JP2003212866A - Method for producing arylamine compound, arylamine compound produced by the production method, and organic electroluminescent element using arylamine compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a highly pure arylamine compound used for organic electroluminescent elements and the like. <P>SOLUTION: This method for producing the arylamine compound comprises reacting a halogenated aromatic compound represented by general formula (1) [X is a halogen atom; (p), (q), (r) and (s) are each 0 or 1; (p)+(q)+(r)+(s) is not 0] with a diaryl-substituted amine compound represented by general formula (2) (Ar<SB>1</SB>and Ar<SB>2</SB>are each a substituted or un-substituted aryl, or Ar<SB>1</SB>and Ar<SB>2</SB>may be bound to each other to form a nitrogen-containing heterocyclic ring) in the presence of a base and a catalyst comprising a palladium compound and a phosphine compound having an alkyl group and an aryl group in the same molecule. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an arylamine compound, an arylamine compound produced by the method, and an organic electroluminescent device containing the arylamine compound.

[0002]

2. Description of the Related Art Conventionally, arylamine compounds have been used as intermediates for producing various dyes, intermediates in the field of medicine and agrochemicals, or various functional materials. As a functional material, for example, a charge transport material for an electrophotographic photoreceptor has been used. Recently, it has been proposed that it is useful as a hole injecting and transporting material for an organic electroluminescent device (organic electroluminescence device: organic EL device) using an organic material as a light emitting material [eg, Appl.Phys.lett. ., 51 , 913 (198
7)].

An organic electroluminescence device has a structure in which a thin film containing a fluorescent organic compound is sandwiched between an anode and a cathode tube, and electrons and holes are injected into the thin film to excite them by recombining. This element emits light by using the light emitted when an exciton is deactivated by generating a child (exington). The organic electroluminescent element can emit light at a low DC voltage of about several V to several tens of V, and various colors (for example, red, blue, green) can be selected by selecting the kind of the fluorescent organic compound. Can emit light. The organic electroluminescent device having such characteristics is expected to be applied to various light emitting devices, display devices and the like. However, in general,
Organic electroluminescent devices have drawbacks such as poor stability and durability. In order to efficiently inject and transport holes into a thin film containing a fluorescent organic compound of an organic electroluminescence device,
It has been proposed to use 4,4′-bis [N-phenyl-N- (3 ″ -methylphenyl) amino] biphenyl as a hole injecting and transporting material [Jpn.J.Appl.Phys., 2
7 , L269 (1988)].

As the hole injecting and transporting material, for example,
It is also proposed to use 9,9-dialkyl-2,7-bis (N, N-diphenylamino) fluorene derivative [for example, 9,9-dimethyl-2,7-bis (N, N-diphenylamino) fluorene]. (Japanese Patent Laid-Open No. 5-25
473).

However, organic electroluminescent devices using these arylamine compounds as hole injecting and transporting materials also have drawbacks such as poor stability and durability.

At present, there is a demand for an organic electroluminescent device having excellent stability and durability, and therefore, a novel arylamine compound exhibiting excellent properties when used as an organic electroluminescent device is desired. Therefore, development of various methods for producing arylamine compounds has been desired.

As a method for producing an arylamine compound, a method for producing an arylamine compound from an aryl halide and an amine compound using a copper catalyst has been known [large organic chemistry,
vol. 16, 52 (1959), Asakura Shoten], Organic Chemistry Course 3, 66 (1983) Maruzen, etc.].

Also, recently, Stephen L. Buchwald et al. Reported a method for producing an arylamine compound from an aryl halide and an amine compound [Angew. Chem. Int. E.
d. Engl., 34, No. 12, 1348 (1995)]. This method uses aryl bromide as a raw material, sodium-tert-butoxide as a base, and bis (dibenzylideneacetone) -bis (tri-o-tolylphosphine) palladium or dichloro-bis (tri-o-tolylphosphine) palladium. It is a method for producing an arylamine compound as a catalyst. Also, in J.Org.Chem., 65,1144 (2000), BI
NAP [2,2'-bis (diphenylphosphino)-
1,1′-binaphthyl group] is used as a ligand to describe a reaction example using a palladium catalyst. However, conventionally, as a method for producing an arylamine compound, it has not been possible to efficiently produce an arylamine compound with high purity even by a production method using these reactions.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a highly pure arylamine compound in a high yield while reducing the production of high molecular weight by-products.

[0010]

[Means for Solving the Problems] The present inventors have completed the present invention as a result of extensive studies on a method for producing an arylamine compound. That is, the present invention is: a halogenated aroma represented by the general formula (1) (Chemical Formula 3) in the presence of a catalyst comprising a phosphine compound having an alkyl group and an aryl group in the same molecule and a palladium compound, and a base. Group compounds,

[0011]

[Chemical 3]

[Wherein X represents a halogen atom, p,
q, r and s represent 0 or 1, and p + q + r + s is not 0] A method for producing an arylamine compound, which comprises reacting a diaryl-substituted amine compound represented by the general formula (2)

[0013]

[Chemical 4]

[In the formula, Ar ₁ and Ar ₂ represent a substituted or unsubstituted aryl group, and Ar ₁ and Ar ₂ may be bonded to each other to form a nitrogen-containing heterocycle]

A method for producing an arylamine compound, wherein X is a bromine atom in the general formula (1): A arylamine compound, wherein r and s are each 1 in the general formula (1) Method: The alkyl group of the phosphine compound having an alkyl group and an aryl group in the same molecule is a cyclohexyl group or te
A method for producing an arylamine compound which is rt-butyl group. An organic electroluminescent device comprising: an arylamine compound produced by the production method according to the above :, and at least one layer containing the arylamine compound according to the above description between at least one kind, between a pair of electrodes; The present invention relates to the organic electroluminescent device as described above, wherein the layer containing the arylamine compound is a hole injecting / transporting layer or a light emitting layer.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The present invention provides a catalyst comprising a phosphine compound having an alkyl group and an aryl group in the same molecule and a palladium compound, and a halogenated aromatic compound represented by the general formula (1) (Chemical Formula 5) in the presence of a base. ,

[0017]

[Chemical 5]

[Wherein, X represents a halogen atom, p,
q, r and s represent 0 or 1, and p + q + r + s is not 0] The present invention relates to a method for producing an arylamine compound, which comprises reacting a diaryl-substituted amine compound represented by the general formula (2) (formula 6).

[0019]

[Chemical 6]

[In the formula, Ar ₁ and Ar ₂ represent a substituted or unsubstituted aryl group, and Ar ₁ and Ar ₂ may be bonded to each other to form a nitrogen-containing heterocycle]

In the halogenated aromatic compound represented by the general formula (1), X represents a halogen atom, preferably iodine atom, bromine atom and chlorine atom. Further, p, q, r and s represent 0 or 1, and p + q +
r + s is not zero. Preferably, r and s are 1 and p and q are 0 or 1, more preferably r and s are 1 and p and q are 0.

Although the specific examples of the halogenated aromatic compound represented by the general formula (1) are not particularly limited, for example, 2- (4'-chlorophenyl) -3,4.
5-triphenylthiophene, 2- (4'-bromophenyl) -3,4,5-triphenylthiophene, 2-
(4'-iodophenyl) -3,4,5-triphenylthiophene, 2,5-bis (4'-chlorophenyl)-
3,4-diphenylthiophene, 2,5-bis (4'-
Bromophenyl) -3,4-diphenylthiophene,
2,5-bis (4'-iodophenyl) -3,4-diphenylthiophene, 2,3,5-tris (4'-chlorophenyl) -4-phenylthiophene, 2,3,5-tris (4'- Bromophenyl) -4-phenylthiophene, 2,3,5-tris (4'-iodophenyl) -4
-Phenylthiophene, 2,3,4-tris (4'-chlorophenyl) -5-phenylthiophene, 2,3,4
-Tris (4'-bromophenyl) -5-phenylthiophene, 2,3,4-tris (4'-iodophenyl)
-5-phenylthiophene, 2- (4'-chlorophenyl) -5- (4 "-bromophenyl) -3,4-diphenylthiophene, 2- (4'-chlorophenyl) -5-
(4 "-iodophenyl) -3,4-diphenylthiophene, 2- (4'-bromophenyl) -5- (4" -iodophenyl) -3,4-diphenylthiophene, 2,
3,4,5-Tetrakis (4'-chlorophenyl) thiophene, 2,3,4,5-Tetrakis (4'-bromophenyl) thiophene, 2,3,4,5-Tetrakis (4'-iodophenyl) thiophene Etc. can be mentioned.

The diaryl-substituted amine compound used in the present invention is a compound represented by the general formula (2) (formula 7).

[0024]

[Chemical 7]

[In the formula, Ar ₁ and Ar ₂ represent a substituted or unsubstituted aryl group, and Ar ₁ and Ar ₂ may combine with each other to form a nitrogen-containing heterocycle]

In the diaryl-substituted amine compound represented by the general formula (2), the aryl group is, for example, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted group. Alternatively, it represents an aromatic ring such as an unsubstituted phenanthrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted pyridyl group. Further, these aryl groups may be bonded to each other to form a nitrogen-containing heterocycle.

Specific examples of the diaryl-substituted amine compound are not particularly limited, but for example, N, N
-Diphenylamine, N-phenyl-N- (1-naphthyl) amine, N-phenyl-N- (2-naphthyl) amine, N, N-di (1-naphthyl) amine, N, N-di (2-naphthyl) ) Amine, N, N-di (4-phenylphenyl) amine, N, N-di (2-phenylphenyl)
Amine, N-phenyl-N- (9-anthracenyl) amine, N-phenyl-N- (2-anthracenyl) amine, N-phenyl-N- (4-phenylphenyl) amine, N-phenyl-N- (2 -Phenylphenyl) amine, N-phenyl-N- (4-cyclohexylphenyl) amine, N-phenyl-N- (2-pyridyl) amine, N-phenyl-N- (3-pyrenyl) amine, N,
N-di (4-methylphenyl) amine, N-phenyl-
N- (4-methylphenyl) amine, N-phenyl-N
-(3-Methylphenyl) amine, N, N-di (3-methylphenyl) amine, N, N-di (3,4-dimethylphenyl) amine, N-phenyl-N- (3,4-dimethylphenyl) ) Amine, N-phenyl-N- (9-phenanthryl) amine, N- (1-naphthyl) -N-
(9'-phenanthryl) amine, N-phenyl-N-
(1-Pyrenyl) amine, N- (1-naphthyl) -N-
(1'-Pyrenyl) amine, N- (1-naphthyl) -N
-(9'-anthracenyl) amine, N- (1-naphthyl) -N- (4'-phenylphenyl) amine, N-
(1-naphthyl) -N- (2'-phenylphenyl) amine, N- (4-phenylphenyl) -N- (9'-anthracenyl) amine, N- (4-phenylphenyl)
-N- (9'-phenanthrenyl) amine, carbazole, 10,11-dihydro-dibenzo [b, f] azepine,
Examples thereof include dibenzo [b, f] azepine, phenothiazine, phenoxazine, and 2-trifluoromethylphenothiazine.

In the production method of the present invention, the diarylamine compound is usually used in an amount of 0.5 to 2 equivalents, preferably 0. Use 8 to 1.5 equivalents.

In the production method of the present invention, examples of the phosphine compound having an alkyl group and an aryl group in the same molecule include methyldiphenylphosphine, dimethylphenylphosphine, ethyldiphenylphosphine, diethylphenylphosphine, n-propyldiphenylphosphine, Di-n-propylphenylphosphine, iso
-Propylphenylphosphine, di-iso-propylphenylphosphine, n-butyldiphenylphosphine,
Di-n-butylphenylphosphine, tert-butyldiphenylphosphine, di-tert-butylphenylphosphine, n-hexyldiphenylphosphine, di-n-hexylphenylphosphine, n-octyldiphenylphosphine, di-n-octylphenylphosphine, Cyclohexyldiphenylphosphine, dicyclohexylphenylphosphine,

Di-tert-butyl- (2-phenylphenyl) phosphine, di-tert-butyl- (2-cyclohexylphenyl) phosphine, di-tert-butyl- [2-
(2'-Dimethylaminophenyl) phenyl] phosphine, 2,2'-bis (di-tert-butylphosphino)-
1,1′-binaphthyl, 1,1′-bis (di-tert-butylphosphino) ferrocene, 1,1′-bis (dimethylphosphino) ferrocene, dicyclohexyl- (2-phenylphenyl) phosphine, dicyclohexyl (2 −
Cyclohexylphenyl) phosphine, dicyclohexyl [2- (2'-dimethylamino) phenyl] phosphine, dicyclohexyl [2- (2'-methylphenyl)
Phenyl] phosphine, dicyclohexyl [2- (2 '
-Iso-propylphenyl) phenyl] phosphine,
2,2'-bis (dicyclohexylphosphino) -1,
1′-binaphthyl, 1,1′-bis (dicyclohexylphosphino) ferrocene, and further 1,2-bis ((diphenylphosphino) ethane [(C ₆ H ₅ ) ₂ P
_{(CH 2) 2 P (C} 6 H 5) 2 ], 1,3-bis (diphenylphosphino) propane _{[(C 6 H 5) 2 P} (CH 2) 3 P
(C ₆ H _{5) 2],} 1,4-bis (diphenylphosphino) butane _{[(C 6 H 5) 2 P} (CH 2) 4 P (C
₆ H _{5) 2],} 1,5-bis (diphenylphosphino) pentane _{[(C 6 H 5) 2 P} (CH 2) 5 P (C 6 H 5) 2 ], tris (diphenylphosphino ethyl) phosphine [P
_{[(C 6 H 5) 2} PCH 2 CH 2] 3 ], 2,3-bis (diphenylphosphino) butane _{[(C 6 H 5) 2 PCH} (C
_{H 3) (CH 3) CHP} (C 6 H 5) 2 ], and the like.

Preferably, dicyclohexylphenylphosphine, di-tert-butylphenylphosphine, dicyclohexyl- (2-phenylphenyl) phosphine, di
-tert-butyl- (2-phenylphenyl) phosphine,
Examples thereof include phosphorus-based ligands having a sterically bulky substituent such as dicyclohexyl- (2-cyclohexylphenyl) phosphine and di-tert-butyl- (2-cyclohexyl) phosphine.

Some of these phosphine compounds are available as reagents, and, for example, J. Org. Chem., Vo.
l65, No4, P1158-1174, (2000), J. Am. Chem. Soc., Vol12
1, p4369-4378 (1999), J. Am. Chem. Soc., Vol120, p7369-73
70 (1998) and the like.

Examples of the base used in the production method of the present invention include inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide and potassium phosphate, sodium-tert-butoxide, potassium-tert. -Butoxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium (2,4,6-tri-tert-butylphenolate), potassium (2,4,6-tri-tert-butylphenoate) And metal alkoxides such as

The amount of the base used is not particularly limited, but is usually 0.5 to 3 equivalents, preferably 0.8 to 3 with respect to the halogen atom of the halogenated aromatic compound.
Use 2 equivalents.

Paradigm used in the production method of the present invention
The um compound is not particularly limited,
For example, palladium chloride (PdCl₂), Paradim bromide
(PdBr₂), Palladium iodide (PdI₂), Acetate
Lazim (Pd (OCOCH₃)₂), Pd (CH₂COC
H₂COCH₃)₂, K₂PdCl_Four, K₂PdCl₆, K₂P
d (NO₃)_Four, Tris (dibenzylideneacetone) dipa
Radium, dichlorobis (ethylene) palladium (Pd
Cl₂(C₂H_Four)₂), Pd (π-C_FiveH_Five)₂Organic distribution
Ligand complex, PdCl₂(NH₃)₂, PdCl₂[N (C₂
H_Five)₃]₂, Pd (NO₃)₂(NH₃)₆N-coordination such as
Complex, Pd [P (CH₃)₃]_Four, Pd [P (C₂H_Five)₃]
_Four, Pd [P (n-C₃H₇)₃] _Four, Pd [P (iso-C₃H
₇)₃]_Four, Pd [P (n-C_FourH₉)₃]_Four, Pd [P (ter
t-C_FourH₉)₃]_Four, Pd [P (Cyc-C₆H₁₁)₃]_Four, Pd
[P (C₆H_Five)₃]_Four, Pd [P (o-CH₃-C₆H_Four)₃]
_Four, PdCO₂[P (C₆H_Five)₃]_Four, Pd (C₂H_Four) [P
(C₆H_Five)₃]₂, PdCl₂[P (C₆H_Five)₃]₂, Pd
Cl₂[P (n-C _FourH₉)₃]₂, PdCl₂[P (tert-
C_FourH₉)₃]₂, PdBr₂[P (C₆H_Five)₃] ₂, PdB
r₂[P (n-C_FourH₉)₃]₂, PdBr₂[P (tert-C
_FourH₉)₃]₂, PdCl₂[P (OCH₃)₃]₂, PdBr
₂[P (OCH₃)₃]₂, PdI₂[P (OCH₃)₃]₂,
PdCl (C₆H_Five) [P (C₆H_Five)₃]₂Like, trivalent
Examples of complexes that use phosphine compounds as ligands
You can

In the production method of the present invention, the combination of the palladium compound and the phosphine compound having an alkyl group and an aryl group in the same molecule is used in a molar ratio of 1 to 10 with respect to the palladium atom of the palladium compound.
0, preferably 1: 1 to 20, more preferably 1: 1
Use an amount of -10. The amount of the palladium compound used is 1: 0.1 to 0.0000 in molar ratio with respect to the halogen atom of the diarylamino-substituted halogenated aromatic compound.
01, preferably 1: 0.05 to 0.00002, more preferably 1: 0.02 to 0.000005.

In the production method of the present invention, the phosphine compound having an alkyl group and an aryl group in the same molecule may be used alone or in combination of two or more. Furthermore, the palladium compounds may be used alone or in combination of two or more.

A preferred combination of a palladium compound and a phosphine compound having an alkyl group and an aryl group in the same molecule is, for example, palladium acetate / di-t.
ert-Butylphenylphosphine, palladium acetate / dicyclohexylphenylphosphine, palladium acetate / di
-tert-butyl- (2-phenylphenyl) phosphine,
Palladium acetate / 2,2'-bis (dicyclohexylphosphino) -1,1'-binaphthyl, dichlorobis (triphenylphosphine) palladium / di-tert-butylphenylphosphine, tetrakis (triphenylphosphine) palladium / di-tert- Butylphenylphosphine,
Tris (dibenzylideneacetone) dipalladium / di-t
ert-Butyl- (2-phenylphenyl) phosphine, tris (dibenzylideneacetone) dipalladium / di-ter
t-Butylphenylphosphine, tris (dibenzylideneacetone) dipalladium / dicyclohexylphenylphosphine, tris (dibenzylideneacetone) dipalladium / di-tert-butyl- (2-cyclohexylphenyl) phosphine, tris (dibenzylideneacetone) dipalladium / 2,2'-bis (di-tert-butylphosphino) -1,1'-binaphthyl can be mentioned.

In the production method of the present invention, an organic solvent can be used if desired. As the organic solvent used as desired, for example, aromatic hydrocarbon solvents such as benzene, toluene, o-xylene, m-xylene, p-xylene, mixed xylene, mesitylene, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether. , Ethylene glycol diethyl ether,
An ether solvent such as diethylene glycol dimethyl ether, diisopropyl ether and diisobutyl ether, an amide solvent such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide and the like can be used, and these can be used alone. They may be used, or a plurality of them may be used in combination.

An aromatic hydrocarbon solvent or an ether solvent is preferable, and an aromatic hydrocarbon solvent is more preferable.

In the production method of the present invention, the amount of the organic solvent used, if desired, is not particularly limited, but the concentration is preferably 0.1 M to 5 M with respect to the halogenated aromatic compound. Amount, more preferably,
The amount is such that the concentration becomes 0.25M to 2M.

The reaction conditions of the production method of the present invention are usually carried out under a stream of an inert gas (eg, nitrogen, argon, helium). The reaction temperature is preferably room temperature or lower to a temperature not higher than the boiling point of the organic solvent to be used, and more preferably room temperature to 150 ° C. or lower. Also,
The reaction may be carried out under normal pressure, or, if necessary, under reduced pressure or increased pressure. It is preferably carried out at normal pressure.

The progress of the reaction can be followed by a conventional method such as chromatography.

The arylamine compound produced by the production method of the present invention is usually subjected to a treatment such as washing with water, and then the organic solvent and the like are removed (under normal pressure or reduced pressure, if necessary), and then recrystallized. It can be purified by a conventional purification method such as column chromatography. It is also preferable that the solvent, low volatile components, and the like be removed under reduced pressure after that to perform sublimation purification under high vacuum. The structure of the product was analyzed by elemental analysis, MS
(FD-MS) analysis, IR analysis, ¹ H-NMR, ¹³ C-
It can be identified by NMR or the like.

The arylamine compound produced by the production method of the present invention is not particularly limited, but examples thereof include the compounds shown below.

1.N, N-diphenyl-2- (4'-aminophenyl) -3,4,5-triphenylthiophene 2.N-phenyl-N- (1 "-naphthyl) -2- (4 '
-Aminophenyl) -3,4,5-triphenylthiophene 3.N-phenyl-N- (2 "-naphthyl) -2- (4 '
-Aminophenyl) -3,4,5-triphenylthiophene 4.N-phenyl-N- (4 "-phenylphenyl) -2
-(4'-aminophenyl) -3,4,5-triphenylthiophene 5.N-phenyl-N- (2 "-phenylphenyl) -2
-(4'-Aminophenyl) -3,4,5-triphenylthiophene 6.N-phenyl-N- (9 "-anthracenyl) -2-
(4'-Aminophenyl) -3,4,5-triphenylthiophene 7.N-phenyl-N- (9 "-phenanthrenyl) -2
-(4'-aminophenyl) -3,4,5-triphenylthiophene 8.N-phenyl-N- (1 "-pyrenyl) -2- (4 '
-Aminophenyl) -3,4,5-triphenylthiophene 9.N, N-di (1 "-naphthyl) -2- (4'-aminophenyl) -3,4,5-triphenylthiophene 10.N , N-di (2 "-naphthyl) -2- (4'-amineophenyl) -3,4,5-triphenylthiophene 11.N, N- (4" -phenylphenyl) -2- (4 '
-Aminophenyl) -3,4,5-triphenylthiophene 12.N- (1 "-naphthyl) -N- (2"'-naphthyl) -2- (4'-aminophenyl) -3,4,5 -Triphenylthiophene 13.N- (1 "-naphthyl) -N- (4"'-phenylphenyl) -2- (4'-aminophenyl) -3,4
5-Triphenylthiophene 14.N- (1 "-naphthyl) -N- (4"'-cyclohexylphenyl) -2- (4'-aminophenyl)-
3,4,5-Triphenylthiophene 15.N- (1 "-naphthyl) -N- (9"'-anthracenyl) -2- (4'-aminophenyl) -3,4,5
-Triphenylthiophene 16.N- (1 "-naphthyl) -N- (9"'-phenanthrenyl) -2- (4'-aminophenyl) -3,4
5-triphenylthiophene 17.N-carbazolyl-2- (4'-aminophenyl)
-3,4,5-Triphenylthiophene 18.N-dibenzo [b, f] azepinyl-2- (4'-aminophenyl) -3,4,5-triphenylthiophene 19.N-phenothiazinyl-2- (4'-Aminophenyl) -3,4,5-triphenylthiophene 20.N, N, N ', N'-tetraphenyl-2,5-bis (4'-aminophenyl) -3,4-diphenyl Thiophene

21. N, N, N ', N'-tetra (1 "-
Naphthyl) -2,5-bis (4'-aminophenyl)-
3,4-diphenylthiophene 22.N, N, N ', N'-tetra (2 "-naphthyl)-
2,5-bis (4'-aminophenyl) -3,4-diphenylthiophene 23.N, N, N ', N'-tetra (4 "-phenylphenyl) -2,5-bis (4'-amino) Phenyl) -3,
4-diphenylthiophene 24.N, N'-diphenyl-N, N'-di (1 "-naphthyl) -2,5-bis (4'-aminophenyl) -3,
4-diphenylthiophene 25.N, N'-diphenyl-N, N'-di (2 "-naphthyl) -2,5-bis (4'-aminophenyl) -3,
4-diphenylthiophene 26.N, N'-diphenyl-N, N'-di (4 "-phenylphenyl) -2,5-bis (4'-aminophenyl) -3,4-diphenylthiophene 27.N, N'-diphenyl-N, N'-di (2 "-phenylphenyl) -2,5-bis (4'-aminophenyl) -3,4-diphenylthiophene 28.N, N'-diphenyl-N, N '-Di (9 "-anthracenyl) -2,5-bis (4'-aminophenyl)
-3,4-Diphenylthiophene 29.N, N'-diphenyl-N, N'-di (9-phenanthrenyl) -2,5-bis (4'-aminophenyl)
-3,4-diphenylthiophene 30.N, N'-di (1 "-naphthyl) -N, N'-di (4"'-phenylphenyl) -2,5-bis (4'-
Aminophenyl) -3,4-diphenylthiophene 31.N, N'-di (1 "-naphthyl) -N, N'-di (2"'-phenylphenyl) -2,5-bis (4'-
Aminophenyl) -3,4-diphenylthiophene 32.N, N'-di (1 "-naphthyl) -N, N'-di (4"'-cyclohexylphenyl) -2,5-bis (4'-amino) Phenyl) -3,4-diphenylthiophene 33.N, N'-di (1 "-naphthyl) -N, N'-di (9"'-anthracenyl) -2,5-bis (4'-aminophenyl) -3,4-diphenylthiophene 34.N, N'-di (1 "-naphthyl) -N, N'-di (9"'-phenanthrenyl) -2,5-bis (4'-
Aminophenyl) -3,4-diphenylthiophene 35.N, N'-di (4 "-phenylphenyl) -N,
N'-di (9 "'-anthracenyl) -2,5-bis (4'-aminophenyl) -3,4-diphenylthiophene 36.N, N'-di (4" -phenylphenyl) -N,
N'-di (9 "'-phenanthrenyl) -2,5-bis (4'-aminophenyl) -3,4-diphenylthiophene 37.N, N'-di (2" -phenylphenyl) -N,
N'-di (4 "'-phenylphenyl) -2,5-bis (4'-aminophenyl) -3,4-diphenylthiophene 38.N, N'-di (2" -phenylphenyl) -N,
N'-di (4 "'-cyclohexylphenyl) -2,5
-Bis (4'-aminophenyl) -3,4-diphenylthiophene 39.N, N'-di (2 "-phenylphenyl) -N,
N'-di (2 "', 6"'-dimethylphenyl) -2,
5-bis (4'-aminophenyl) -3,4-diphenylthiophene 40.N, N'-bis (carbazolyl) -2,5-bis (4'-aminophenyl) -3,4-diphenylthiophene

41. N, N'-bis (dibenzo [b, f] azepinyl) -2,5-bis (4'-aminophenyl) -3,
4-diphenylthiophene 42.N, N'-bis (phenothiazinyl) -2,5-bis (4'-aminophenyl) -3,4-diphenylthiophene 43.N, N, N ', N'-tetraphenyl -2,3-Bis (4'-aminophenyl) -4,5-diphenylthiophene 44.N, N, N ', N'-tetra (1 "-naphthyl)-
2,3-bis (4'-aminophenyl) -4,5-diphenylthiophene 45.N, N, N ', N'-tetraphenyl-2,4-bis (4'-aminophenyl) -3,5 -Diphenylthiophene 46.N, N, N ', N'-tetra (1 "-naphthyl)-
2,4-bis (4'-aminophenyl) -3,5-diphenylthiophene 47.N, N'-bis (carbazolyl) -2,3-bis (4'-aminophenyl) -4,5-diphenylthiophene 48.N, N'-bis (phenothiazinyl) -2,3-bis (4'-aminophenyl) -4,5-diphenylthiophene 49.N, N, N ', N', N ", N"- Hexaphenyl-2,3,5-tris (4'-aminophenyl) -4-
Phenylthiophene 50. N, N, N ', N', N ", N" -hexa (1 "-
Naphthyl) -2,3,5-tris (4'-phenyl)-
4-Phenylthiophene 51. N, N, N ', N', N ", N" -hexaphenyl-2,4,5-tris (4'-aminophenyl) -3-
Phenylthiophene 52.N, N, N ', N', N ", N" -hexa (1 "-
Naphthyl) -2,4,5-tris (4'-aminophenyl) -3-phenylthiophene 53.N, N ', N "-tris (carbazolyl) -2,
3,5-Tris (4'-aminophenyl) -4-phenylthiophene 54.N, N ', N "-tris (phenothiazinyl)-
2,3,5-Tris (4'-aminopheniur) -4-
Phenylthiophene 55.N, N ', N "-tris (carbazolyl) -2,
4,5-Tris (4'-aminophenyl) -3-phenylthiophene 56.N, N ', N "-tris (dibenzo [b, f] azepinyl) -2,4,5-tris (4'-amino) Phenyl)-
3-phenylthiophene 57.N, N, N ', N', N ", N", N "', N"'
-Octaphenyl-2,3,4,5-tetrakis (4 '
-Aminophenyl) thiophene 58.N, N, N ', N', N ", N", N "', N"'
-Octa (1 "-naphthyl) -2,3,4,5-tetrakis (4'-aminophenyl) thiophene 59.N, N, N ', N', N", N ", N"', N "'
-Octa (2 "-naphthyl) -2,3,4,5-tetrakis (4'-aminophenyl) thiophene 60.N, N ', N", N "'-tetraphenyl-N,
N ', N ", N"'-tetra (1 "-naphthyl) -2,
3,4,5-Tetrakis (4'-aminophenyl) thiophene 61.N, N ', N ", N"'-tetraphenyl-N,
N ', N ", N"'-tetra (2 "-naphthyl) -2,
3,4,5-Tetrakis (4'-aminophenyl) thiophene 62.N, N ', N ", N"'-tetraphenyl-N,
N ', N ", N"'-tetra (2 "-phenylphenyl) -2,3,4,5-tetrakis (4'-aminophenyl) thiophene 63.N, N ', N", N "'- Tetrakis (carbazolyl) -2,3,4,5-tetrakis (4'-aminophenyl) thiophene

Next, the organic electroluminescent device using the arylamine compound manufactured by the manufacturing method of the present invention will be described in detail.

The organic electroluminescent device of the present invention is an organic electroluminescent device in which at least one layer containing at least one arylamine compound produced by the production method of the present invention is sandwiched between a pair of electrodes.

The organic electroluminescent element usually comprises at least one light emitting layer containing at least one light emitting component sandwiched between a pair of electrodes. Considering the respective functional levels of hole injection and hole transport, electron injection and electron transport of the compound used for the light emitting layer, and if desired, a hole injection transport layer and / or electron injection containing a hole injection component. An electron injecting and transporting layer containing a transporting component can also be provided.

For example, when the compound used for the light emitting layer has a good hole injecting function, a hole transporting function and / or an electron injecting function, and an electron transporting function, the light emitting layer is a hole injecting and transporting layer and / or an electron. A single-layer element structure can be used as the element structure that also serves as the injection and transport layer. When the light emitting layer has a poor hole injecting function and / or hole transporting function, a two-layer type element structure in which a hole injecting and transporting layer is provided on the anode side of the light emitting layer, and the light emitting layer has an electron injecting function and / or Alternatively, when the electron transporting function is poor, a two-layer element structure can be used in which an electron injecting and transporting layer is provided on the cathode side of the light emitting layer.
Further, it is also possible to form a three-layer type device structure in which the light emitting layer is sandwiched between the hole injecting and transporting layer and the electron injecting and transporting layer.

Each of the hole injecting and transporting layer, the electron injecting and transporting layer and the light emitting layer may have a single-layer structure or a multi-layered structure, and the hole injecting and transporting layer and the electron injecting and transporting layer are In each layer, a layer having an injection function and a layer having a transport function may be separately provided.

In the organic electroluminescent device of the present invention, the arylamine compound produced by the production method of the present invention is preferably used as a constituent component of the hole injecting and transporting layer and / or the light emitting layer. More preferably, it is used as a constituent of the layer.

In the organic electroluminescent device of the present invention, the arylamine compound produced by the production method of the present invention may be used alone or in combination.

The constitution of the organic electroluminescent device of the present invention is not particularly limited, but for example, (A) anode / hole injecting / transporting layer / light emitting layer / electron injecting / transporting layer / cathode type device (see FIG. 1), (B) anode / hole injecting / transporting layer / light emitting layer /
Examples include a cathode type device (FIG. 2), (C) anode / light emitting layer / electron injecting / transporting layer / cathode type device (FIG. 3), (D) anode / light emitting layer / cathode type device (FIG. 4), and the like. it can. Further, (E) anode / hole injecting / transporting layer / electron injecting / transporting layer / light emitting layer / electron injecting / transporting layer / cathode type element (FIG. 5) in which the light emitting layer is sandwiched between electron injecting and transporting layers may be used. it can. The (D) type element structure is a type element in which a light emitting component is sandwiched between a pair of electrodes in a single layer as a light emitting layer,
(F) A device of a type in which a hole injection / transport component, a light emitting component and an electron injection component are mixed as a light emitting layer and sandwiched between a pair of electrodes (FIG. 6), and (G) a hole injection is performed as a light emitting layer. An element of a type in which a transport component and a light emitting component are mixed and sandwiched between a pair of electrodes (FIG. 7), and (H) a pair of electrodes in a single layer in which a light emitting component and an electron injection component are mixed as a light emitting layer. It may be any of the types of elements sandwiched between them (FIG. 8).

The organic electroluminescent element of the present invention is not limited to these element configurations, and a plurality of hole injecting and transporting layers, light emitting layers and electron injecting and transporting layers may be provided in each type of element. Is. Further, in each type of device, the hole injecting and transporting layer is provided between the light emitting layer, the mixed layer of the hole injecting and transporting component and the light emitting component and / or the light emitting component is provided between the light emitting layer and the electron injecting and transporting layer. It is also possible to provide a mixed layer of the electron injecting and transporting component.

A preferable structure of the organic electroluminescence device is as follows.
(A) type element, (B) type element, (E) type element, (F) type element or (G) type element, and more preferably,
It is an (A) type element, a (B) type element or a (G) type element.

The constituent elements of the organic electroluminescent device of the present invention will be described in detail below. As an example, (A) anode / hole injecting / transporting layer / light emitting layer / electron injecting / transporting layer / cathode type element shown in FIG. 1 will be described.

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

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

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

The anode can be formed on the substrate by using these electrode materials by a method such as a vapor deposition method or a sputtering method. The anode may have a single layer structure or a multilayer structure. The sheet electric resistance of the anode is preferably set to several hundreds Ω / □ or less, more preferably about 5 to 50Ω / □. Although the thickness of the anode depends on the material of the electrode material used, it is generally 5 to 100.
The thickness is set to about 0 nm, more preferably about 10 to 500 nm.

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

The hole injecting and transporting layer comprises the compound represented by the general formula (1), the compound represented by the general formula (2) and / or another compound having a hole injecting and transporting function (for example, a phthalocyanine derivative, Triarylamine derivative, triarylmethane derivative, oxazole derivative, hydrazone derivative, stilbene derivative, pyrazoline derivative, polysilane derivative, polyphenylene vinylene and its derivatives, polythiophene and its derivatives, poly-N-vinylcarbazole, etc.) Can be formed. The compound having a hole injection / transport function is
They may be used alone or in combination.

The organic electroluminescence device of the present invention preferably contains the arylamine compound produced by the production method of the present invention in the hole injecting and transporting layer. Compounds having a hole injecting and transporting function other than the arylamine compound produced by the production method of the present invention which can be used in the organic electroluminescent device of the present invention include triarylamine derivatives (for example, 4, 4'-bis [N-phenyl-N- (4 "-methylphenyl) amino] biphenyl, 4,4'-bis [N-phenyl-N- (3" -methylphenyl) amino] biphenyl, 4,4 ' -Bis [N
-Phenyl-N- (3 "-methoxyphenyl) amino]
Biphenyl, 4,4'-bis [N-phenyl-N-
(1 "-naphthyl) amino] biphenyl, 3,3'-dimethyl-4,4'-bis [N-phenyl-N- (3"-
Methylphenyl) amino] biphenyl, 1,1-bis [4 ′-[N, N-di (4 ″ -methylphenyl) amino] phenyl] cyclohexane, 9,10-bis [N-
(4'-Methylphenyl) -N- (4 "-n-butylphenyl) amino] phenanthrene, 3,8-bis (N,
N-diphenylamino) -6-phenylphenanthridine, 4-methyl-N, N-bis [4 ", 4"'-bis[N',N'-di (4-methylphenyl) amino] biphenyl-4 -Yl] aniline, N, N'-bis [4-
(Diphenylamino) phenyl] -N, N'-diphenyl-1,3-diaminobenzene, N, N'-bis [4-
(Diphenylamino) phenyl] -N, N'-diphenyl-1,4-diaminobenzene, 5,5 "-bis [4-
(Bis [4-methylphenyl] amino] phenyl-2,
2 ': 5', 2 "-terthiophene, 1,3,5-tris (diphenylamino) benzene, 4,4 ', 4" -tris (N-carbazolyyl) triphenylamine, 4,
4 ', 4 "-tris [N, N-bis (4"'-tert-butylbiphenyl-4 ""-yl) amino] triphenylamine, 1,3,5-tris [N- (4'-diphenyl) Amino] benzene and other polythiophenes and their derivatives, and poly-N-vinylcarbazole and its derivatives are more preferred.

When the arylamine compound produced by the production method of the present invention is used in combination with another compound having a hole injection function, the arylamine compound produced by the production method of the present invention occupies in the hole injection transport layer. The content of
It is preferably 0.1% by weight or more, and more preferably 0.1% by weight.
5 to 99.9% by weight, more preferably 3 to 97% by weight
Is.

The light emitting layer 4 has a function of injecting holes and electrons,
It is a layer containing a compound having a function of transporting them and a function of generating excitons by recombination of holes and electrons. The light-emitting layer uses the arylamine compound produced by the production method of the present invention as a host material and contains at least one compound having a light-emitting function other than the asymmetric arylamine of the present invention.
It can be used as a seed guest material and formed.

Examples of the compound (guest material) having a light emitting function other than the arylamine compound of the present invention include:
Acridone derivatives, quinacridone derivatives, diketopyrrolopyrrole derivatives, polycyclic aromatic compounds [for example, rubrene, anthracene, tetracene, pyrene, perylene, chrysene, decacyclene, coronene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, 9,10- Diphenylanthracene, 9,10-bis (phenylethynyl) anthracene, 1,4-bis (9'-ethynylanthocenyl) benzene, 4,4'-
Bis (9 "-ethynylanthracenyl) biphenyl, dibenzo [f, f] diindeno [1,2,3-cd: 1 ', 2', 3'-lm] perylene derivative], triarylamine derivative (for example,
Examples of the compound having a hole injecting / transporting function include the compounds described above), organometallic complexes [eg, tris (8-quinolinolato) aluminum, bis (10-
Benzo [h] quinolinolato) beryllium, 2- (2 '
Zinc salt of -hydroxyphenyl) benzothiazole, 4
-Zinc salt of hydroxyacridine, zinc salt of 3-hydroxyflavone, beryllium salt of 5-hydroxyflavone, aluminum salt of 5-hydroxyflavone], stilbene derivative [eg 1,1,4,4-tetraphenyl-1, 3-butadiene, 4,4'-bis (2,2-diphenylvinyl) biphenyl, 4,4'-bis [(1,
1,2-triphenyl) ethenyl] biphenyl], coumarin derivative (for example, coumarin 1, coumarin 6, coumarin 7, coumarin 30, coumarin 106, coumarin 13)
8, coumarin 151, coumarin 152, coumarin 15
3, coumarin 307, coumarin 311, coumarin 31
4, coumarin 334, coumarin 338, coumarin 34
3, coumarin 500), pyran derivative (eg DCM
1, DCM2), oxazone derivative (for example, Nile red), benzothiazole derivative, benzoxazole derivative, benzimidazole derivative, pyrazine derivative,
Cinnamic acid ester derivative, poly-N-vinylcarbazole and its derivative, polythiophene and its derivative, polyphenylene and its derivative, polyfluorene and its derivative, polyphenylenevinylene and its derivative, polybiphenylenevinylene and its derivative,
Examples thereof include polyterphenylene vinylene and its derivatives, polynaphthylene vinylene and its derivatives, polythienylene vinylene and its derivatives, and the like. As the compound (guest material) having a light emitting function other than the arylamine compound of the present invention, acridone derivatives, quinacridone derivatives, polycyclic aromatic compounds, triarylamine derivatives, organometallic complexes and stilbene derivatives are preferable, and polycyclic aromatic compounds are preferable. Compounds and organometallic complexes are more preferred.

The organic electroluminescent device of the present invention preferably contains the arylamine compound produced by the production method of the present invention as a host material in the light emitting layer. When the arylamine compound produced by the production method of the present invention is used as a host material in combination with another compound having a light emitting function, the content of the arylamine compound produced by the production method of the present invention in the light emitting layer is , Preferably 4
0.0.about.99.9%, more preferably 60.
It is 0 to 99.9% by weight.

The amount of the guest material used is 0.0 with respect to the arylamine compound produced by the production method of the present invention.
It is from 01 to 40% by weight, preferably from 0.05 to 30% by weight, more preferably from 0.1 to 20% by weight. The guest materials may be used alone or in combination of two or more.

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

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

(Q) ₃ -Al (a) (wherein Q represents a substituted or unsubstituted 8-quinolinolate ligand) (Q) ₂ -Al-OL '(b) (wherein Q represents a substituted or unsubstituted 8-quinolinolate ligand, OL ′ represents a phenolate ligand,
L ′ represents a hydrocarbon group having a phenyl group and having 6 to 24 carbon atoms. (Q) ₂ —Al—O—Al— (Q) ₂ (c) (In the formula, Q is a substituted or unsubstituted 8- Represents a quinolinolato ligand)

Specific examples of the organoaluminum complex having a substituted or unsubstituted 8-quinolinolate ligand include:
For example, tris (8-quinolinolato) aluminum,
Tris (4-methyl-8-quinolinolato) aluminum, tris (5-methyl-8-quinolinolato) aluminum, tris (3,4-dimethyl-8-quinolinolato) aluminum, tris (4,5-dimethyl-8-quinolinolato) Aluminum, tris (4,6-dimethyl-8-quinolinolato) aluminum,

Bis (2-methyl-8-quinolinolate)
(Phenolato) aluminum, bis (2-methyl-8)
-Quinolinolate) (2-methylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (3
-Methylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (4-methylphenolate)
Aluminum, bis (2-methyl-8-quinolinolato) (2-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum, bis (2-methyl-8-quinolinolate) (2,
3-Dimethylphenolate) aluminum, bis (2-
Methyl-8-quinolinolato) (2,6-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3,4-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato)
(3,5-Dimethylphenolate) aluminum, bis (2-methyl-8-quinolinoleate) (3,5-di-ter
t-butylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (2,6-diphenylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (2,4,6-triphenylphenolate) ) Aluminum, bis (2-methyl-8-quinolinolate) (2,4,6-trimethylphenolate) aluminum, bis (2-methyl-8-quinolinolate)
(2,4,5,6-tetramethylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (1
-Naphtholate) aluminum, bis (2-methyl-8)
-Quinolinolato) (2-naphtholate) aluminum, bis (2,4-dimethyl-8-quinolinolato)
(2-Phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3-phenylphenolato) aluminum, bis (2,4-dimethyl-8-quinolinolato) (4-phenylphenolato) aluminum , Bis (2,4-dimethyl-8-quinolinolate) (3,5-dimethylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolate) (3,5-di-tert-butylphenolate) aluminum ,

Bis (2-methyl-8-quinolinolate)
Aluminum-μ-oxo-bis (2-methyl-8-quinolinolato) aluminum, bis (2,4-dimethyl-8-quinolinolato) aluminum-μ-oxo-bis (2,4-dimethyl-8-quinolinolato) aluminum, Bis (2-methyl-4-ethyl-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-)
4-Ethyl-8-quinolinolato) aluminum, bis (2-methyl-4-methoxy-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-4-methoxy-8-quinolinolato) aluminum, bis (2-
Methyl-5-cyano-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-5-cyano-8-
Quinolinolato) aluminum, bis (2-methyl-5)
-Trifluoromethyl-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum. The compound having an electron injection function may be used alone or in combination of two or more.

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

For the cathode, these electrode materials can be formed on the electron injecting / transporting layer by, for example, the vapor deposition method, the sputtering method, the ion vapor deposition method, the ion plating method or the cluster ion beam method. The cathode may have a single layer structure or a multilayer structure. The sheet electric resistance of the cathode is preferably several hundred Ω / □ or less. The thickness of the cathode depends on the electrode material used, but is usually 5 to 1
The thickness is 000 nm, preferably 10 to 500 nm. In order to extract light emitted from the organic electroluminescent element of the present invention with high efficiency, at least one of the anode and the cathode is preferably transparent or semitransparent, and generally the transmittance of emitted light is 70% or more. Material of anode or cathode,
It is preferable to set the thickness.

In the organic electroluminescent device of the present invention, at least one of the hole injecting and transporting layer, the light emitting layer and the electron injecting and transporting layer may contain a singlet oxygen quencher. The singlet oxygen quencher is not particularly limited, but examples thereof include rubrene, nickel complex, and diphenylisobenzofuran, and rubrene is preferable.

The layer containing the singlet oxygen quencher is not particularly limited, but is preferably a light emitting layer or a hole injecting / transporting layer, and more preferably a hole injecting / transporting layer. is there. When the hole injecting and transporting layer contains a singlet oxygen quencher, it may be uniformly contained in the hole injecting and transporting layer, and a layer adjacent to the hole injecting and transporting layer (for example, a light emitting layer, a light emitting function). May be included in the vicinity of the electron injecting and transporting layer). The content of the singlet oxygen quencher is 0.01 to 50% by weight, preferably 0.05 to 30% by weight, based on the total amount of the layer (for example, the hole injecting and transporting layer) contained. Preferably,
It is 0.1 to 20% by weight.

Hole injecting / transporting layer, light emitting layer, electron injecting / transporting layer
The method of forming is not particularly limited,
For example, vacuum deposition method, ionization deposition method, solution coating method (example
For example, spin coating, casting, dip coating
Method, bar coat method, roll coat method, Langmuir Bou
Can be used.
Wear. Hole injecting and transporting layer, emitting layer, electron by vacuum evaporation method
When forming each layer such as injecting and transporting layer, vacuum deposition conditions
Ha. , But is not particularly limited, usually 10 ^-FiveT
Under a vacuum of about orr or less, a bow of about 50 to 500 ° C
Temperature (deposition source temperature), substrate temperature of about -50 to 300 ° C
Deposition rate of 0.005 to 50 nm / sec.
It is preferable to apply. In this case, the hole injection transport layer
Each layer such as the light layer and the electron injecting and transporting layer is continuously placed under vacuum.
It is preferably formed. By continuously forming
It is possible to manufacture organic electroluminescent devices with excellent characteristics.
Become. By vacuum evaporation method, hole injection transport layer, light emitting layer,
Each layer such as child injection transport layer is formed using multiple compounds
Temperature control for each boat containing compound
Therefore, co-evaporation is preferable.

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

Further, as the binder resin which can be used for each layer such as the hole injecting and transporting layer, the light emitting layer and the electron injecting and transporting layer,
Poly-N-vinylcarbazole, polyarylate, polystyrene, polyester, polysiloxane, polymethylmethacrylate, polymethylacrylate, polyether, polycarbonate, polyamide, polyimide, polyamideimide, polyparaxylene, polyethylene, polyphenylene oxide, polyether sulfone , Polyaniline and its derivatives, polythiophene and its derivatives, polyphenylene vinylene and its derivatives, polyfluorene and its derivatives, polythienylene vinylene and its derivatives, and the like. The binder resins may be used alone or in combination of two or more. The concentration of the coating liquid is not particularly limited, but can be set within a concentration range suitable for producing a desired thickness by the coating method to be performed, and is usually 0.1 to 50% by weight, preferably , 1 to 30% by weight
Set to. When a binder resin is used, the amount thereof is not particularly limited, but is usually relative to the total amount of the component and the binder resin forming each layer such as the hole injecting and transporting layer, the light emitting layer and the electron injecting and transporting layer. The binder resin content (based on the total amount of each component in the case of forming a one-layer type element) is 5 to 99.9% by weight, preferably 10 to 9
It is used so as to be 9% by weight.

The film pressure of each layer such as the hole injecting / transporting layer, the light emitting layer and the electron injecting / transporting layer is not particularly limited, but is usually 5 nm to 5 μm.

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

Further, in the organic electroluminescent element of the present invention, a metal oxide film (eg, aluminum oxide film) or a metal fluoride film can be provided on the electrode as a protective film. In the organic electroluminescent element of the present invention, an interface layer (intermediate layer) can be provided on the surface of the anode. Examples of the material of the interface layer include organic phosphorus compounds, polysilanes, aromatic amine derivatives, and phthalocyanine derivatives. Further, an electrode, for example, an anode, can be used by treating its surface with acid, ammonia / hydrogen peroxide, or plasma.

The organic electroluminescent device of the present invention can be usually used as a DC drive type device, but can also be used as an AC drive type device. Further, the organic electroluminescent element of the present invention may be of a passive drive type such as a segment type or a simple matrix drive type, or an active drive type such as a TFT (thin film transistor) type or a MIM (metal-insulator-metal) type. May be The drive voltage is usually 2 to 30V. The organic electroluminescent device of the present invention includes a panel type light source (for example, a backlight such as a watch and a liquid crystal panel), various light emitting devices (for example, a light emitting device such as an LED), and various display devices [for example, information display. It can be used for devices (PC monitors, display devices for mobile phones and mobile terminals), various signs, various sensors, etc.

[0089]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

Example 1: Exemplified compound 25 [N, N'-diphenyl-N, N'-di (2 "-naphthyl) -2,5-
Preparation of bis (4'-aminophenyl) -3,4-diphenylthiophene] 2,5-bis (4'-bromophenyl) -3,4-diphenylthiophene 21.8 g (0.04 mol), N-
Phenyl-N- (2-naphthyl) amine 17.6 g
(0.08 mol), tert-butoxy sodium 1
0.96 g of dicyclohexylphenylphosphine was added to a mixture of 0.8 g (0.11 mol), tris (benzylideneacetone) dipalladium 0.4 g (0.44 mmol) and o-xylene 70 g under a nitrogen atmosphere.
(3.5 mmol) was added, and then the mixture was heated with stirring at 120 ° C. for 4 hours. The reaction mixture after heating for 4 hours was analyzed by GPC. As a result, the target product, N, N'-diphenyl-N, N'-di (2 "-naphthyl) -2,5-bis (4'-aminophenyl), was obtained. The content of -3,4-diphenylthiophene was 95% by area, and formation of a compound having a molecular weight higher than that of the target product was not observed, after which the reaction mixture was cooled to room temperature and discharged into 800 ml of methanol to produce the same. The crystals were separated by filtration, dissolved in toluene, purified by column chromatography, and recrystallized from toluene / hexane to give the desired N, N '.
-Diphenyl-N, N'-di (2 "-naphthyl) -2,
29.8 g of 5-bis (4'-aminophenyl) -3,4-diphenylthiophene was obtained as yellow crystals. Further, this compound was purified by sublimation at 360 ° C. and 1 × 10 ⁻⁴ Pa for 8 hours. The absorption maximum wavelength of this compound is 376.
nm, and the fluorescence maximum wavelength was 461 nm. The HOMO level of this compound determined from the redox potential was -5.17 eV.

Comparative Example 1 For comparison, a compound of Exemplified Compound 25 was produced using a copper catalyst. That is, 21.8 g of 2,5-bis (4′-bromophenyl) -3,4-diphenylthiophene
(0.04 mol), N-phenyl-N- (2-naphthyl) amine 17.6 g (0.08 mol), potassium carbonate 15.2 g (0.11 mol) 18-6-crown ether 1.0 g, copper chloride 0 A mixture of 0.5 g and 70 g of o-dichlorobenzene was heated at 180 ° C. under a nitrogen stream.
To 40 ° C., and the mixture was heated and stirred at the same temperature for 40 hours. The reaction mixture after heating for 40 hours was analyzed by GPC.
-Naphthyl) -2,5-bis (4'-aminophenyl)
The content of -3,4-diphenylthiophene is 22 area%
In addition, 68 area% of a high molecular weight compound was formed. Then, the reaction mixture was cooled to room temperature, 100 g of toluene was added, and the insoluble matter was filtered off. Toluene was distilled off from the filtrate under reduced pressure, and the residue was purified by silica gel column chromatography.

Comparative Example 2 For comparison, a compound of Exemplified Compound 25 was produced using tris (aryl) phosphine and a palladium compound.
That is, 2,5-bis (4'-bromophenyl)-
21.8 g (0.04 m) of 3,4-diphenylthiophene
ol), N-phenyl-N- (2-naphthyl) amine 1
A mixture of 7.6 g (0.08 mol), tris (2-methylphenyl) phosphine 1.064 g (3.5 mmol) and o-xylene 70 g was added under a nitrogen stream.
0.99 g (0.44 mmol) of palladium acetate was added, and then the reaction mixture was heated to 100 ° C. and heated and stirred at the same temperature for 6 hours. After 6 hours, the reaction mixture was subjected to GPC.
Content of the target N, N′-diphenyl-N, N′-di (2 ″ -naphthyl) -2,5-bis (4′-aminophenyl) -3,4-diphenylthiophene as analyzed by Was 15 area% and a high molecular weight product was 40 area% .After that, the reaction mixture was cooled to room temperature, 100 g of toluene was added, and the insoluble matter was separated by filtration. The solvent was distilled off and the residue was purified by silica gel column chromatography.

Example 2: Preparation of Exemplified Compound 26 Instead of using 17.6 g (0.08 mol) of N-phenyl-N- (2-naphthyl) amine in Example 1, N-phenyl-N- ( 4-phenylphenyl)
Exemplified Compound 26 was produced according to the procedure described in Example 1 except that 19.6 g (0.08 mol) of amine was used. From the GPC analysis at the end of the reaction, the target product was produced in an area of 97% by area, and formation of a high molecular weight compound was not observed. The maximum absorption wavelength of this compound is 337 nm.
And the maximum fluorescence wavelength was 461 nm. The HOMO level of this compound calculated from the redox potential is-
It was 5.18 eV.

Example 3: Preparation of Exemplified Compound 22 In Example 1, 17.6 g (0.08 mol) of N-phenyl-N- (2-naphthyl) amine, 0.4 g of tris (dibenzylideneacetone) dipalladium ( 0.4
4 mmol) and 0.96 g (3.5 mmol) of dicyclohexylphenylphosphine,
N, N-di (2-naphthyl) amine 21.5 g (0.0
8 mol), 0.099 g of palladium acetate (0.44 m
mol) and di-tert-butyl- (2-phenylphenyl) phosphine (1.043 g, 3.5 mmol) were used, following the procedure described in Example 1 for Exemplified Compound 2
2 was produced. From the GPC analysis after the completion of the reaction, the target product was produced in an area of 94% by area, and formation of a high molecular weight compound was not observed. The maximum absorption wavelength of this compound is 37
It was 6 nm and the fluorescence maximum wavelength was 461 nm. The HOMO level of this compound determined from the redox potential was -5.17 eV.

Example 4: Preparation of Exemplified Compound 40 In Example 1, 17.6 g (0.08 mol) of N-phenyl-N- (2-naphthyl) amine, 0.4 g (0% of tris (benzylideneacetone) dipalladium) .44
Instead of using 0.96 g (3.5 mmol) of dicyclohexylphenylphosphine and 13.4 g (0.08 mol) of carbazole, 0.099 g (0.44 mmol) of palladium acetate and di-tert-.
Exemplified compound 40 was produced according to the procedure described in Example 1 except that 1.064 g (3.5 mmol) of butyl- (2-cyclohexylphenyl) phosphine was used.
From the GPC analysis at the end of the reaction, 98 area% of the target product was formed, and formation of a high molecular weight product was not observed.
The absorption maximum wavelength of this compound was 344 nm, and the fluorescence maximum wavelength was 440 nm. Further, the HOMO level of this compound determined from the redox potential was −5.49 eV.
Met.

Example 5: Preparation of Exemplified Compound 28 Instead of using 17.6 g (0.08 mol) of N-phenyl-N- (2-naphthyl) amine in Example 1, N-phenyl-N- ( Exemplified Compound 28 was produced according to the procedure described in Example 1 except that 21.5 g (0.08 mol) of 9-anthracenyl) amine was used. GPC analysis of the reaction mixture at the end of the reaction revealed that the content of the target substance was 96 area%, and formation of a high molecular weight compound was not observed. The maximum absorption wavelength of this compound is 3
It was 60 nm and the fluorescence maximum wavelength was 520 nm.
The HOMO level of this compound determined from the redox potential was -5.20 eV.

Example 6: Preparation of Exemplified Compound 30 Instead of using 17.6 g (0.08 mol) of N-phenyl-N- (2-naphthyl) amine in Example 1, N- (1-naphthyl) was used. Exemplified Compound 30 was produced according to the procedure described in Example 1 except that 23.6 g (0.08 mol) of -N- (4'-phenylphenyl) -amine was used. GPC analysis of the reaction mixture at the end of the reaction revealed that the content of the target substance was 95% by area, and formation of a high molecular weight compound was not observed. The maximum absorption wavelength of this compound is 370 nm, and the maximum fluorescence wavelength is 460 nm.
was nm. The HOMO level of this compound determined from the redox potential was -5.15 eV.

Example 7: Preparation of Exemplified Compound 42 Instead of using 17.6 g (0.08 mol) of N-phenyl-N- (2-naphthyl) amine in Example 1, 15.9 g of phenothiazine (0. 08 mol)
Exemplified Compound 42 was produced according to the procedure described in Example 1 except that was used. GP of the reaction mixture at the end of the reaction
In the C analysis, the content of the target substance was 96 area%, and formation of a high molecular weight compound was not recognized. The absorption maximum wavelength of this compound is 368 nm, and the fluorescence maximum wavelength is 4
It was 62 nm. The HOMO level of this compound determined from the redox potential was -5.09 eV.

Example 8: Preparation of Exemplified Compound 29 Instead of using 17.6 g (0.08 mol) of N-phenyl-N- (2-naphthyl) amine in Example 1, N-phenyl-N- ( 9-phenanthrenyl)
Exemplified Compound 29 was produced according to the procedure described in Example 1 except that 21.5 g (0.08 mol) of amine was used. GPC analysis of the reaction mixture at the end of the reaction revealed that the content of the target substance was 93 area%, and formation of a high molecular weight compound was not observed. The absorption maximum wavelength of this compound was 372 nm, and the fluorescence maximum wavelength was 456 nm. In addition, the HOMO of this compound determined from the redox potential
The level was -5.10 eV.

Example 9: Preparation of Exemplified Compound 23 Instead of using 17.6 g (0.08 mol) of N-phenyl-N- (2-naphthyl) amine in Example 1, N, N-di (4 -Phenylphenyl) amine 2
Exemplified compound 23 was produced according to the procedure described in Example 1 except that 5.7 g (0.08 mol) was used. GPC analysis of the reaction mixture at the end of the reaction revealed that the content of the target substance was 97 area%, and formation of a high-molecular weight compound was not observed. The maximum absorption wavelength of this compound is 355n.
m, and the fluorescence maximum wavelength was 466 nm. The HOMO level of this compound calculated from the redox potential is-
It was 5.10 eV.

Example 10: Preparation of Exemplified Compound 34 Instead of using 17.6 g (0.08 mol) of N-phenyl-N- (2-naphthyl) amine in Example 1, N- (1-naphthyl) was used. Exemplified compound 34 was produced according to the procedure described in Example 1 except that 25.5 g (0.08 mol) of -N- (9'-phenanthrenyl) amine was used. GPC analysis of the reaction mixture at the end of the reaction revealed that the content of the target substance was 92 area%, and formation of a high molecular weight compound was not observed. The maximum absorption wavelength of this compound is 372 nm, and the maximum fluorescence wavelength is 455 n.
It was m. The HOMO level of this compound determined from the redox potential was -5.13 eV.

Example 11: Preparation of Exemplified Compound 36 Instead of using 17.6 g (0.08 mol) of N-phenyl-N- (2-naphthyl) amine in Example 1, N- (4-phenylphenyl) was used. ) -N- (9'-
Phenanthrenyl) amine 27.6g (0.08mo
According to the procedure described in Example 1, except that l) was used,
Exemplified compound 36 was produced. GPC analysis of the reaction mixture at the end of the reaction revealed that the content of the target substance was 94 area%, and formation of a high molecular weight compound was not observed. The absorption maximum wavelength of this compound was 368 nm, and the fluorescence maximum wavelength was 460 nm. The HOMO level of this compound determined from the redox potential was -5.12 eV.

Example 12: Preparation of Exemplified Compound 35 Instead of using 17.6 g (0.08 mol) of N-phenyl-N- (2-naphthyl) amine in Example 1, N- (4-phenylphenyl) was used. ) -N- (9'-
Anthracenyl) amine 27.6 g (0.08 mol)
Exemplified Compound 35 was produced according to the procedure described in Example 1 except that was used. GP of the reaction mixture at the end of the reaction
In the C analysis, the content of the target substance was 96 area%, and formation of a high molecular weight compound was not recognized. The absorption maximum wavelength of this compound is 378 nm, and the fluorescence maximum wavelength is 5
It was 21 nm. The HOMO level of this compound determined from the redox potential was -5.12 eV.

Example 13: Preparation of Exemplified Compound 21 Instead of using 17.6 g (0.08 mol) of N-phenyl-N- (2-naphthyl) amine in Example 1, N, N-di (1 -Naphthyl) amine 21.5 g
Exemplified Compound 21 was produced according to the procedure described in Example 1 except that (0.08 mol) was used. GPC analysis of the reaction mixture at the end of the reaction revealed that the content of the target substance was 91 area%, and formation of a high-molecular weight compound was not observed. The maximum absorption wavelength of this compound was 371 nm, and the maximum fluorescence wavelength was 455 nm. Further, the HOMO level of this compound determined from the redox potential was -5.1.
It was 1 eV.

Example 14: Preparation of Exemplified Compound 24 Instead of using 17.6 g (0.08 mol) of N-phenyl-N- (2-naphthyl) amine in Example 1, N-phenyl-N- ( 1-naphthyl) amine 1
Exemplified Compound 24 was produced according to the procedure described in Example 1 except that 7.6 g (0.08 mol) was used. GPC analysis of the reaction mixture at the end of the reaction revealed that the content of the target substance was 96 area%, and formation of a high molecular weight compound was not observed. The maximum absorption wavelength of this compound is 370n.
m, and the fluorescence maximum wavelength was 456 nm. The HOMO level of this compound calculated from the redox potential is-
It was 5.10 eV.

Example 15: Preparation of organic electroluminescent device An organic electroluminescent device was prepared in order to investigate the characteristics of the arylamine compound produced by the production method of the present invention as an organic electroluminescent device material. The arylamine compounds produced in Example 1, Comparative Example 1 and Comparative Example 2 are
Sublimation purification was performed before it was used for producing an organic electroluminescent device. A glass substrate having a 200 nm thick ITO transparent electrode (anode) was ultrasonically cleaned using neutral detergent, semicoclean (manufactured by Furuuchi Chemical Co., Ltd.), ultrapure water, acetone, and ethanol. This substrate was dried using nitrogen gas, further washed with UV / ozone, fixed on a substrate holder of a vapor deposition apparatus, and the vapor deposition tank was depressurized to 3 × 10 ⁻⁶ Torr. First, IT
A compound of Exemplified Compound 25 produced in Example 1 was vapor-deposited on the O transparent electrode at a vapor deposition rate of 0.2 nm / sec to a thickness of 75 nm to form a hole injecting and transporting layer. Next, tris (8-quinolinolato) aluminum was vapor-deposited on the hole injecting and transporting layer at a vapor deposition rate of 0.2 nm / sec to a thickness of 50 nm to form a light emitting layer also serving as an electron injecting and transporting layer.
Further, magnesium and silver were co-deposited as a cathode at a vapor deposition rate of 0.2 nm / sec to a thickness of 200 nm (weight ratio 10: 1) to form a cathode, and an organic electroluminescence device was produced. The vapor deposition was carried out while keeping the vacuum state of the vapor deposition tank. A direct current voltage was applied to the produced organic electroluminescence device, and it was continuously driven at a constant current density of 10 mA / cm ^{2 in} a dry atmosphere at 50 ° C. Initially 6.3V, brightness 48
A green emission of 0 cd / m ² was confirmed. The half-life of brightness was 750 hours.

Comparative Example 3 For comparison, in Example 15, instead of using the compound of Exemplified Compound 25 prepared in Example 1 in the formation of the hole injecting and transporting layer, Exemplified Compound 25 prepared in Comparative Example 1 was used. An organic electroluminescent device was produced by following the procedure described in Example 15 except that the compound of Example 1 was used. Green light emission was confirmed from the device. A direct current voltage is applied to the produced organic electroluminescence device, and the current is 10 mA / cm in a dry atmosphere at 50 ° C.
^It was continuously driven at a constant current density of ² . Initially 6.5
A green light emission with V and a luminance of 460 cd / m ² was confirmed.
The half-life of brightness was 500 hours. Comparison with Example 15 shows that the organic electroluminescent device using the arylamine compound manufactured by the manufacturing method of the present invention has a longer half-life of luminance.

Comparative Example 4 In Example 15, in forming the hole injecting and transporting layer,
An organic electroluminescent device was produced according to the procedure described in Example 15 except that the compound of Exemplified Compound 25 prepared in Example 1 was used instead of the compound of Exemplified Compound 25 prepared in Example 1. A direct current voltage is applied to the produced organic electroluminescent device at 50 ° C. in a dry atmosphere at 10 mA /
It was continuously driven at a constant current density of cm ² . Initially, 6.
Green light emission at 5 V and a luminance of 460 cd / m ² was confirmed. The half-life of brightness was 500 hours. Comparison with Example 15 shows that the organic electroluminescent device using the arylamine compound manufactured by the manufacturing method of the present invention has a longer half-life of luminance.

[0109]

INDUSTRIAL APPLICABILITY According to the present invention, it becomes possible to produce an arylamine compound having a low content of impurities while suppressing the production of a high molecular weight compound. Further, by using the arylamine compound of the present invention, light emission It has become possible to provide an organic electroluminescent device having a long life and excellent durability.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of an example of an organic electroluminescent device.

FIG. 2 is a schematic cross-sectional view of an example of an organic electroluminescent device.

FIG. 3 is a schematic cross-sectional view of an example of an organic electroluminescent device.

FIG. 4 is a schematic cross-sectional view of an example of an organic electroluminescent device.

FIG. 5 is a schematic cross-sectional view of an example of an organic electroluminescent device.

FIG. 6 is a schematic cross-sectional view of an example of an organic electroluminescent device.

FIG. 7 is a schematic cross-sectional view of an example of an organic electroluminescent device.

FIG. 8 is a schematic cross-sectional view of an example of an organic electroluminescent device.

[Explanation of symbols]

1: substrate 2: Anode 3: Hole injection transport layer 3a: hole injecting and transporting component 4: Light emitting layer 4a: luminous component 5: Electron injection transport layer 5 ": electron injection transport layer 5a: electron injection transport component 6: Cathode 7: Power supply

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI theme code (reference) // C07B 61/00 300 C07B 61/00 300 (72) Inventor Tsutomu Ishida 580-32 Nagaura, Sodegaura, Chiba Prefecture Mitsui Chemical Co., Ltd. In-company (72) Inventor Masakatsu Nakatsuka 580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemical Co., Ltd. In-company F-term (reference) 3K007 AB11 DB03 4C023 CA07 4C063 AA03 BB09 CC92 DD08 EE10 4H039 CA71 CD10 CD20

Claims (7)

[Claims] 1. A halogenated aromatic compound represented by the general formula (1) (formula 1) in the presence of a catalyst comprising a phosphine compound having an alkyl group and an aryl group in the same molecule and a palladium compound, and a base. And, [In the formula, X represents a halogen atom, and p, q, r and s
Represents 0 or 1, and p + q + r + s is not 0] A method for producing an arylamine compound, which comprises reacting a diaryl-substituted amine compound represented by the general formula (2) (formula 2). [Chemical 2] [In the formula, Ar ₁ and Ar ₂ represent a substituted or unsubstituted aryl group, and Ar ₁ and Ar ₂ may combine with each other to form a nitrogen-containing heterocycle] 2. The method for producing an arylamine compound according to claim 1, wherein X in the general formula (1) is a bromine atom. 3. The method for producing an arylamine compound according to claim 1, wherein in the general formula (1), r and s are each 1. 4. The method for producing an arylamine compound according to claim 1, wherein the alkyl group of the phosphine compound having an alkyl group and an aryl group in the same molecule is a cyclohexyl group or a tert-butyl group. 5. An arylamine compound produced by the production method according to any one of claims 1 to 4. 6. The arylamine compound according to claim 5,
An organic electroluminescence device comprising at least one layer containing at least one kind of material sandwiched between a pair of electrodes. 7. The layer containing the arylamine compound according to claim 5 is a hole injecting and transporting layer or a light emitting layer.
The organic electroluminescent element as described.