ H-NMR (CDCl ₃ ) δ (ppm); 8.63 (d, 1H), 8.13 (d, 2H), 8.05 (d, 2H), 7.73 (d, 2H), 7 .54-7.62 (m, 6H), 7.10-7.49 (m, 20H)
¹³ C-NMR (CDCl ₃ ) δ (ppm); 156.38, 149.70, 147.26, 146.02, 141.66, 141.18, 140.60, 138.23, 138.09, 136 88, 134.96, 128.69, 128.42, 127.72, 126.92, 126.73, 126.62, 125.47, 123.64, 123.44, 122.34, 121.13 120.56, 120.36, 119.94, 119.85, 119.03, 109.80, 106.92.
Example 2 (Synthesis of Compound (A45))
In a 100 mL three-necked flask under a nitrogen stream, 3.2 g (16.0 mmol) of 2-chlorocarbazole obtained in Synthesis Example 2 and 1-methyl-2- (4-bromophenyl) -4, obtained in Synthesis Example 6 were obtained. 6.0 g (16.0 mmol) of 5-diphenyl-imidazole, 3.1 g (22.4 mmol) of potassium carbonate, and 40 mL of o-xylene were added, and 35 mg (0.16 mmol) of palladium acetate was added to the slurry reaction solution. -Butyl) phosphine 113 mg (0.56 mmol) was added and stirred at 130 ° C. for 20 hours. After cooling to room temperature, 20 mL of water was added and the organic layer was separated. The organic layer was washed with water and further washed with saturated brine, dried over anhydrous magnesium sulfate, and filtered to remove insolubles. The solution obtained by filtration was charged into a 100 mL three-necked flask. To the solution, 4.1 g (16.0 mmol) of N- (4-biphenylyl) -N- (p-tolyl) amine, 2.1 g (22.4 mmol) of sodium tert-butoxide, 35 mg (0.16 mmol) of palladium acetate Then, 113 mg (0.56 mmol) of tri (tert-butyl) phosphine was added and stirred at 130 ° C. for 4 hours. After cooling to room temperature, 20 mL of water was added. The deposited precipitate was collected by filtration, and the resulting precipitate was washed with water and further washed with ethanol. After drying under reduced pressure, recrystallization from o-xylene was performed to isolate 7.90 g (10.8 mmol) of a pale yellow powder of compound (A45) (yield 68%).

  The compound was identified by FDMS.

FDMS (m / z); 732 (M +)
Example 3 (Synthesis of Compound (A52))
In a 200 mL three-necked flask under a nitrogen stream, 5.0 g (24.7 mmol) of 2-chlorocarbazole obtained in Synthesis Example 2 and 1-methyl-2- (4-bromophenyl) benzimidazole obtained in Synthesis Example 7 7 0.0 g (24.7 mmol), 4.8 g (34.7 mmol) of potassium carbonate, and 75 mL of o-xylene are added, and 55 mg (0.24 mmol) of palladium acetate and 174 mg of tri (tert-butyl) phosphine are added to the slurry reaction solution. 0.86 mmol) was added and stirred at 130 ° C. for 18 hours. After cooling to room temperature, 30 mL of water was added and the organic layer was separated. The organic layer was washed with water, further washed with saturated brine, dried over anhydrous magnesium sulfate, and insolubles were removed by filtration. The solution obtained by filtration was charged into a 200 mL three-necked flask. To the solution, 7.9 g (24.7 mmol) of N, N-bis (4-biphenylyl) amine, 3.3 g (34.5 mmol) of sodium-tert-butoxide, 55 mg (0.24 mmol) of palladium acetate, tri (tert- 174 mg (0.86 mmol) of butyl) phosphine was added and stirred at 130 ° C. for 5 hours. After cooling to room temperature, 30 mL of water was added. The deposited precipitate was collected by filtration, and the obtained precipitate was washed with water and further washed with ethanol. After drying under reduced pressure, recrystallization from o-xylene was performed to isolate 10.2 g (14.8 mmol) of a pale yellow powder of compound (A52) (yield 60%).

  The compound was identified by FDMS.

FDMS (m / z); 692 (M +)
Example 4 (Synthesis of Compound (A57))
In a 50 mL three-necked flask under a nitrogen stream, 2.0 g (7.2 mmol) of 2-chlorocarbazole obtained in Synthesis Example 2 and 1- (4-bromophenyl) -2-phenylbenzimidazole obtained in Synthesis Example 8 2 0.5 g (7.2 mmol), 1.4 g (10.1 mmol) of potassium carbonate and 20 mL of o-xylene were added, and 16 mg (0.07 mmol) of palladium acetate and 49 mg of tri (tert-butyl) phosphine were added to the slurry reaction solution. 0.24 mmol) was added and stirred at 130 ° C. for 18 hours. After cooling to room temperature, 10 mL of water was added and the organic layer was separated. The organic layer was washed with water, further washed with saturated brine, dried over anhydrous magnesium sulfate, and insolubles were removed by filtration. The solution obtained by filtration was charged into a 50 mL three-necked flask. To the solution, 1.8 g (7.2 mmol) of N- (4-biphenylyl) -N- (p-tolyl) amine, 968 mg (10.1 mmol) of sodium tert-butoxide, 16 mg (0.07 mmol) of palladium acetate, 49 mg (0.24 mmol) of (tert-butyl) phosphine was added and stirred at 130 ° C. for 6 hours. After cooling to room temperature, 10 mL of water was added. The deposited precipitate was collected by filtration, and the obtained precipitate was washed with water and further washed with ethanol. After drying under reduced pressure, it was recrystallized from o-xylene to isolate 3.2 g (4.7 mmol) of white powder of compound (A57) (yield 66%).

  The compound was identified by FDMS.

FDMS (m / z); 692 (M +)
Example 5 (Synthesis of Compound (A59))
Under a nitrogen stream, in a 100 mL three-necked flask, 6.9 g (34.4 mmol) of 2-chlorocarbazole obtained in Synthesis Example 2, 10.0 g (34.4 mmol) of 4- (2-benzothiazolyl) bromobenzene, potassium carbonate 6 .6 g (48.1 mmol) and o-xylene 60 mL were added, and 77 mg (0.34 mmol) of palladium acetate and 243 mg (1.2 mmol) of tri (tert-butyl) phosphine were added to the slurry reaction solution at 130 ° C. Stir for 20 hours. After cooling to room temperature, 30 mL of water was added and the organic layer was separated. The organic layer was washed with water, further washed with saturated brine, dried over anhydrous magnesium sulfate, and insolubles were removed by filtration. The solution obtained by filtration was charged into a 50 mL three-necked flask. To the solution, 11.0 g (34.4 mmol) of N, N-bis (4-biphenylyl) amine, 4.6 g (48.1 mmol) of sodium-tert-butoxide, 77 mg (0.34 mmol) of palladium acetate, tri (tert- 243 mg (1.2 mmol) of butyl) phosphine was added and stirred at 130 ° C. for 5 hours. After cooling to room temperature, 20 mL of water was added. The deposited precipitate was collected by filtration, and the obtained precipitate was washed with water and further washed with ethanol. After drying under reduced pressure, recrystallization from o-xylene was performed to isolate 18.8 g (27.1 mmol) of a pale yellow powder of compound (A59) (yield 79%). The compound was identified by FDMS.

FDMS (m / z); 695 (M +)
Example 6 (Synthesis of Compound (B3))
N-phenyl-N- (2- (N- (4-biphenylyl)) carbazolyl) amine 3.0 g (7.3 mmol), 4- (2) obtained in Synthesis Example 4 was placed in a 50 mL three-necked flask under a nitrogen stream. -Pyridyl) bromobenzene 1.7 g (7.3 mmol), sodium-tert-butoxide 0.98 g (10.2 mmol), o-xylene 15 mL were added, and the slurry reaction solution was added with palladium acetate 16 mg (0.07 mmol), 49 mg (0.24 mmol) of tri (tert-butyl) phosphine was added and stirred at 130 ° C. for 5 hours. After cooling to room temperature, 10 mL of water was added and the organic layer was separated. The organic layer was washed with water, further washed with saturated brine, dried over anhydrous magnesium sulfate, and the solution from which insoluble materials were removed by filtration was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane), and 3.4 g (6.2 mmol) of a glassy solid of compound (B3) was isolated (yield 85%).

  The compound was identified by FDMS.

FDMS (m / z); 563 (M +)
Example 7 (Synthesis of Compound (B10))
In a 50 mL three-necked flask under a nitrogen stream, 0.90 g (2.2 mmol) of N-phenyl-N- (2- (N- (4-biphenylyl)) carbazolyl) amine obtained in Synthesis Example 4 was used. 0.62 g (2.2 mmol) of 1-methyl-2- (4-bromophenyl) benzimidazole obtained, 0.28 g (3.0 mmol) of sodium-tert-butoxide, and 10 mL of o-xylene were added to form a slurry reaction. To the solution, 5 mg (0.02 mmol) of palladium acetate and 14 mg (0.07 mmol) of tri (tert-butyl) phosphine were added and stirred at 130 ° C. for 5 hours. After cooling to room temperature, 5 mL of water was added and the organic layer was separated. The organic layer was washed with water, further washed with saturated brine, dried over anhydrous magnesium sulfate, and insolubles were removed by filtration. The solution obtained by filtration was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane), and 0.92 g (1.5 mmol) of a glassy solid of compound (B10) was isolated (yield 72%).

  The compound was identified by FDMS.

FDMS (m / z); 616 (M +)
Example 8 (Synthesis of Compound (B13))
In a 50 mL three-neck flask under a nitrogen stream, 0.82 g (2.0 mmol) of N-phenyl-N- (2- (N- (4-biphenylyl)) carbazolyl) amine obtained in Synthesis Example 4 was used. 0.69 g (2.0 mmol) of 1- (4-bromophenyl) -2-phenylbenzimidazole obtained, 0.27 g (2.8 mmol) of sodium-tert-butoxide and 10 mL of o-xylene were added, and the reaction in a slurry state To the solution, 5 mg (0.02 mmol) of palladium acetate and 14 mg (0.07 mmol) of tri (tert-butyl) phosphine were added and stirred at 130 ° C. for 5 hours. After cooling to room temperature, 5 mL of water was added and the organic layer was separated. The organic layer was washed with water, further washed with saturated brine, dried over anhydrous magnesium sulfate, and insolubles were removed by filtration. The solution obtained by filtration was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane), and 0.82 g (1.2 mmol) of a glassy solid of compound (B13) was isolated (yield 60%).

  The compound was identified by FDMS.

FDMS (m / z); 678 (M +)
Example 9 (Synthesis of Compound (B14))
In a 50 mL three-necked flask under a nitrogen stream, 1.5 g (3.6 mmol) of N-phenyl-N- (2- (N- (4-biphenylyl)) carbazolyl) amine obtained in Synthesis Example 4 was used. Obtained 1-methyl-2- (4-bromophenyl) -4,5-diphenyl-imidazole 1.3 g (3.6 mmol), sodium tert-butoxide 0.48 g (5.0 mmol), o-xylene 15 mL. In addition, 7 mg (0.03 mmol) of palladium acetate and 21 mg (0.10 mmol) of tri (tert-butyl) phosphine were added to the slurry reaction solution, and the mixture was stirred at 130 ° C. for 7 hours. After cooling to room temperature, 10 mL of water was added and the organic layer was separated. The organic layer was washed with water, washed with saturated brine, dried over anhydrous magnesium sulfate, and insolubles were removed by filtration. The solution obtained by filtration was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane), and 2.0 g (2.8 mmol) of a glassy solid of compound (B14) was isolated (yield 79%).

  The compound was identified by FDMS.

FDMS (m / z); 718 (M +)
Example 10 (Synthesis of Compound (B19))
In a 50 mL three-necked flask under a nitrogen stream, 3.7 g (9.0 mmol) of 4-N2 (N-phenyl-N- (2- (N- (4-biphenylyl)) carbazolyl) amine obtained in Synthesis Example 4 was obtained. -Benzothiazolyl) bromobenzene 2.6 g (9.0 mmol), sodium-tert-butoxide 1.2 g (12.6 mmol), o-xylene 25 mL were added, and 20 mg (0.09 mmol) of palladium acetate was added to the slurry reaction solution. Tri (tert-butyl) phosphine 63 mg (0.31 mmol) was added, and the mixture was stirred at 130 ° C. for 5 hours. After cooling to room temperature, 10 mL of water was added and the organic layer was separated. The organic layer was washed with water, further washed with saturated brine, dried over anhydrous magnesium sulfate, and insolubles were removed by filtration. The solution obtained by filtration was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane), and 4.5 g (7.3 mmol) of a glassy solid of compound (B19) was isolated (yield 82%).

  The compound was identified by FDMS.

FDMS (m / z); 619 (M +)
Example 11 (Reduction characteristic evaluation of compound (A2))
Compound (A2) was dissolved at a concentration of 0.001 mol / L in an anhydrous tetrahydrofuran solution having a tetrabutylammonium perchlorate concentration of 0.1 mol / L, and the reduction potential was measured by cyclic voltammetry. Glassy carbon was used for the working electrode, platinum wire was used for the counter electrode, and silver wire immersed in an acetonitrile solution of AgNO ₃ was used for the reference electrode. Compound (A2) has a concentration of -2.88 V vs. ferrocene based on the redox potential of ferrocene. Reduction waves were observed in Fc / Fc ⁺ , confirming electron acceptability.

Example 12 (Reduction characteristic evaluation of compound (A45))
In Example 11, except that the compound (A45) was used instead of the compound (A2), the reduction characteristics were evaluated by the same method as in Example 11. As a result, the compound (A45) was determined based on the oxidation-reduction potential of ferrocene. -2.98V vs. Reduction waves were observed in Fc / Fc ⁺ , confirming electron acceptability.

Example 13 (Reduction characteristic evaluation of compound (A52))
In Example 11, except that the compound (A52) was used instead of the compound (A2), the reduction characteristics were evaluated by the same method as in Example 11. As a result, the compound (A52) was based on the oxidation-reduction potential of ferrocene. -2.93V vs. Reduction waves were observed in Fc / Fc ⁺ , confirming electron acceptability.

Example 14 (Reduction characteristic evaluation of compound (A57))
In Example 11, except that the compound (A57) was used instead of the compound (A2), the reduction characteristics were evaluated by the same method as in Example 11. As a result, the compound (A57) was based on the oxidation-reduction potential of ferrocene. -2.95V vs. Reduction waves were observed in Fc / Fc ⁺ , confirming electron acceptability.

Example 15 (Reduction characteristic evaluation of compound (A59))
In Example 11, except that the compound (A59) was used instead of the compound (A2), the reduction characteristics were evaluated by the same method as in Example 11. As a result, the compound (A59) was based on the oxidation-reduction potential of ferrocene. -2.48V vs.. Reduction waves were observed in Fc / Fc ⁺ , confirming electron acceptability. The results of cyclic voltammetry measurement are shown in FIG.

Example 16 (Reduction characteristic evaluation of compound (B3))
In Example 11, except that the compound (B3) was used instead of the compound (A2), the reduction characteristics were evaluated by the same method as in Example 11. As a result, the compound (B3) was based on the oxidation-reduction potential of ferrocene. -3.08V vs. Reduction waves were observed in Fc / Fc ⁺ , confirming electron acceptability.

Example 17 (Reduction characteristic evaluation of compound (B13))
In Example 11, except that the compound (B13) was used instead of the compound (A2), the reduction characteristics were evaluated by the same method as in Example 11. As a result, the compound (B13) was based on the oxidation-reduction potential of ferrocene. -3.15 V vs. Reduction waves were observed in Fc / Fc ⁺ , confirming electron acceptability.

Example 18 (Reduction characteristic evaluation of compound (B14))
In Example 11, except that the compound (B14) was used instead of the compound (A2), the reduction characteristics were evaluated by the same method as in Example 11. As a result, the compound (B14) was based on the oxidation-reduction potential of ferrocene. -3.18V vs. Reduction waves were observed in Fc / Fc ⁺ , confirming electron acceptability.

Example 19 (Reduction characteristic evaluation of compound (B19))
In Example 11, except that the compound (B19) was used instead of the compound (A2), the reduction characteristics were evaluated by the same method as in Example 11. As a result, the compound (B19) was based on the oxidation-reduction potential of ferrocene. -2.75V vs. Reduction waves were observed in Fc / Fc ⁺ , confirming electron acceptability.

Comparative Example 1 (Reduction characteristic evaluation of comparative compound (a))
In Example 11, except that the compound (a) was used in place of the compound (A2), the reduction characteristics were evaluated by the same method as in Example 11. As a result, the compound (a) was based on the oxidation-reduction potential of ferrocene. -3.30V vs. Although it ran to Fc / Fc ⁺ , no reduction wave was observed.

Example 20 (Element evaluation of compound (A2))
The glass substrate on which the ITO transparent electrode (anode) having a thickness of 200 nm was laminated was subjected to ultrasonic cleaning with acetone and pure water and boiling cleaning with isopropyl alcohol. Furthermore, ultraviolet / ozone cleaning was performed, and after evacuation with a vacuum pump until it was 1 × 10 ⁻⁴ Pa after installation in a vacuum deposition apparatus. First, NPD was deposited on the ITO transparent electrode at a deposition rate of 0.3 nm / second to form a 20 nm hole injection layer. Subsequently, after depositing compound (A2) at a deposition rate of 0.3 nm / second for 30 nm, phosphorous dopant material tris (2-phenylpyridine) iridium (Ir (ppy) ₃ ) and host material 4,4′- Bis (N-carbazolyl) biphenyl (CBP) was co-evaporated at a deposition rate of 0.25 nm / second so that the weight ratio was 1: 11.5 to obtain a 20 nm light emitting layer. Next, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) was deposited at a deposition rate of 0.3 nm / second to form an exciton block layer having a thickness of 10 nm, and further, Alq ₃ (Tris (8-quinolinolato) aluminum) was deposited at 0.3 nm / second to form a 30 nm electron transport layer. Subsequently, lithium fluoride was deposited as an electron injection layer to a thickness of 0.5 nm at a deposition rate of 0.01 nm / second, and aluminum was further deposited to a thickness of 100 nm at a deposition rate of 0.25 nm / second to form a cathode. In a nitrogen atmosphere, a sealing glass plate was bonded with a UV curable resin to obtain an organic EL element for evaluation. A current of 20 mA / cm ² was applied to the device thus fabricated, and driving voltage and external quantum efficiency were measured. The results are shown in Table 1.

Example 21 (Element evaluation of compound (A45))
An organic EL device was produced in the same manner as in Example 20 except that the compound (A2) was changed to the compound (A45). Table 1 shows the driving voltage and the external quantum efficiency when a current of 20 mA / cm ² is applied.

Example 22 (Element evaluation of compound (A52))
An organic EL device was produced in the same manner as in Example 20 except that the compound (A2) was changed to the compound (A52). Table 1 shows the driving voltage and the external quantum efficiency when a current of 20 mA / cm ² is applied.

Example 23 (Element evaluation of compound (A57))
An organic EL device was produced in the same manner as in Example 20 except that the compound (A2) was changed to the compound (A57). Table 1 shows the driving voltage and the external quantum efficiency when a current of 20 mA / cm ² is applied.

Example 24 (Element Evaluation of Compound (A59))
An organic EL device was produced in the same manner as in Example 20 except that the compound (A2) was changed to the compound (A59). Table 1 shows the driving voltage and the external quantum efficiency when a current of 20 mA / cm ² is applied.

Example 25 (Element evaluation of compound (B3))
An organic EL device was produced in the same manner as in Example 20 except that the compound (A2) was changed to the compound (B3). Table 1 shows the driving voltage and the external quantum efficiency when a current of 20 mA / cm ² is applied.

Example 26 (Element Evaluation of Compound (B13))
An organic EL device was produced in the same manner as in Example 20 except that the compound (A2) was changed to the compound (B13). Table 1 shows the driving voltage and the external quantum efficiency when a current of 20 mA / cm ² is applied.

Comparative Example 2 (NPD element evaluation)
An organic EL device was produced in the same manner as in Example 20 except that the compound (A2) was changed to NPD. Table 1 shows the driving voltage and the external quantum efficiency when a current of 20 mA / cm ² is applied.

Example 27 (Evaluation of device lifetime of compound (A2))
The glass substrate on which the ITO transparent electrode (anode) having a thickness of 200 nm was laminated was subjected to ultrasonic cleaning with acetone and pure water and boiling cleaning with isopropyl alcohol. Furthermore, ultraviolet / ozone cleaning was performed, and after evacuation with a vacuum pump until it was 1 × 10 ⁻⁴ Pa after installation in a vacuum deposition apparatus. First, copper phthalocyanine was deposited on the ITO transparent electrode at a deposition rate of 0.1 nm / second to form a 10 nm hole injection layer. Subsequently, NPD was deposited at a deposition rate of 0.3 nm / second to 25 nm, and then compound (A2) was deposited at a deposition rate of 0.1 nm / second to 5 nm. Subsequently, tris (2-phenylpyridine) iridium (Ir (ppy) ₃ ) as a phosphorescent dopant material and 4,4′-bis (N-carbazolyl) biphenyl (CBP) as a host material have a weight ratio of 1:11. Co-deposited at a deposition rate of 0.25 nm / second to obtain a 30 nm emission layer. Next, BAlq (bis (2-methyl-8-quinolinolato) (p-phenylphenolato) aluminum) was deposited at a deposition rate of 0.3 nm / second to form a 5 nm exciton block layer, and then Alq ₃ (Tris (8-quinolinolato) aluminum) was deposited at 0.3 nm / second to form a 45 nm electron transport layer. Subsequently, lithium fluoride was deposited as an electron injection layer to a thickness of 0.5 nm at a deposition rate of 0.01 nm / second, and aluminum was further deposited to a thickness of 100 nm at a deposition rate of 0.25 nm / second to form a cathode. In a nitrogen atmosphere, a sealing glass plate was bonded with a UV curable resin to obtain an organic EL element for evaluation. A current of 6.25 mA / cm ² was applied to the device thus fabricated, and the luminance half time was evaluated. The results are shown in Table 2.

Example 28 (Device Life Evaluation of Compound (A57))
An organic EL device was produced in the same manner as in Example 27 except that the compound (A2) was changed to the compound (A57). Table 2 shows the luminance half time when a current of 6.25 mA / cm ² was applied.

Example 29 (Evaluation of device lifetime of compound (A59))
An organic EL device was produced in the same manner as in Example 27 except that the compound (A2) was changed to the compound (A59). Table 2 shows the luminance half time when a current of 6.25 mA / cm ² was applied.

Reference Example 1 (Evaluation of Device Life of Reference Compound (a))
An organic EL device was produced in the same manner as in Example 27 except that the compound (A2) was changed to the reference compound (a). Table 2 shows the luminance half time when a current of 6.25 mA / cm ² was applied.

Claims (3)

General formula (1)

(In the formula, Ar is an aryl group having 6 to 30 carbon atoms, and the aryl group having 6 to 30 carbon atoms is a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, or 1 to 36 carbon atoms. A linear, branched or cyclic alkoxy group, an aryloxy group having 1 to 36 carbon atoms, a trialkylsilyl group having 1 to 36 carbon atoms, a triarylsilyl group having 1 to 36 carbon atoms, a 9-carbazolyl group, or a halogen atoms each independently of good .A and B as a substituent, a heteroaryl group having 3 to 20 carbon atoms and having at least one C = N bond, said at least one C = N The heteroaryl group having 3 to 20 carbon atoms having a bond is a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 36 carbon atoms, or 1 to 36 carbon atoms. The aryl Alkoxy group, a trialkylsilyl group having 1 to 36 carbon atoms, triarylsilyl group having 1 to 36 carbon atoms, 9-carbazolyl group, or optionally .X ¹ and ^{X 2} may have a halogen atom as a substituent Each independently represents a carbon atom or a nitrogen atom, each of R ¹ , R ² and R ^{4 to} R ⁷ is independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms; linear 1 to 18 carbon atoms, branched or cyclic alkoxy group, an aryl group of the aryl group (carbon number of 6 to 30 carbon number 6 to 30 is a linear 1 to 36 carbon atoms, alkyl branched or cyclic Group, a linear, branched or cyclic alkoxy group having 1 to 36 carbon atoms, an aryloxy group having 1 to 36 carbon atoms, a trialkylsilyl group having 1 to 36 carbon atoms, a triarylsilyl group having 1 to 36 carbon atoms, 9-carba Zoriru group, or a halogen atom as a substituent group), or a heteroaryl group heteroaryl group (carbon number 4 to 20 of carbon number 4 to 20 is a linear 1 to 36 carbon atoms A branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group having 1 to 36 carbon atoms, an aryloxy group having 1 to 36 carbon atoms, a trialkylsilyl group having 1 to 36 carbon atoms, or 1 to 36 carbon atoms R ³ is a hydrogen atom, a halogen atom, a straight-chain, branched or cyclic group having 1 to 18 carbon atoms, optionally having a triarylsilyl group, 9-carbazolyl group, or halogen atom as a substituent . Represents an alkyl group or a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, wherein R ⁸ and R ⁹ each independently represent a halogen atom, a linear, branched or cyclic atom having 1 to 18 carbon atoms; Alkyl group, straight-chain having 1 to 18 carbon atoms, branched or cyclic alkoxy group, or an aryl group the aryl group (carbon number of 6 to 30 carbon number 6 to 30 is a linear 1 to 36 carbon atoms, A branched or cyclic alkyl group, a straight-chain, branched or cyclic alkoxy group having 1 to 36 carbon atoms, an aryloxy group having 1 to 36 carbon atoms, a trialkylsilyl group having 1 to 36 carbon atoms, a 1 to 36 carbon atoms A triarylsilyl group, a 9-carbazolyl group, or a halogen atom which may have a substituent . m and n each independently represents an integer of 0 or 1 [provided that m + n is 1 or 2], and p and q each independently represents an integer of 0 to 4. )
An amine compound represented by In the general formula (1), A and B are each independently, Lee imidazolyl group, a thiazolyl group, a pyridyl group, pyrimidyl group, pyrazinyl group, 1,3,5-triazyl group, benzimidazolyl group, benzothiazolyl group and, A quinoxalyl group (these groups are a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 36 carbon atoms, an aryloxy group having 1 to 36 carbon atoms, A substituent selected from a trialkylsilyl group having 1 to 36 carbon atoms, a triarylsilyl group having 1 to 36 carbon atoms, a 9-carbazolyl group, or a halogen atom (which may have a halogen atom as a substituent). The amine compound according to claim 1, which is characterized by the following . An organic EL device, wherein the amine compound according to claim 1 or 2 is used in any of a light emitting layer, a hole transport layer, and a hole injection layer.

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