JP2001039934A - Amine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound comprising a specific amine compound, useful as a hole injection transportation material for an organic electroluminescent element. SOLUTION: This compound is shown by formula I [Ar1 to Ar4 are each an aryl or the like; R1 and R2 are each H, an alkyl or the like; Z1 and Z2 are each H, a halogen or the like; and X1 and X2 are each a group of the formula-(A1-X11)m-A2-(A1 and A2 are each phenylene or the like; X11 is a single bond, O or the like; (m) is 0 or 1)] such as a compound of formula II. The compound of formula I is obtained by reacting a compound of formula V (Y1 is a halogen) e.g. N,N-di[4-(N',N'-diphenylamino)phenyl]amine, etc.}, obtained from a compound of formula III and a compound of formula IV with a compound of formula VI (Y2 is a halogen) (e.g. 9,9-dimethyl-9H-2-iodofluorene, etc.), in the presence of a copper compound (e.g. metal copper powder, etc.), and anhydrous potassium carbonate in o-dichlorobenzene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel amine compound.

[0002]

2. Description of the Related Art Conventionally, amine compounds have been used as intermediates for producing various dyes or as various functional materials. As a functional material, for example, it has been used as a charge transport material for an electrophotographic photosensitive member. Furthermore, recently, it has been proposed to be useful as a hole injection / transport material for an organic electroluminescence device (organic electroluminescence device: organic EL device) using an organic material as a light emitting material [for example, App.
l. Phys. Lett., 51 , 913 (1987)]. It has been proposed to use 4,4′-bis [N-phenyl-N- (3 ″ -methylphenyl) amino] biphenyl as a hole injection / transport material for organic electroluminescent devices [Jpn. J. Appl. Ph
ys., 27 , L269 (1988)]. Further, as a hole injection / transport material for an organic electroluminescent device, for example, a 9,9-dialkyl-2,7-bis (N, N-diphenylamino) fluorene derivative [eg, 9,9-dimethyl-2,7- It has been proposed to use bis (N, N-diphenylamino) fluorene] (JP-A-5-25473).
However, organic electroluminescent devices using these amine compounds as hole injecting and transporting materials have disadvantages such as poor stability and durability. At present, a novel amine compound is desired to obtain a more improved organic electroluminescent device.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel amine compound. More specifically, it is an object of the present invention to provide a novel amine compound suitable for a hole injection / transport material of an organic electroluminescent device.

[0004]

Means for Solving the Problems The present inventors have made intensive studies on various amine compounds, and as a result, completed the present invention. That is, the present invention relates to an amine compound represented by the general formula (1).

[0005]

Embedded image[Wherein, Ar₁~ Ar_FourIs a substituted or unsubstituted aryl
A group represented by Ar ₁And Ar_TwoAnd Ar_ThreeAnd Ar
_FourForms a nitrogen-containing heterocycle with the attached nitrogen atom
May represent R₁And R_TwoIs a hydrogen atom,
Chain, branched or cyclic alkyl group, substituted or unsubstituted
Aryl group or substituted or unsubstituted aralkyl group
And Z₁And Z_TwoIs a hydrogen atom, a halogen atom,
Chain, branched or cyclic alkyl group, straight chain, branched or cyclic
Alkoxy group or substituted or unsubstituted aryl
X represents₁And X_TwoIs-(A₁-X₁₁)_m-A
_Two-(However, A₁And A_TwoIs substituted or unsubstituted
Phenylene group or substituted or unsubstituted naphthyl
X₁₁Represents a single bond, an oxygen atom or a sulfur atom
And m represents 0 or 1)]

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The present invention relates to an amine compound represented by the general formula (1).

Embedded image[Wherein, Ar₁~ Ar_FourIs a substituted or unsubstituted aryl
A group represented by Ar ₁And Ar_TwoAnd Ar_ThreeAnd Ar
_FourForms a nitrogen-containing heterocycle with the attached nitrogen atom
May represent R₁And R_TwoIs a hydrogen atom,
Chain, branched or cyclic alkyl group, substituted or unsubstituted
Aryl group or substituted or unsubstituted aralkyl group
And Z₁And Z_TwoIs a hydrogen atom, a halogen atom,
Chain, branched or cyclic alkyl group, straight chain, branched or cyclic
Alkoxy group or substituted or unsubstituted aryl
X represents₁And X_TwoIs-(A₁-X₁₁)_m-A
_Two-(However, A₁And A_TwoIs substituted or unsubstituted
Phenylene group or substituted or unsubstituted naphthyl
X₁₁Represents a single bond, an oxygen atom or a sulfur atom
And m represents 0 or 1)]

In the general formula (1), Ar _{1 to} Ar ₄ represent a substituted or unsubstituted aryl group. Note that the aryl group represents a carbocyclic aromatic group such as a phenyl group, a naphthyl group, and an anthryl group, and a heterocyclic aromatic group such as a furyl group, a thienyl group, and a pyridyl group.

Ar _{1 to} Ar ₄ are preferably unsubstituted,
Alternatively, as the substituent, for example, a carbocyclic aromatic group having a total of 6 to 20 carbon atoms, which may be mono- or polysubstituted by a halogen atom, an alkyl group, an alkoxy group, or an aryl group, or a total of 3 to 3 carbon atoms 20 heterocyclic aromatic groups, more preferably an unsubstituted or halogen atom, an alkyl group having 1 to 14 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, or an aryl group having 6 to 10 carbon atoms A total of 6 to 20 carbon atoms which may be mono- or polysubstituted
And more preferably an unsubstituted or halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 6 to 6 carbon atoms.
It is a carbocyclic aromatic group having 6 to 16 carbon atoms, which may be mono- or polysubstituted with 10 aryl groups.

Specific examples of Ar _{1 to} Ar ₄ include, for example, phenyl, 1-naphthyl, 2-naphthyl, 2
-Anthryl group, 9-anthryl group, 2-fluorenyl group, 4-quinolyl group, 4-pyridyl group, 3-pyridyl group, 2-pyridyl group, 3-furyl group, 2-furyl group, 3
-Thienyl group, 2-thienyl group, 2-oxazolyl group,
2-thiazolyl group, 2-benzooxazolyl group, 2-benzothiazolyl group, 2-benzimidazolyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 3-ethyl Phenyl 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, 2-neopentylphenyl group, 4-tert-pentylphenyl group, 4-n-hexylphenyl Group, 4-
(2′-ethylbutyl) phenyl group, 4-n-heptylphenyl group, 4-n-octylphenyl group, 4- (2 ′
-Ethylhexyl) phenyl group, 4-tert-octylphenyl group, 4-n-decylphenyl group, 4-n-dodecylphenyl group, 4-n-tetradecylphenyl group, 4-
Cyclopentylphenyl group, 4-cyclohexylphenyl group, 4- (4'-methylcyclohexyl) phenyl group, 4- (4'-tert-butylcyclohexyl) phenyl group, 3-cyclohexylphenyl group, 2-cyclohexylphenyl group, 4- Ethyl-1-naphthyl group, 6-n
-Butyl-2-naphthyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,6-dimethylphenyl group, 2, 4-diethylphenyl group, 2,
3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 3,4,5-trimethylphenyl group,
2,6-diethylphenyl group, 2,5-diisopropylphenyl group, 2,6-diisobutylphenyl group, 2,4
-Di-tert-butylphenyl group, 2,5-di-tert-butylphenyl group, 4,6-di-tert-butyl-2-methylphenyl group, 5-tert-butyl-2-methylphenyl group, 4 A tert-butyl-2,6-dimethylphenyl group,
9-methyl-2-fluorenyl group, 9-ethyl-2-fluorenyl group, 9-n-hexyl-2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, 9,9-
Diethyl-2-fluorenyl group, 9,9-di-n-propyl-2-fluorenyl group,

4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 4-ethoxyphenyl, 3-ethoxyphenyl, 2-ethoxyphenyl, 4-n-propoxyphenyl, 3-n -Propoxyphenyl group, 4-isopropoxyphenyl group, 2-
Isopropoxyphenyl group, 4-n-butoxyphenyl group, 4-isobutoxyphenyl group, 2-sec-butoxyphenyl group, 4-n-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, 2-methoxy-1-naphthyl group,
4-methoxy-1-naphthyl group, 4-n-butoxy-1
-Naphthyl group, 5-ethoxy-1-naphthyl group, 6-methoxy-2-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-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-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-phenylphenyl group, 3-
Phenylphenyl group, 2-phenylphenyl group, 4-
(4'-methylphenyl) phenyl group, 4- (3'-methylphenyl) phenyl group, 4- (4'-methoxyphenyl) phenyl group, 4- (4'-n-butoxyphenyl) phenyl group, 2- (2′-methoxyphenyl) phenyl group, 4- (4′-chlorophenyl) phenyl group, 3
-Methyl-4-phenylphenyl group, 3-methoxy-4
-Phenylphenyl group, 9-phenyl-2-fluorenyl group,

4-fluorophenyl, 3-fluorophenyl, 2-fluorophenyl, 4-chlorophenyl, 3-chlorophenyl, 2-chlorophenyl,
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, 3,4
-Dichlorophenyl group, 3,5-dichlorophenyl group,
2,5-dibromophenyl group, 2,4,6-trichlorophenyl group, 2,4-dichloro-1-naphthyl group,
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, 2 -Methyl-4-fluorophenyl group, 2-methyl-5-fluorophenyl group, 3
-Methyl-4-fluorophenyl group, 2-chloro-4-
Methylphenyl group, 2-chloro-5-methylphenyl group, 2-chloro-6-methylphenyl group, 2-methyl-
3-chlorophenyl group, 2-methyl-4-chlorophenyl group, 3-chloro-4-methylphenyl group, 3-methyl-4-chlorophenyl group, 2-chloro-4,6-dimethylphenyl group, 2-methoxy-4 -Fluorophenyl group, 2-fluoro-4-methoxyphenyl group, 2-fluoro-4-ethoxyphenyl group, 2-fluoro-6-methoxyphenyl group, 3-fluoro-4-ethoxyphenyl group, 3-chloro-4 -Methoxyphenyl group, 2-methoxy-5-chlorophenyl group, 3-methoxy-6-chlorophenyl group, 5-chloro-2,4-dimethoxyphenyl group, and the like, but are not limited thereto. .

In the compound represented by the general formula (1),
Further, Ar₁And Ar_TwoAnd Ar _ThreeAnd Ar_FourJoins
May form a nitrogen-containing heterocyclic ring with the nitrogen atom
And preferably -NAr₁Ar_TwoAnd -NAr_ThreeA
r_FourIs a substituted or unsubstituted -N-carbazolyyl group,
A substituted or unsubstituted -N-phenoxazinyl group,
Or a substituted or unsubstituted -N-phenothiadinyl group
May be formed, preferably unsubstituted, or
As the substituent, for example, a halogen atom, a carbon number of 1 to 10
An alkyl group, an alkoxy group having 1 to 10 carbon atoms, or
Is a mono- or polysubstituted aryl group having 6 to 10 carbon atoms.
-N-carbazolyyl group, -N-pheno
Oxazinyl group or -N-phenothiazinyl group
And more preferably unsubstituted or halogen
Atom, alkyl group having 1 to 4 carbon atoms, alkyl group having 1 to 4 carbon atoms
Coxy group or aryl group having 6 to 10 carbon atoms
-N-carbazolyi optionally substituted or polysubstituted
Group, -N-phenoxazinyl group, or -N-phenyl
Enothiazinyl group, more preferably unsubstituted
-N-carbazolyyl group, unsubstituted -N-phenoxa
Dinyl group or unsubstituted -N-phenothiazinii
Group.

--NAr ₁ Ar ₂ and --NAr ₃ Ar ₄
May form a nitrogen-containing heterocyclic ring, and specific examples include, for example, -N-carbazolyyl group, 2-methyl-N
-Carbazolyyl group, 3-methyl-N-carbazolyyl group, 4-methyl-N-carbazolyyl group, 3-n-butyl-N-carbazolyyl group, 3-n-hexyl-N-carbazolyyl group, 3-n-octyl- N-carbazolyyl group, 3-n-decyl-N-carbazolyyl group, 3,6
-Dimethyl-N-carbazolyyl group, 2-methoxy-N
-Carbazolyyl group, 3-methoxy-N-carbazolyyl group, 3-ethoxy-N-carbazolyyl group, 3-isopropoxy-N-carbazolyyl group, 3-n-butoxy-N-carbazolyyl group, 3-n-octyloxy- N
-Carbazolyyl group, 3-n-decyloxy-N-carbazolyyl group, 3-phenyl-N-carbazolyyl group,
3- (4'-methylphenyl) -N-carbazolyyl group, 3- (4'-tert-butylphenyl) -N-carbazolyyl group, 3-chloro-N-carbazolyyl group, -N
-Phenoxadinyl group, -N-phenothiadinyl group, 2-methyl-N-phenothiadinyl group and the like.

In the compound represented by the general formula (1),
R ₁ and R ₂ represent a hydrogen atom, a linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, preferably a hydrogen atom, having 1 to 16 carbon atoms. A linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group having 4 to 16 carbon atoms, or a substituted or unsubstituted aralkyl group having 5 to 16 carbon atoms, more preferably a hydrogen atom, a carbon atom 1
-8 linear, branched or cyclic alkyl groups, 6-6 carbon atoms
A substituted or unsubstituted aryl group having 12 or a substituted or unsubstituted aralkyl group having 7 to 12 carbon atoms, and more preferably, R ₁ and R ₂ are linear, branched or cyclic having 1 to 8 carbon atoms. An alkyl group, a carbocyclic aromatic group having 6 to 10 carbon atoms, or a carbocyclic aralkyl group having 7 to 10 carbon atoms.

Specific examples of the substituted or unsubstituted aryl groups for R ₁ and R ₂ include, for example, Ar _{1 to} Ar ₄
The substituted or unsubstituted aryl group mentioned as a specific example can be exemplified.

Specific examples of the linear, branched or cyclic alkyl group of R ₁ and R ₂ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- Butyl group, tert-butyl group,
n-pentyl group, isopentyl group, neopentyl group, te
rt-pentyl group, cyclopentyl group, n-hexyl group,
2-ethylbutyl group, 3,3-dimethylbutyl group, cyclohexyl group, n-heptyl group, cyclohexylmethyl group, n-octyl group, tert-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, Examples thereof include an n-dodecyl group, an n-tetradecyl group, and an n-hexadecyl group, but are not limited thereto.

Specific examples of the substituted or unsubstituted aralkyl group of R ₁ and R ₂ include, for example, benzyl group, phenethyl group, α-methylbenzyl group, α, α-dimethylbenzyl group, 1-naphthylmethyl Group, 2-naphthylmethyl group, furfuryl group, 2-methylbenzyl group, 3
-Methylbenzyl group, 4-methylbenzyl group, 4-ethylbenzyl group, 4-isopropylbenzyl group, 4-tert
-Butylbenzyl group, 4-n-hexylbenzyl group, 4
-Nonylbenzyl group, 3,4-dimethylbenzyl group, 3
-Methoxybenzyl group, 4-methoxybenzyl group, 4-
Ethoxybenzyl group, 4-n-butoxybenzyl group, 4
Aralkyl groups such as -n-hexyloxybenzyl group, 4-nonyloxybenzyl group, 4-fluorobenzyl group, 3-fluorobenzyl group, 2-chlorobenzyl group, and 4-chlorobenzyl group; It is not limited to these.

Z ₁ and Z ₂ represent a hydrogen atom, a halogen atom, a straight-chain, branched or cyclic alkyl group, a straight-chain, branched or cyclic alkoxy group, or a substituted or unsubstituted aryl group. Atom, halogen atom, C1-C16 linear, branched or cyclic alkyl group, C1-C16 linear, branched or cyclic alkoxy group, or C4-C20 substituted or unsubstituted aryl And more preferably a hydrogen atom, a halogen atom, 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, or 6 carbon atoms. To 12 substituted or unsubstituted aryl groups, more preferably a hydrogen atom.

Specific examples of the linear, branched or cyclic alkyl groups of Z ₁ and Z ₂ include, for example, the linear, branched or cyclic alkyl groups mentioned as specific examples of R ₁ and R _2. can do. Z ₁ and Z ₂
As specific examples of the substituted or unsubstituted aryl group, there can be mentioned, for example, the substituted or unsubstituted aryl groups mentioned as specific examples of Ar _{1 to} Ar ₄ .

Specific examples of the halogen atom of Z ₁ and Z ₂ , a linear, branched or cyclic alkoxy group include, for example, a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, for example, a methoxy group, an ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, n-pentyloxy group, isopentyloxy group, neopentyloxy group, cyclopentyloxy group, n-hexyloxy group, 2- Ethyl butoxy group, 3,3-dimethylbutoxy group, cyclohexyloxy group, n-heptyloxy group, cyclohexylmethyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group,
n-dodecyloxy group, n-tetradecyloxy group, n
-An alkoxy group such as a hexadecyloxy group.

In the compound represented by the general formula (1),
X₁And X_TwoIs-(A₁-X₁₁) _m-A_TwoRepresents-.
(However, A₁And A_TwoIs substituted or unsubstituted phenyle
Group or a substituted or unsubstituted naphthylene group
Then X₁₁Represents a single bond, an oxygen atom or a sulfur atom, and m
Represents 0 or 1)

A ₁ and A ₂ represent a substituted or unsubstituted phenylene group or a substituted or unsubstituted naphthylene group, preferably a substituted or unsubstituted 1,3-phenylene group, a substituted or unsubstituted 1,3-phenylene group. 4-phenylene group, substituted or unsubstituted 1,4-naphthylene group, substituted or unsubstituted 1,5-naphthylene group, substituted or unsubstituted 2,
6-naphthylene group or substituted or unsubstituted 2,7
-A naphthylene group, more preferably a substituted or unsubstituted 1,4-phenylene group, a substituted or unsubstituted 1,4-phenylene group;
It is a 4-naphthylene group, a substituted or unsubstituted 1,5-naphthylene group, or a substituted or unsubstituted 2,6-naphthylene group. X ₁₁ represents a single bond, an oxygen atom or a sulfur atom. m represents 0 or 1. When m represents 1, more preferably, A ₁ is a substituted or unsubstituted 1,4-phenylene group.

In the compound represented by the general formula (1),
X ₁ and X ₂ are more preferably represented by the general formula (2)
-A) an arylene group represented by the general formula (2-g) or the general formula (2-g).

[0024]

Embedded image (Wherein, Z ₁₁ and Z ₁₂ represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, or a substituted or unsubstituted aryl group)

[0025]

Embedded image (Wherein, Z ₂₁ and Z ₂₂ represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, or a substituted or unsubstituted aryl group)

[0026]

Embedded image (Wherein, Z ₃₁ and Z ₃₂ represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, or a substituted or unsubstituted aryl group)

[0027]

Embedded image (Wherein, Z ₄₁ and Z ₄₂ represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, or a substituted or unsubstituted aryl group)

[0028]

Embedded image (Wherein, Z ₅₁ and Z ₅₂ represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, or a substituted or unsubstituted aryl group)

[0029]

Embedded image (Wherein, Z ₆₁ and Z ₆₂ represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, or a substituted or unsubstituted aryl group)

[0030]

Embedded image (Wherein, Z ₇₁ and Z ₇₂ represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, or a substituted or unsubstituted aryl group)

In general formulas (2-a) to (2-g),
And Z₁₁, Z₁₂, Z_{twenty one}, Z_{twenty two}, Z ₃₁, Z₃₂, Z₄₁, Z
₄₂, Z₅₁, Z₅₂, Z₆₁, Z₆₂, Z₇₁And Z₇₂(Less than,
Z₁₁~ Z₇₂Abbreviated as) is a hydrogen atom, a halogen atom,
Chain, branched or cyclic alkyl group, straight chain, branched or cyclic
Alkoxy group or substituted or unsubstituted aryl
A hydrogen atom, a halogen atom,
A linear, branched or cyclic alkyl group having 1 to 16 primes,
A linear, branched or cyclic alkoxy group having a prime number of 1 to 16,
Alternatively, a substituted or unsubstituted aryl having 4 to 20 carbon atoms
Group, more preferably a hydrogen atom, a halogen atom,
A linear, branched or cyclic alkyl group having 1 to 8 carbon atoms,
A linear, branched or cyclic alkoxy group having a prime number of 1 to 8,
Or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms
And more preferably a hydrogen atom.

Specific examples of the linear, branched or cyclic alkyl group of Z _{11 to} Z ₇₂ include, for example, the linear, branched or cyclic alkyl groups mentioned as specific examples of R ₁ and R _2. Can be. Specific examples of the substituted or unsubstituted aryl group of Z _{11 to} Z ₇₂ include, for example, Ar ₁
Can be exemplified substituted or unsubstituted aryl groups exemplified as specific examples of the to Ar _4. Further, specific examples of the halogen atom, linear, branched or cyclic alkoxy group of Z _{11 to} Z ₇₂ include, for example, the halogen atom, linear, branched or cyclic alkoxy group exemplified as specific examples of Z ₁ and Z _2. A group can be exemplified.

Specific examples of the compound represented by the general formula (1) according to the present invention include, for example, the following compounds (Chemical Formulas 11 to 11).
Chemical formula 41) can be mentioned, but the present invention is not limited to these. In the formula, Ph represents a phenyl group, and Bz represents a benzyl group.

[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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The compound represented by the general formula (1) according to the present invention can be produced by a method known per se.
That is, for example, a compound represented by the general formula (5), which can be produced from a compound represented by the general formula (3) and a compound represented by the general formula (4), and a compound represented by the general formula (6) It can be produced by reacting the represented compound in the presence of a copper compound (Ullman reaction).

[0066]

Embedded image [Wherein, Y _{1 to} Y ₂ represent a halogen atom, and Ar _{1 to} A
r ₄ , R ₁ , R ₂ , Z ₁ , Z ₂ , X ₁ and X ₂ represent the same meaning as in the general formula (1).

Further, for example, a compound represented by the general formula (7), a compound represented by the general formula (8) and a compound represented by the general formula (9)
Can be produced by reacting the compound represented by the formula (Ullman reaction) in the presence of a copper compound.

[0068]

Embedded image [Wherein, Y _{3 to} Y ₄ represent a halogen atom, and Ar _{1 to} A
r ₄ , R ₁ , R ₂ , Z ₁ , Z ₂ , X ₁ and X ₂ represent the same meaning as in the general formula (1).

In the above formula, Y _{1 to} Y ₄ represent a halogen atom, preferably a chlorine atom, a bromine atom or an iodine atom, more preferably a bromine atom or an iodine atom, particularly preferably an iodine atom Represents

[0070]

The present invention will be described in more detail with reference to the following examples, which, of course, are not intended to limit the scope of the present invention. Example 1 Production of Compound of Exemplified Compound No. A-1 Under a nitrogen atmosphere, 10 g of N, N-di [4- (N ′, N′-diphenylamino) phenyl] amine, 9,9-dimethyl-9H-2 6.5 g of iodofluorene, 10 g of metallic copper powder, and 20 g of anhydrous potassium carbonate were stirred in o-dichlorobenzene (100 g) at 190 ° C. for 8 hours.
After the reaction mixture was cooled to 100 ° C. and filtered hot, methanol (200 g) was added to the filtrate, and the precipitated pale yellow solid was filtered and dried. The solid was treated by alumina column chromatography (eluent: toluene) and then recrystallized using a mixed solvent of toluene and n-hexane. Thereafter, sublimation purification (350 ° C) under reduced pressure (10 ^-6 torr)
Then, 9.5 g of the compound of Exemplified Compound No. A-1 was obtained as pale yellow crystals. Glass transition temperature 87 ° C

Example 2 Preparation of Compound of Exemplified Compound No. A-2 In Example 1, N, N-di [4- (N ′, N′-diphenylamino) phenyl] amine was replaced with N, N-di [4- (N ′, N′-diphenylamino) phenyl] amine. Exemplified compound No. A- according to the method described in Example 1 except that N-di [4- (N ', N'-di [4'-methylphenyl] amino) phenyl] amine was used.
Two compounds were prepared. Glass transition temperature 92 ° C

Example 3 Preparation of Compound of Exemplified Compound No. A-4 In Example 1, N, N-di [4- (N ′, N′-diphenylamino) phenyl] amine was replaced with N, N-di [4- (N ′, N′-diphenylamino) phenyl] amine. N-di [4- (N '-[1'-naphthyl]-
Exemplified compound No. A according to the method described in Example 1 except that N'-phenylamino) phenyl] amine was used.
-4 was prepared. Glass transition temperature 99 ° C

Example 4 Preparation of Compound of Exemplified Compound No. A-8 In Example 1, N, N-di [4- (N ′, N′-diphenylamino) phenyl] amine was replaced with N, N-di [4- (N ′, N′-diphenylamino) phenyl] amine. Compound of Exemplified Compound No. A-8 according to the method described in Example 1 except that N-di [4- (N '-[4'-phenylphenyl] -N'-phenylamino) phenyl] amine was used. Was manufactured. Glass transition temperature 106 ° C

Example 5 Preparation of Compound of Exemplified Compound No. A-13 In Example 1, instead of using 9,9-dimethyl-9H-2-iodofluorene, 9,9-diethyl-
A compound of Exemplified Compound No. A-13 was produced according to the method described in Example 1 except that 9H-2-iodofluorene was used. Glass transition temperature 96 ° C

Example 6 Preparation of Compound of Exemplified Compound No. A-17 In Example 1, N, N-di [4- (N ′, N′-diphenylamino) phenyl] amine was replaced with N, N-di [4- (N ′, N′-diphenylamino) phenyl] amine. A compound of Exemplified Compound No. A-17 was produced according to the method described in Example 1 except that N-di [4- (N′-carbazolyyl) phenyl] amine was used. Glass transition temperature 112 ° C

Example 7 Preparation of Compound of Exemplified Compound No. B-3 In Example 1, N-N-di [4- (N ′, N′-diphenylamino) phenyl] amine was replaced with N-N-di [4- (N ′, N′-diphenylamino) phenyl] amine. Described in Example 1 except that [4- (N ', N'-diphenylamino) phenyl] -N- [4'-(N ", N" -diphenylamino) -1'-naphthyl] amine was used. The compound of Exemplified Compound No. B-3 was produced according to the method described above. Glass transition temperature 98 ° C

Example 8 Preparation of Compound of Exemplified Compound No. C-3 In Example 1, N-N-di [4- (N ′, N′-diphenylamino) phenyl] amine was replaced with N-N-di [4- (N ′, N′-diphenylamino) phenyl] amine. [4- (N ', N'-di [4'-methylphenyl] amino) phenyl] -N- [5 "-(N", N "-
A compound of Exemplified Compound No. C-3 was produced according to the method described in Example 1 except that di [4 ′ ″-methylphenyl] amino) -1 ″ -naphthyl] amine was used. ° C

Example 9 Preparation of Compound of Exemplified Compound No. D-3 In Example 1, N-N-di [4- (N ′, N′-diphenylamino) phenyl] amine was replaced with N-N-di [4- (N ′, N′-diphenylamino) phenyl] amine. [4- (N'-phenyl-N '-[3'-methylphenyl] amino) phenyl] -N- [6 "-(N"
A compound of Exemplified Compound No. D-3 was produced according to the method described in Example 1 except that-[3 '"-methylphenyl] -N" -phenylamino) -2 "-naphthyl] amine was used. . Glass transition temperature 107 ° C

Example 10 Preparation of Compound of Exemplified Compound No. E-3 In Example 1, N-N-di [4- (N ′, N′-diphenylamino) phenyl] amine was replaced with N-N-di [4- (N ′, N′-diphenylamino) phenyl] amine. Described in Example 1 except that [4- (N ', N'-diphenylamino) phenyl] -N- [4'-(N ", N" -diphenylamino) -4 "-biphenyl] amine was used. The compound of Exemplified Compound No. E-3 was produced according to the method described in Example 1. Glass transition temperature 114 ° C.

Example 11 Preparation of Compound of Exemplified Compound No. E-5 In Example 1, N-N-di [4- (N ′, N′-diphenylamino) phenyl] amine was replaced with N-N-di [4- (N ′, N′-diphenylamino) phenyl] amine. [4- (N '-[4'-methoxyphenyl]-
N'-phenylamino) phenyl] -N- [4 "-
Exemplified compound No. E according to the method described in Example 1 except that (N "-[4""-methoxyphenyl]-N" -phenylamino) -4 '"-biphenyl] amine was used.
Compound -5 was prepared. Glass transition temperature 118 ° C

Example 12 Preparation of Compound of Exemplified Compound No. E-10 In Example 1, N-N-di [4- (N ′, N′-diphenylamino) phenyl] amine was replaced with N-N-di [4- (N ′, N′-diphenylamino) phenyl] amine. [4- (N'-phenyl-N '-[3'-methylphenyl] amino) phenyl] -N- [4 "-(N"
-Phenyl-N "-[3""-methylphenyl] amino) -4""-biphenyl] amine,
According to the method described in Example 1, Exemplified Compound No. E-10
Was prepared. Glass transition temperature 110 ° C

Example 13 Preparation of Compound of Exemplified Compound No. E-13 In Example 1, N-N-di [4- (N ′, N′-diphenylamino) phenyl] amine was replaced with N-N-di [4- (N ′, N′-diphenylamino) phenyl] amine. [4- (N '-[2'-naphthyl] -N'-phenylamino) phenyl] -N- [4 "-(N", N "
-Diphenylamino) -4 ″ ′-biphenyl] amine was used to prepare the compound of Exemplified Compound No. E-13 according to the method described in Example 1. Glass transition temperature 118 ° C

Example 14 Preparation of Compound of Exemplified Compound No. E-17 In Example 1, instead of using N, N-di [4- (N ′, N′-diphenylamino) phenyl] amine, N- [4- (N′-phenoxazinyl) amino)
Phenyl] -N- [4 '-(N ", N" -diphenylamino) -4 "-biphenyl)] amine, except that Exemplified Compound No. E- was used according to the method described in Example 1.
Seventeen compounds were prepared. Glass transition temperature 125 ° C

Example 15 Preparation of Compound of Exemplified Compound No. E-25 In Example 1, N-N-di [4- (N ′, N′-diphenylamino) phenyl] amine was replaced with N-N-di [4- (N ′, N′-diphenylamino) phenyl] amine. [4- (N '-[4'-ethylphenyl]-
N'-phenylamino) -1-naphthyl] -N- [4 "
A compound of Exemplified Compound No. E-25 was produced according to the method described in Example 1 except that-(N ", N" -diphenylamino) -4 '"-biphenyl] amine was used. Glass transition temperature 122 ° C

Example 16 Preparation of Compound of Exemplified Compound No. E-28 In Example 1, N, N-di [4- (N ′, N′-diphenylamino) phenyl] amine was replaced with N, N-di [4- (N ′, N′-diphenylamino) phenyl] amine. According to the method described in Example 1, except that N-di [4- (N '-[3'-methylphenyl] -N'-phenylamino) -4 "-biphenyl] amine was used.
The compound of Exemplified Compound No. E-28 was produced. Glass transition temperature 125 ° C

Example 17 Preparation of Compound of Exemplified Compound No. E-30 In Example 1, N, N-di [4- (N ′, N′-diphenylamino) phenyl] amine was replaced with N, N-di [4- (N ′, N′-diphenylamino) phenyl] amine. A compound of Exemplified Compound No. E-30 was produced according to the method described in Example 1 except that N-di [4- (N ′, N′-diphenylamino) -4 ″ -biphenyl] amine was used. Glass transition temperature 123 ° C

Example 18 Preparation of Compound of Exemplified Compound No. F-5 In Example 1, instead of using N, N-di [4- (N ′, N′-diphenylamino) phenyl] amine, N- [4- (N ', N'-diphenylamino) -1
-Naphthyl] -N- [4 '-(4 "-[N", N "-diphenylamino] phenyloxy) phenyl] amine, according to the method described in Example 1, except that Compound No. F- The compound of No. 5 was produced: Glass transition temperature 108 ° C.

Example 19 Preparation of Compound of Exemplified Compound No. G-7 In Example 1, N-N-di [4- (N ′, N′-diphenylamino) phenyl] amine was replaced with N-N-di [4- (N ′, N′-diphenylamino) phenyl] amine. [4- (N ', N'-di [4 "-methylphenyl] amino) -4'-biphenyl] -N- [4'"-
A compound of Exemplified Compound No. G-7 was produced according to the method described in Example 1 except that (4 ″ ″-[N ″, N ″ -diphenylamino] phenylthio) phenyl] amine was used. Glass transition temperature 117 ° C

Application Example 1 A glass substrate having a 200-nm-thick ITO transparent electrode (anode) was subjected to ultrasonic cleaning using a neutral detergent, acetone, and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, the compound of Exemplified Compound No. A-4 was deposited on the ITO transparent electrode to a thickness of 75 nm at a deposition rate of 0.2 nm / sec to form a hole injection transport layer. Next, tris (8-quinolinolato) aluminum was deposited thereon at a deposition rate of 0.2 nm / sec to a thickness of 50 nm to form a light-emitting layer also serving as an electron injection / transport layer. Further, magnesium and silver were co-deposited thereon as a cathode at a deposition rate of 0.2 nm / sec to a thickness of 200 nm (weight ratio: 10: 1) to produce an organic electroluminescent device. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. A DC voltage is applied to the produced organic electroluminescent device, and the temperature is set to 50 ° C. in a dry atmosphere.
The device was continuously driven at a constant current density of 10 mA / cm ² . Initially, green light emission of 6.8 V and luminance of 460 cd / m ² was confirmed. The half life of the luminance was 510 hours.

Application Examples 2 to 10 In Application Example 1, instead of using the compound of Exemplified Compound No. A-4 in forming the hole injecting and transporting layer, instead of using the compound of Exemplified Compound No. A-8 (Application Example 2), Compound of Exemplified Compound No. A-17 (Application Example 3), Exemplified Compound No. B-
Compound No. 3 (Application Example 4), Compound Compound No. D-3 (Application Example 5), Compound Compound No. E-5 (Application Example 6), Compound Compound No. E-10 (Application Example 7) A compound of Exemplified Compound No. E-25 (Application Example 8),
An organic electroluminescent device was prepared by the method described in Application Example 1, except that the compound of Exemplified Compound No. E-28 (Application Example 9) and the compound of Exemplified Compound No. G-7 (Application Example 10) were used. Green light emission was confirmed from each element. The characteristics were further examined, and the results are shown in Table 1.

Comparative Examples 1-2 In the application example 1, when forming the hole injection transport layer, instead of using the compound of Exemplified Compound No. A-4,
4'-bis [N-phenyl-N- (3 "-methylphenyl) amino] biphenyl (Comparative Example 1), 9,9-dimethyl-2,7-bis (N, N-diphenylamino) fluorene (Comparative Example) An organic electroluminescent device was prepared by the method described in Application Example 1 except that 2) was used, and green light emission was confirmed from each device, and its characteristics were further examined, and the results are shown in Table 1. .

[0092]

[Table 1]

[0093]

According to the present invention, it has become possible to provide a novel amine compound. In particular, it has become possible to provide an amine compound having excellent characteristics as a hole injection / transport material for an organic electroluminescent device.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C07D 265/38 C07D 265/38 333/34 333/34

Claims (1)

[Claims] 1. An amine compound represented by the general formula (1). Embedded image[Wherein, Ar₁~ Ar_FourIs a substituted or unsubstituted aryl
A group represented by Ar ₁And Ar_TwoAnd Ar_ThreeAnd Ar
_FourForms a nitrogen-containing heterocycle with the attached nitrogen atom
May represent R₁And R_TwoIs a hydrogen atom,
Chain, branched or cyclic alkyl group, substituted or unsubstituted
Aryl group or substituted or unsubstituted aralkyl group
And Z₁And Z_TwoIs a hydrogen atom, a halogen atom,
Chain, branched or cyclic alkyl group, straight chain, branched or cyclic
Alkoxy group or substituted or unsubstituted aryl
X represents₁And X_TwoIs-(A₁-X₁₁)_m-A
_Two-(However, A₁And A_TwoIs substituted or unsubstituted
Phenylene group or substituted or unsubstituted naphthyl
X₁₁Represents a single bond, an oxygen atom or a sulfur atom
And m represents 0 or 1)]