JP2001131128A - Bis(aminostyryl)stibene-based compound, its synthetic intermediate, method for producing the same and organic electroluminescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a bis(aminostyryl)stilbene-based compound capable of assuming a strong light emission and providing a green to a red luminous material and to provide a general and highly efficient method for producing the compound. SOLUTION: This bis(aminostyryl)stilbene-based compound is represented by the general formula [I] or the like (wherein R1 and R4 are each an unsubstituted aryl group; R2 and R3 are each an aryl group having a specific substituent group such as methoxy group; R5, R6, R7, R8, R9, R10, R10 and R12 are each mutually the same or a different group and at least one thereof is hydrogen atom, a saturated or an unsubstituted hydrocarbon group, cyano group, nitro group, trifluoromethyl group or a halogen atom; and k is an integer of >=1). The method for producing the compound comprises condensation of, e.g. a 4-(N,N-diarylamino)benzaldehyde with a diphosphonic acid ester or a diphosphosnium salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to bis (aminostyryl), which is suitable as an organic luminescent material exhibiting a desired luminescent color.
The present invention relates to a stilbene compound and a synthetic intermediate thereof, a production method thereof, and an organic electroluminescent device.

[0002]

2. Description of the Related Art Organic electroluminescent elements (EL elements) and the like have recently attracted attention as one candidate for flat panel displays that are self-luminous, have a high response speed, and have no viewing angle dependence. There is an increasing interest in organic light emitting materials as constituent materials. The first advantage of organic light emitting materials is that
The optical properties of the material can be controlled to some extent by molecular design, which makes it possible to realize a full-color organic light-emitting device in which all of the three primary colors of red, blue and green are made of the respective light-emitting materials.

A bis (aminostyryl) benzene compound represented by the following general formula [A] emits strong blue to red light in the visible region depending on the substituent to be introduced. Not limited to materials, it can be used for various applications. Furthermore, these materials are sublimable,
There is an advantage that a uniform amorphous film can be formed by the vacuum deposition process. Nowadays, the optical properties of materials can be predicted to some extent by molecular orbital calculations, etc., but in practice, the technology to manufacture the required materials with high efficiency is the most important in the industry. Nor.

[0004]

Embedded image (However, in the general formula [A], Ar is an aryl group which may have a substituent, and ^Ra and ^Rb each have a hydrogen atom, a saturated or unsaturated hydrocarbon group, and a substituent. And an aryl group, a cyano group, a halogen atom, a nitro group, and an alkoxyl group, which may be the same or different.)

[0005]

A number of compounds belonging to the above general formula [A] have been produced as organic light-emitting materials. However, many of these materials have been considered for practical use.
Issues remain in terms of higher efficiency and longer life [IEICE, Technical Research Report, Organic Electronics, 17 , 7 (1992), Inorganic and Organic Electroluminum
escence 96 Berlin, 101 (1996)], and a highly efficient production method thereof has not been established.

SUMMARY OF THE INVENTION In view of the above situation, an object of the present invention is to provide a compound which emits strong light and is particularly suitable as an organic light-emitting material for green to red light, a synthetic intermediate thereof, a method for producing these compounds with high efficiency, and An object of the present invention is to provide an organic electroluminescent device.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the following general formula [I]:
The bis (aminostyryl) stilbene compound represented by [II], [III] or [IV] exhibits strong luminescence,
The present inventors have found that the material can be used as a red light emitting material, established a general and highly efficient manufacturing method thereof, and have reached the present invention.

That is, the present invention firstly provides the following general formula [I]:
It relates to a bis (aminostyryl) stilbene compound represented by the formula [II], [III] or [IV] (hereinafter referred to as the compound of the present invention).

Embedded image [However, in the general formula [I], R ¹ and R ⁴ are an unsubstituted aryl group, and R ² and R ³ are an aryl group represented by the following general formula (1).

Embedded image (However, in the general formula (1), R ¹³ , R ¹⁴ ,
R ¹⁵ , R ¹⁶ and R ¹⁷ are the same or different groups, and at least one of them is a saturated or unsaturated hydrocarbon oxy group having 1 or more carbon atoms, or a hydrocarbon group. ), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are the same or different groups, and at least one of them is a hydrogen atom, a saturated or unsaturated carbon atom. A hydrogen group, a cyano group, a nitro group, a trifluoromethyl group, or a halogen atom (F, Cl, Br, I, and the like; the same applies hereinafter), and k is an integer of 1 or more. ]

Embedded image [However, in the general formula [II], R ¹⁸ , R ¹⁹ , R ²⁰
And R ²¹ are the same or different groups, and are aryl groups represented by the following general formula (2).

Embedded image (However, in the general formula (2), R ³⁰ , R ³¹ ,
R ³² , R ³³ and R ³⁴ are the same or different groups, and at least one of them is a saturated or unsaturated hydrocarbon oxy group having 1 or more carbon atoms or a hydrocarbon group. ), R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ are the same or different groups, and at least one of them is a hydrogen atom, a saturated or unsaturated carbon atom. A hydrogen group, a cyano group, a nitro group, a trifluoromethyl group or a halogen atom, and k is an integer of 1 or more. ]

Embedded image [However, in the general formula [III], R ³⁵ , R ³⁶ , R
^At least one of ³⁷ and ^R38 is an aryl group represented by the following general formula (3), and the rest is an unsubstituted aryl group.

Embedded image (However, in the general formula (3), R ⁴⁷ , R ⁴⁸ ,
R ⁴⁹ , R ⁵⁰ and R ⁵¹ are the same or different groups, and at least one of them is a saturated or unsaturated hydrocarbon amino group having 1 or more carbon atoms. ), R ³⁹ , R ⁴⁰ , R
⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are the same or different groups, and at least one of them is a hydrogen atom, a saturated or unsaturated hydrocarbon group, a cyano group, a nitro group, A trifluoromethyl group or a halogen atom,
Is an integer of 1 or more. ]

Embedded image [However, in the general formula [IV], R ⁵³ and R ⁵⁵ are the same or different groups, and are an aryl group represented by the following general formula (4).

Embedded image (However, in the general formula (4), R ⁶⁴ , R ⁶⁵ ,
R ⁶⁶ , R ⁶⁷ and R ⁶⁸ are the same or different groups, and each has a hydrogen atom or at least one of them having 1 carbon atom.
The above is a saturated or unsaturated hydrocarbon oxy group or hydrocarbon group. ), R ⁵² and R ⁵⁴ are the same or different groups, and are aryl groups represented by the following general formula (5).

Embedded image(However, in the general formula (5), R⁶⁹, R⁷⁰,
R⁷¹, R⁷², R⁷³, R⁷⁴And R⁷⁵Are the same or different
A hydrogen atom or at least one of them
A saturated or unsaturated hydrocarbon oxy having one or more carbon atoms
Group, a hydrocarbon group, or a hydrocarbon amino group. ), R
⁵⁶, R⁵⁷, R⁵⁸, R⁵⁹, R⁶⁰, R⁶¹, R⁶²And R ⁶³Are
The same or different groups, at least
One of which is a hydrogen atom, a saturated or unsaturated hydrocarbon group,
Group, nitro group, trifluoromethyl group or halogen atom
And k is an integer of 1 or more. ]

The compound of the present invention can be effectively used as an organic light emitting material which emits green to red light, and has a high glass transition point and a high melting point.
In addition to being excellent in electrical, thermal or chemical stability, it can be easily formed into a glass state in an amorphous state, so that vapor deposition or the like can be performed.

The compound of the present invention is preferably represented by the following general formula.

Embedded image [However, in the general formula (6), Ar ¹ , Ar ² ,
At least one of Ar ³ and Ar ⁴ has the following general formula (7), (8), (9), (10), (11), (1)
2) a group selected from aryl groups represented by (12 ′) or (12 ″), and the rest being unsubstituted aryl groups;

Embedded image (However, the general formulas (7), (8), (9), (1
0), (11), (12), (12 ') and (12 ")
In the above, R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² , R ⁸³ ,
R ⁸⁴ , R ⁸⁵ and R ^{86 each} represent a saturated or unsaturated hydrocarbon group having 1 or more carbon atoms (especially, those having 6 or less carbon atoms are preferable (unsubstituted when having 0 carbon atoms); Is an integer of 0 to 5, m is an integer of 0 to 3, and 1 is an integer of 0 to 4. ), R ⁷⁶ and R ⁷⁷ are the same or different groups, and at least one of them is a hydrogen atom,
To 6 saturated or unsaturated hydrocarbon groups. ]

The compounds of the present invention are more specifically represented by the following general formulas (13), (14), (15), (16),
(17), (18), (19), (20) or (21)
What is expressed by is good.

Embedded image (However, in the general formula (13), R ⁸⁷ and R ^87
88 is the same or different and is a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. )

Embedded image (However, in the general formula (14), R ⁸⁹ and R
⁹⁰ is the same or different saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. )

Embedded image (However, in the general formula (15), R ⁹¹ , R ⁹² , R
⁹³ and R ⁹⁴ are the same or different and are each a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. )

Embedded image (However, in the above general formula (16), R ⁹⁵ , R ⁹⁶ , R
⁹⁷ and R ⁹⁸ are the same or different and are each a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. )

Embedded image (However, in the general formula (17), R ⁹⁹ and R ¹⁰⁰
Are the same or different saturated or unsaturated hydrocarbon groups having 1 to 6 carbon atoms. )

Embedded image (However, in the general formula (18), R ¹⁰¹ and R
¹⁰² is the same or different and is a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. )

Embedded image (However, in the general formula (19), R ¹⁰³ ,
R ¹⁰⁴ , R ¹⁰⁵ and R ¹⁰⁶ are the same or different and are each a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. )

Embedded image (However, in the general formula (20), R ¹⁰⁷ ,
R ¹⁰⁸ , R ¹⁰⁹ and R ¹¹⁰ are the same or different and are each a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. )

Embedded image (However, in the general formula (21), R ¹¹¹ and R
¹¹² is the same or different and is a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. )

The compound of the present invention has the following structural formula (22)-
1, (22) -2, (22) -3, (22) -4, (2
2) -5, (22) -6, (22) -7, (22)-
8, (22) -9, (22) -10, (22) -11,
What is represented by (22) -12 or (22) -13 is specifically illustrated.

Embedded image

The present invention also provides a method for producing the compound of the present invention with high efficiency, which comprises at least one of 4- (N, N-diarylamino) benzaldehyde represented by the following general formula [V] or [VI]. And a diphosphonate represented by the following general formula [VII] or a diphosphonium salt represented by the following general formula [VIII];
The present invention also provides a process for producing a bis (aminostyryl) stilbene compound represented by the general formula [I], [II], [III] or [IV].

Embedded image (However, in the general formulas [V] and [VI], R ¹¹³
And R ¹¹⁴ are each R ¹ , R ² , R ¹⁸ , R ¹⁹ ,
An aryl group corresponding to R ³⁵ , R ³⁶ , R ⁵² or R ⁵³ , wherein R ¹¹⁵ and R ¹¹⁶ are each R ³ , R ⁴ , R
^20, an aryl group corresponding to ^{R 21, R 37, R 38} , R 54 or R ^55. )

Embedded image (However, in the general formulas [VII] and [VIII], R
¹¹⁷ and R ¹¹⁸ are the same or different hydrocarbon groups (particularly, preferably a saturated hydrocarbon group having 1 to 6 carbon atoms; the same applies hereinafter), and R ¹¹⁹ , R ¹²⁰ , R ¹²¹ , R
¹²² , R ¹²³ , R ¹²⁴ , R ¹²⁵ and R ¹²⁶ are each
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ ,
R ¹² , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R
^{39, R 40, R 41,} R 42, R 43, R 44, R 45, R 46,
A group corresponding to R ⁵⁶ , R ⁵⁷ , R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² or R ⁶³ , X is a halogen atom, and k is an integer of 1 or more. )

In the method for producing the compound of the present invention, specifically, the condensation is carried out by Wittig-Horne.
r) reaction or Wittig reaction,
The diphosphonic acid ester and / or the diphosphonium salt is treated with a base in a solvent to generate a carbanion, and the carbanion and the 4- (N,
(N-diarylamino) benzaldehyde.

For example, in obtaining a bis (aminostyryl) stilbene compound represented by the following general formula (6):

Embedded image (However, in the general formula (6), Ar ¹ , Ar ² ,
Ar ³ , Ar ⁴ , R ⁷⁶ and R ⁷⁷ are the same as those described above. ), The following general formula (23) or (24)
And at least one of 4- (N, N-diarylamino) benzaldehyde represented by the formula: a diphosphonic acid ester represented by the general formula [VII] or a diphosphonium salt represented by the general formula [VIII]; Is condensed.

Embedded image (However, in the general formulas (23) and (24), A
r ¹ , Ar ² , Ar ³ and Ar ⁴ are the same as described above. )

This reaction is represented by a scheme, for example, as shown in the following reaction scheme 1.

Embedded image

In this reaction, first, the compound represented by the general formula (30) or (3)
The treatment begins with the generation of a carbanion by treating the compound of 1) with a base in a suitable solvent, and is then completed by condensing this carbanion with an aldehyde of the general formula (23). The following can be considered as combinations of the base and the solvent.

Sodium hydroxide / water, sodium carbonate /
Water, potassium carbonate / water, sodium ethoxide / ethanol or dimethylformamide, sodium methoxide / methanol-diethyl ether mixed solvent or dimethylformamide, triethylamine / ethanol or diglyme or chloroform or nitromethane, pyridine /
Methylene chloride or nitromethane, 1,5-diazabicyclo [4.3.0] non-5-ene / dimethylsulfoxide, potassium t-butoxide / dimethylsulfoxide or tetrahydrofuran or benzene or dimethylformamide, phenyllithium / diethylether or tetrahydrofuran, sodium amide / Ammonia, sodium hydride / dimethylformamide or tetrahydrofuran and the like.

This reaction is carried out at a relatively low temperature (-30 ° C. to 30 ° C.).
° C), which is selective and facilitates purification of the target compound by chromatography. In addition, since the compound of the present invention of the general formula (6) has high crystallinity, the purity is improved by recrystallization. Can be done. The method of recrystallization is not particularly limited, but a method of dissolving in acetone and adding hexane, or a method of dissolving by heating in toluene, concentrating,
The cooling method is simple. The reaction is carried out at normal pressure for 3 to 24
You may go in time.

According to the method for producing the compound of the present invention, the compounds represented by the above general formulas (13), (14), (15), (16) and (1)
The bis (aminostyryl) stilbene-based compound represented by 7), (20) or (21) can be obtained. Specifically, the structural formulas (22) -1, (22) -2, and (2)
2) -3, (22) -4, (22) -5, (22)-
6, (22) -7, (22) -8, (22) -9, (2
2) -10, (22) -11, (22) -12 or (2)
2) A bis (aminostyryl) stilbene compound represented by -13 can be obtained.

The present invention also provides various compounds suitable as intermediates for synthesizing the compounds of the present invention.

That is, the above general formulas [I], [II] and [III]
Or a diphosphonic ester represented by the general formula [VII] or a diphosphonic ester represented by the general formula [VIII], which is used as an intermediate for synthesizing a bis (aminostyryl) stilbene compound represented by the formula [IV]. It is a phosphonium salt.

This synthetic intermediate (hereinafter referred to as synthetic intermediate 1 of the present invention) is specifically represented by the following general formula (25):
(26), (27), (28), (29) or (30)
It is represented by

Embedded image (However, the general formulas (25), (26), (27),
In (28), (29) and (30), R ¹¹⁷ , R
¹¹⁸ and X are the same as described above. )

The synthetic intermediate 1 of the present invention can be derived from the synthetic intermediate as its precursor as follows.

That is, an aryl halide compound represented by the following general formula [IX] and a trialkyl phosphite or triphenylphosphine (PP) represented by the following general formula [X]
h ₃ ) to react with the general formula [VII
Or a diphosphonium salt represented by the general formula [VIII] as a synthetic intermediate. This reaction is carried out in a solvent such as xylene having a boiling point of 120 ° C. or higher, or in a large excess of trialkyl phosphite at a reaction temperature of 120 ° C. to 160 ° C. and a normal reaction time of 30 minutes to 24 hours. Good.

Embedded image (However, in the general formula [IX], R ¹¹⁹ , R ¹²⁰ ,
R ¹²¹ , R ¹²² , R ¹²³ , R ¹²⁴ , R ¹²⁵ and R ¹²⁶ are the same or different groups, and at least one of them is a hydrogen atom, a saturated or unsaturated hydrocarbon group, a cyano group, A nitro group, a trifluoromethyl group or a halogen atom, X is a halogen atom, and k is 1
Is an integer greater than or equal to. General formula [X]: P (OR ¹²⁷ ) ₃ or P (OR ¹²⁸ ) ₃ (However, in the above general formula [X], R ¹²⁷ and R ¹²⁸
Are respectively the same or different hydrocarbon groups, especially saturated or unsaturated hydrocarbon groups having 1 to 6 carbon atoms. )

In the present invention, as a synthetic intermediate for obtaining the synthetic intermediate 1, an aryl halide compound represented by the above general formula [IX] (hereinafter referred to as the synthetic intermediate 2 of the present invention) is also used. To provide.

The synthetic intermediate 2 of the present invention has the following general formula [X
The compound can be obtained by reacting a dimethylstilbene compound represented by the formula [I] with an N-halogenated succinimide represented by the following general formula [XII] under light irradiation. For example, in a solvent such as carbon tetrachloride, chloroform, benzene, and chlorobenzene, a light source such as a high-pressure mercury lamp, a low-pressure mercury lamp, a xenon lamp, a halogen lamp, sunlight, and a fluorescent lamp is used. React with a reaction time of ~ 48 hours.

Embedded image (However, in the general formula [XI], R ¹¹⁹ , R ¹²⁰ ,
R ¹²¹ , R ¹²² , R ¹²³ , R ¹²⁴ , R ¹²⁵ and R ¹²⁶ are the same or different groups, and at least one of them is a hydrogen atom, a saturated or unsaturated hydrocarbon group,
A cyano group, a nitro group, a trifluoromethyl group or a halogen atom, X is a halogen atom, and k is an integer of 1 or more. )

Embedded image (However, in the general formula [XII], X is a halogen atom.)

The reaction for obtaining each of the synthetic intermediates 1 and 2 described above can be shown, for example, in the following reaction scheme 2.

[0029]

Embedded image

FIGS. 2 to 5 show examples of an organic electroluminescent device (EL device) using the compound of the present invention as an organic light emitting material.

The compound of the present invention used in the organic EL device may be any one of the compounds represented by the general formulas [I], [II], [III] or [IV], in particular, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^9, R ^{10,
R 1, R 12, R 22} , R 23, R 24, R 25, R 26, R 27, R
^{28, R 29, R 39,} R 40, R 41, R 42, R 43, R 44,
R ⁴⁵ , R ⁴⁶ , R ⁵⁶ , R ⁵⁷ , R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R
^{Preferably, 62} and R ⁶³ are groups selected from the group consisting of a hydrogen atom, a saturated or unsaturated hydrocarbon group and a trifluoromethyl group.

FIG. 2 shows a transmission type organic electroluminescent device A in which light emission 20 passes through the cathode 3, and the light emission 20 can be observed also from the protective layer 4 side. FIG. 3 shows a reflective organic electroluminescent device B that also obtains light reflected at the cathode 3 as light emission 20.

In the drawing, reference numeral 1 denotes a substrate for forming an organic electroluminescent device, which can be made of glass, plastic or other appropriate material. When the organic electroluminescent device is used in combination with another display device, the substrate can be shared. 2 is a transparent electrode (anode);
TO (Indium tin oxide), SnO ₂ or the like can be used.

Reference numeral 5 denotes an organic light-emitting layer, which contains the compound of the present invention as a light-emitting material. With respect to this light-emitting layer, conventionally known various structures can be used as a layer structure for obtaining the organic electroluminescence 20. As described below,
For example, when a material constituting either the hole transport layer or the electron transport layer has a light emitting property, a structure in which these thin films are stacked can be used. Further, in order to enhance the charge transport performance in a range satisfying the object of the present invention, one or both of the hole transport layer and the electron transport layer has a structure in which thin films of a plurality of types of materials are stacked, or a plurality of types of materials. Does not prevent the use of a thin film having a composition containing Further, in order to improve the light emission performance, a structure in which this thin film is sandwiched between a hole transport layer and an electron transport layer using at least one kind of fluorescent material,
Further, a structure in which at least one or more fluorescent materials are included in the hole transport layer or the electron transport layer, or both of them may be used. In these cases, in order to improve luminous efficiency, a thin film for controlling the transport of holes or electrons can be included in the layer structure.

When the compound of the present invention has both electron transporting performance and hole transporting performance, it may be used as a light emitting layer also serving as an electron transporting layer or a light emitting layer also serving as a hole transporting layer in the device. It can be used. Further, it is also possible to adopt a structure in which the compound of the present invention is used as a light-emitting layer and sandwiched between an electron transport layer and a hole transport layer.

In FIGS. 2 and 3, reference numeral 3 denotes a cathode;
As the electrode material, an alloy of an active metal such as Li, Mg, and Ca and a metal such as Ag, Al, and In, or a structure in which these are laminated can be used. In a transmission type organic electroluminescent device, by adjusting the thickness of the cathode, a light transmittance suitable for the intended use can be obtained. In the figure, reference numeral 4 denotes a sealing / protecting layer, and the effect is improved by adopting a structure that covers the entire organic electroluminescent element. If airtightness is maintained, an appropriate material can be used. Reference numeral 8 denotes a drive power supply for current injection.

In this organic electroluminescent device, the organic layer has an organic laminated structure (single heterostructure) in which a hole transport layer and an electron transport layer are laminated, and the organic layer has a hole transport layer or an electron transport layer. The compounds of the present invention may be used as forming materials. Alternatively, the organic layer has an organic laminated structure (double hetero structure) in which a hole transport layer, a light emitting layer, and an electron transport layer are sequentially laminated, and the compound of the present invention is used as a material for forming the light emitting layer. May be.

FIG. 4 shows an example of an organic electroluminescent device having such an organic laminated structure.
It has a laminated structure in which a translucent anode 2, an organic layer 5 a including a hole transport layer 6 and an electron transport layer 7, and a cathode 3 are sequentially laminated, and this laminated structure is sealed with a protective film 4. This is an organic electroluminescent device C having a single hetero structure.

As shown in FIG. 4, in the case of the layer structure in which the light emitting layer is omitted, light emission 20 of a predetermined wavelength is generated from the interface between the hole transport layer 6 and the electron transport layer 7. These lights are emitted from the substrate 1
Observed from the side.

FIG. 5 shows a light-transmissive anode 2, an organic layer 5 b composed of a hole transport layer 10, a light-emitting layer 11 and an electron transport layer 12, and a cathode 3 on a translucent substrate 1. Is a double hetero-structure organic electroluminescent element D having a laminated structure in which are sequentially laminated, and the laminated structure is sealed with a protective film 4.

In the organic electroluminescent device shown in FIG. 5, by applying a DC voltage between the anode 2 and the cathode 3, holes injected from the anode 2 pass through the hole transport layer 10, and Electrons injected from 3 reach the light emitting layer 11 via the electron transport layer 12 respectively. As a result, electron / hole recombination occurs in the light emitting layer 11 to generate singlet excitons, and the singlet excitons emit light of a predetermined wavelength.

In each of the organic electroluminescent elements C and D described above, the substrate 1 can be made of a light-transmissive material such as glass or plastic. The substrate may be shared when used in combination with another display element or when the stacked structures shown in FIGS. 4 and 5 are arranged in a matrix. In addition, each of the elements C and D can take any of a transmission type and a reflection type structure.

The anode 2 is a transparent electrode and is made of ITO.
(Indium tin oxide) or SnO ₂ can be used. A thin film made of an organic substance or an organometallic compound may be provided between the anode 2 and the hole transport layer 6 (or the hole transport layer 10) for the purpose of improving the charge injection efficiency. When the protective film 4 is formed of a conductive material such as a metal,
An insulating layer may be provided on the side surface of the anode 2.

The organic layer 5a in the organic electroluminescent device C is an organic layer in which a hole transport layer 6 and an electron transport layer 7 are laminated, and one or both of them are formed by the above-mentioned compound of the present invention. It may be contained to form the luminescent hole transport layer 6 or the electron transport layer 7. The organic layer 5b in the organic electroluminescent device D is an organic layer in which the hole transport layer 10, the light emitting layer 11 containing the compound of the present invention described above, and the electron transport layer 12 are laminated, and various other laminated layers Can take structure. For example, one or both of the hole transport layer and the electron transport layer may have a light emitting property.

It is particularly desirable that the hole transporting layer 6, the electron transporting layer 7, and the light emitting layer 11 are made of the compound of the present invention, but these layers may be formed of only the compound of the present invention, or Alternatively, it may be formed by co-evaporation of the compound of the present invention and another hole or electron transporting material (for example, aromatic amines and pyrazolines). Further, in the hole transport layer, a hole transport layer in which a plurality of types of hole transport materials are stacked may be formed in order to improve hole transport performance.

In the organic electroluminescent device C, the light emitting layer may be the electron transporting light emitting layer 7, but depending on the voltage applied from the power supply 8, the light emitting layer may emit light at the hole transporting layer 6 or its interface. There is. Similarly, in the organic electroluminescent device D, the light emitting layer may be the electron transport layer 12 or the hole transport layer 10 other than the layer 11. In order to improve the light emitting performance, it is preferable that the light emitting layer 11 using at least one kind of fluorescent material is sandwiched between the hole transport layer 10 and the electron transport layer 12. Alternatively, a structure in which this fluorescent material is contained in the hole transport layer or the electron transport layer, or in both of these layers, may be configured. In such a case, in order to improve luminous efficiency, a thin film (such as a hole blocking layer or an exciton generation layer) for controlling the transport of holes or electrons can be included in the layer configuration.

The material used for the cathode 3 is L
An alloy of an active metal such as i, Mg and Ca and a metal such as Ag, Al and In can be used, and a structure in which these metals are laminated may be used. Incidentally, by appropriately selecting the thickness and material of the cathode, an organic electroluminescent device suitable for the intended use can be produced.

The protective layer 4 functions as a sealing film, and by having a structure covering the entire organic electroluminescent element, the charge injection efficiency and the luminous efficiency can be improved. As long as the airtightness is maintained, the material can be appropriately selected, such as a single metal such as aluminum, gold, and chromium, or an alloy.

The current applied to each of the above-mentioned organic electroluminescent elements is usually a direct current, but a pulse current or an alternating current may be used. The current value and the voltage value are not particularly limited as long as they are within a range that does not cause element destruction. However, in consideration of power consumption and life of the organic electroluminescent element, it is desirable to emit light efficiently with as little electric energy as possible.

Next, FIG. 6 is a configuration diagram of a flat display using an organic electroluminescent device. As illustrated, for example, in the case of a full color display, the organic layer 5 (5) capable of emitting three primary colors of red (R), green (G), and blue (B) is provided.
a, 5b) are arranged between the cathode 3 and the anode 2.
The cathode 3 and the anode 2 can be provided in a stripe shape crossing each other, and are selected by the luminance signal circuit 14 and the control circuit 15 with a built-in shift register, and a signal voltage is applied to each of them. The organic layer at a position (pixel) where the anode 3 and the anode 2 intersect is configured to emit light.

That is, FIG. 6 shows, for example, an 8 × 3 RGB simple matrix in which a laminate 5 comprising a hole transport layer and at least one of a light emitting layer and an electron transport layer is provided between the cathode 3 and the anode 2. (FIG. 4 or FIG. 5)
reference). The cathode and anode are both patterned in stripes, and are orthogonal to each other in a matrix,
The control circuits 15 and 14 with a built-in shift register apply a signal voltage in a time-series manner, and emit light at the intersection. The EL element having such a configuration can be used not only as a display for characters and symbols, but also as an image reproducing device. In addition, a stripe pattern of the cathode 3 and the anode 2 is arranged for each color of red (R), green (G), and blue (B), so that a multi-color or full-color all solid-state flat panel display can be configured. Becomes

[0052]

The present invention will now be described by way of examples, which should not be construed as limiting the invention.

[0053]

Embedded image R R ′ Structural formula ────────────────────────────── Example 1 OCH ₃ H (22) -1 Example 2 H H (22) -2 Example 3 CH ₃ H (22) -3 Example 4 C (CH ₃ ) ₃ H (22) -4 Example 5 OC (CH ₃ ) ₃ H (22) -5 Example 6 CH ₃ CH ₃ (22) -6 example _{7 OCH 3 OCH 3 (22)} -7 ───────────────────────────── ─

Example 1 <1,2- [1,4-bis [2- [4- (N-4-methoxyphenyl-N-phenyl) aminophenyl] ethenyl] phenyl] ethene (Structural Formula (22)- Synthesis example of 1)>

To a suspension of sodium hydride (60% mineral oil suspension, 158 mg, 3.96 mmol) in tetrahydrofuran (THF) (20 ml) was added [(1,2
-Ethenediylbis (4,1-phenylenemethylene)]
Bisphosphonic acid tetraethyl ester) (950 mg,
1.98 mmol) of a THF solution (20 ml) was added dropwise with stirring at room temperature. The resulting mixture is at room temperature
After stirring for 1 hour, (4-N-methoxyphenyl-N-
Phenyl) aminobenzaldehyde (1.20 g, 3.
96 mmol) in THF (20 ml) was added dropwise.

After the obtained mixture was stirred at room temperature for 6 hours, sodium hydride (60% mineral oil suspension,
100 mg (2.50 mmol) and (4-N-methoxyphenyl-N-phenylamino) benzaldehyde (500 mg, 1.65 mmol) were added, and the mixture was further stirred at room temperature for 6 hours. Water (50 m) was added to the obtained mixture.
l) was added dropwise and extracted three times with chloroform. The obtained organic layer was washed with saturated saline, dried over anhydrous sodium sulfate, and filtered.

The filtrate was concentrated under reduced pressure, and the residue was purified by silica gel chromatography and recrystallized from ethyl acetate-hexane to give the desired compound (Structural Formula (22)-
1) (924 mg, yield 65%) was obtained as yellow crystals. The identity of this product was determined by ¹ H NMR and FAB
-Performed by MS measurement. ¹ H NMR and FAB-
The target was identified by MS measurement (yield: 14%). ¹
_{H NMR (CDC1 3) δ (} ppm): 3.81 (s, 3H), 6.83-7.49
(40H) The ¹ H NMR spectrum of this product was as shown in FIG. 1 (H ₂ O in the figure is residual water in the measurement solvent, and TMS was a standard added when measuring the ¹ H NMR spectrum. Peak of the substance tetramethylsilane:
Similar). The product had a glass transition point of 87 ° C. and a melting point of 172 ° C.

A toluene solution of this product (1.6 × 10
^-6 mol / l: hereinafter the same) is 42.
4 nm and the maximum fluorescence wavelength was 475 nm.

Example 2 <Synthesis example of 1,2- [1,4-bis [2- [4- (N-diphenyl) aminophenyl] ethenyl] phenyl] ethene (Structural Formula (22) -2)>

Sodium hydride (60% mineral oil suspension, 200 mg, 5.02 mmol), [[1,2
-Ethenediylbis (4,1-phenylenemethylene)]] bisphosphonic acid tetraethyl ester (754
mg, 1.57 mmol) and N, N-diphenylaminobenzaldehyde (1.20 g, 4.40 mmol), and was synthesized in the same manner as in Example 1.

As a result, the desired product (Structural Formula (22) -2)
(745 mg, yield 66%) was obtained as yellow crystals. The product was identified by ¹ H NMR and FAB-MS.
The measurement was performed. _{^{1 H NMR (CDC1 3) δ}} (ppm): 7.10-7.54 (s, 42H) Glass transition temperature of the product 96 ° C., a melting point of 185 ° C..

The toluene solution of this product had a visible absorption maximum wavelength of 414 nm and a fluorescence maximum wavelength of 455 nm.

Example 3 <1,2- [1,4-bis [2- [4- (N-4-methylphenyl-N-phenyl) aminophenyl] ethenyl] phenyl] ethene (Structural Formula (22)- Synthesis example of 3)>

Sodium hydride (60% mineral oil suspension, 196 mg, 4.90 mmol) [[1,2-
Ethenediylbis (4,1-phenylenemethylene)]]
Bisphosphonic acid tetraethyl ester (672 mg,
1.40 mmol), (4-N-methylphenyl-N-
Phenyl) aminobenzaldehyde (1.21 g, 4.
20 mmol) and synthesized in the same manner as in Example 1.

As a result, the target compound (Structural Formula (22) -3)
(678 mg, 62% yield) as yellow-orange crystals.
The product was identified by ¹ H NMR and FAB-M
It was performed by S measurement. _{^{1 H NMR (CDC1 3) δ}} (ppm): 2.33
(S, 6H), 7.04-7.50 (40H) The glass transition point of this product was 99 ° C and the melting point was 181 ° C.

The toluene solution of this product had a visible absorption maximum wavelength of 419 nm and a fluorescence maximum wavelength of 465 nm.

Example 4 <1,2- [1,4-bis [2- [4- (N-4-t-
Synthesis Example of Butylphenyl-N-phenyl) aminophenyl] ethenyl] phenyl] ethene (Structural Formula (22) -4)

Sodium hydride (60% mineral oil suspension, 92.8 mg, 2.52 mmol) [[1,2
-Ethenediylbis (4,1-phenylenemethylene)]] bisphosphonic acid tetraethyl ester (276
mg, 0.580 mmol), (4-Nt-butylphenyl-N-phenyl) aminobenzaldehyde (66
(9 mg, 2.03 mmol) and synthesized in the same manner as in Example 1.

As a result, the target compound (Structural Formula (22) -4)
(241 mg, 50% yield) were obtained as yellow-orange crystals.
The identity of this product was determined by ¹ H NMR and FAB-
Performed by MS measurement. _{^{1 H NMR (CDC1 3) δ}} (ppm): 1.41 (s, 36H), 7.02-7.
52 (40H) This product has a glass transition temperature of 96 ° C and a melting point of 200 ° C.
Met.

The toluene solution of this product had a maximum visible absorption wavelength of 419 nm and a maximum fluorescence wavelength of 465 nm.

Example 5 <1,2- [1,4-bis [2- [4- (N-4-t-
Synthesis Example of Butoxyphenyl-N-phenyl) aminophenyl] ethenyl] phenyl] ethene (Structural Formula (22) -5)>

Sodium hydride (60% mineral oil suspension, 155 mg, 3.87 mmol) [[1,2-
Ethenediylbis (4,1-phenylenemethylene)]]
Bisphosphonic acid tetraethyl ester (489 mg,
1.02 mmol), (4-Nt-butoxyphenyl-N-phenyl) aminobenzaldehyde (1.23
g, 3.56 mmol) in the same manner as in Example 1.

As a result, the target compound (Structural Formula (22) -5)
(448 mg, 51% yield) was obtained as yellow crystals. The product was identified by ¹ H NMR and FAB-MS.
The measurement was performed. _{^{1 H NMR (CDC1 3) δ}} (ppm): 1.38 (s, 36H), 6.78-
7.50 (40H) Glass transition temperature of this product is 99 ℃, melting point is 210 ℃
Met.

The toluene solution of this product had a maximum visible absorption wavelength of 421 nm and a maximum fluorescence wavelength of 470 nm.

Example 6 <1,2- [1,4-bis [2- [4- [bis-N-
(4-methylphenyl)] aminophenyl] ethenyl]
Synthesis Example of Phenyl] ethene (Structural Formula (22) -6)

Sodium hydride (60% mineral oil suspension, 245 mg, 6.13 mmol) [[1,2-
Ethenediylbis (4,1-phenylenemethylene)]]
Bisphosphonic acid tetraethyl ester (776 mg,
1.61 mmol), [bis-N- (4-methylphenyl) aminobenzaldehyde (1.61 g, 5.33 m
mol) was synthesized in the same manner as in Example 1.

As a result, the target compound (Structural Formula (22) -6)
(58.8 mg, yield 47%) was obtained as yellow crystals.
The product was identified by ¹ H NMR and FAB-M
It was performed by S measurement. _{^{1 H NMR (CDC1 3) δ}} (ppm): 2.35 (s, 12H), 7.06-7.
54 (40H) This product has a glass transition temperature of 99 ° C and a melting point of 181 ° C.
Met.

The toluene solution of this product had a visible absorption maximum wavelength of 426 nm and a fluorescence maximum wavelength of 470 nm.

Example 7 <1,2- [1,4-bis [2- [4- [bis-N-
Synthesis Example of (4-methoxyphenyl)] aminophenyl] ethenyl] phenyl] ethene (Structural Formula (22) -7)>

Sodium hydride (60% mineral oil suspension, 62.8 mg, 1.57 mmol) [[1,2
-Ethenediylbis (4,1-phenylenemethylene)]] bisphosphonic acid tetraethyl ester (168
mg, 0.348 mmol), [bis-N- (4-methoxyphenyl)] aminobenzaldehyde (465 m
g, 1.40 mmol) in the same manner as in Example 1.

As a result, the target compound (Structural Formula (22) -7)
(138 mg, yield 49%) was obtained as yellow-orange crystals.
The product was identified by ¹ H NMR and FAB-M
It was performed by S measurement. _{^{1 H NMR (CDC1 3) δ}} (ppm): 3.78 (s, 12H), 6.72-7.
60 (40H) The glass transition temperature of this product is 95 ° C, melting point is 164 ° C
Met.

The visible light absorption maximum wavelength of the toluene solution of this product was 432 nm, and the fluorescence maximum wavelength was 495 nm.

Example 8 This example relates to a compound of the following structural formula (22) -1 having a methoxy group at R ¹ and R ⁴ among the bis (aminostyryl) stilbene compounds of the above general formula [I]. In this example, an organic electroluminescent device having a single hetero structure was manufactured by using as an electron transporting light emitting material.

[0084]

Embedded image

First, in a vacuum deposition apparatus, a 30 mm-thick anode made of ITO having a thickness of 100 nm was formed on one surface.
A 30 mm glass substrate was set. A metal mask having a plurality of 2.0 mm × 2.0 mm unit openings is disposed close to the substrate as a vapor deposition mask, and the following structural formula is used as a hole transport material under a vacuum of 10 ⁻⁴ Pa or less by a vacuum vapor deposition method. Α-NPD (α-naphthylphenyldiamine) was formed into a film having a thickness of, for example, 50 nm. The deposition rate was 0.1 nm / sec.

[0086]

Embedded image

Further, a compound of the above structural formula (22) -1 was deposited as an electron transport layer material in contact with the hole transport layer. The thickness of the electron transporting layer (also serving as a light emitting layer) made of the compound of the above structural formula (22) -1 was, for example, 50 nm, and the deposition rate was 0.2 nm / sec.

As the cathode material, a laminated film of Mg and Ag was adopted, and this was also formed by vapor deposition to a thickness of, for example, 50 nm (Mg) and 150 nm (Ag film) at a vapor deposition rate of 1 nm / sec. To produce an organic electroluminescent device as shown in FIG.

The organic electroluminescent device manufactured as described above includes:
The emission characteristics were evaluated by applying a forward bias DC voltage under a nitrogen atmosphere. The emission color is green and 100 cd /
A luminance of m ² was obtained. After manufacturing this organic electroluminescent device, it was left under a nitrogen atmosphere for one month, but no device deterioration was observed.

Example 9 In this example, among the styryl compounds of the above general formula [I], the following structural formula (22) -7 having a methoxy group at R ¹ , R ² , R ³ and R ⁴ . This is an example in which a compound is used as an electron-transporting light-emitting material to produce an organic electroluminescence device having a single heterostructure. An organic electroluminescent device was manufactured according to Example 8 in both the layer structure and the film forming method.

[0091]

Embedded image

The organic electroluminescent device of this example manufactured as described above was evaluated for light emission characteristics by applying a forward bias DC voltage under a nitrogen atmosphere. Emission color is green, 7 at 10V
A luminance of 5 cd / m ² was obtained. After manufacturing this organic electroluminescent device, it was left under a nitrogen atmosphere for one month, but no device deterioration was observed.

[0093]

The compound of the present invention can be effectively used as an organic light emitting material which emits green to red strong light depending on the substituents to be introduced, and has a high glass transition point and a high melting point. It is a substance and has excellent heat resistance,
It is excellent in electrical, thermal or chemical stability, can easily form an amorphous glass state, has a sublimation property, and can form a uniform amorphous film by vacuum deposition or the like. Further, the compound of the present invention can be produced by a general and highly efficient method via the synthetic intermediate of the present invention.

[Brief description of the drawings]

FIG. 1 illustrates a ¹ H NMR spectrum of a bis (aminostyryl) stilbene compound (Structural Formula (22) -1) of the present invention.

FIG. 2 is a schematic sectional view of a main part of an organic electroluminescent device according to the present invention.

FIG. 3 is a schematic sectional view of a main part of another organic electroluminescent device.

FIG. 4 is a schematic sectional view of a main part of another organic electroluminescent device.

FIG. 5 is a schematic sectional view of a main part of another organic electroluminescent device.

FIG. 6 is a configuration diagram of a multi- or full-color flat display using the organic electroluminescent device.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Substrate, 2 ... Transparent electrode (anode), 3 ... Cathode, 4 ... Protective film, 5 5a, 5b ... Organic layer, 6 ... Hole transport layer, 7 ... Electron transport layer, 8 ... Power supply, 10 ... Positive Hole transporting layer, 11 light emitting layer, 12 electron transporting layer, 14 luminance signal circuit, 15 control circuit, 20 light emission, A, B, C, D organic electroluminescent element

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07F 9/40 C07F 9/40 E C09B 57/00 C09B 57/00 S C09K 11/06 625 C09K 11/06 625 H05B 33/14 H05B 33/14 B 33/22 33/22 DB (72) Inventor Yoshiyoshi Ishibashi 6-7-35 Kita-Shinagawa, Shinagawa-ku, Tokyo Inside Sony Corporation (72) Inventor Shinichiro Tamura Tokyo 6-7-35 Kita Shinagawa, Shinagawa-ku Sony Corporation F-term (reference) 3K007 AB02 AB03 AB04 AB12 AB14 BA06 DA00 DB03 EB00 FA01 4H006 AA01 AA02 AB92 AC22 BJ50 BP30 BU46 4H050 AA01 AA02 AB84 WA11 WA13 WA26 WA29 4H056 DA03 DB10 FA10

Claims (28)

[Claims] 1. A bis (aminostyryl) stilbene compound represented by the following general formula [I], [II], [III] or [IV]. Embedded image [However, in the general formula [I], R ¹ and R ⁴ are an unsubstituted aryl group, and R ² and R ³ are an aryl group represented by the following general formula (1). (However, in the general formula (1), R ¹³ , R ¹⁴ ,
R ¹⁵ , R ¹⁶ and R ¹⁷ are the same or different groups, and at least one of them is a saturated or unsaturated hydrocarbon oxy group having 1 or more carbon atoms, or a hydrocarbon group. ), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are the same or different groups, and at least one of them is a hydrogen atom, a saturated or unsaturated carbon atom. A hydrogen group, a cyano group, a nitro group, a trifluoromethyl group or a halogen atom, and k is an integer of 1 or more. [Chemical formula 3] [However, in the general formula [II], R ¹⁸ , R ¹⁹ , R ²⁰
And R ²¹ are the same or different groups, and are aryl groups represented by the following general formula (2). (However, in the general formula (2), R ³⁰ , R ³¹ ,
R ³² , R ³³ and R ³⁴ are the same or different groups, and at least one of them is a saturated or unsaturated hydrocarbon oxy group having 1 or more carbon atoms, or a hydrocarbon group. ), R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ are the same or different groups, and at least one of them is a hydrogen atom, a saturated or unsaturated carbon atom. A hydrogen group, a cyano group, a nitro group, a trifluoromethyl group or a halogen atom, and k is an integer of 1 or more. [Chemical formula 5] [However, in the general formula [III], R ³⁵ , R ³⁶ , R
^At least one of ³⁷ and R ³⁸ is an aryl group represented by the following general formula (3), and the rest is an unsubstituted aryl group. (However, in the general formula (3), R ⁴⁷ , R ⁴⁸ ,
R ⁴⁹ , R ⁵⁰ and R ⁵¹ are the same or different groups, and at least one of them is a saturated or unsaturated hydrocarbon amino group having 1 or more carbon atoms. ), R ³⁹ , R ⁴⁰ , R
⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are the same or different groups, and at least one of them is a hydrogen atom, a saturated or unsaturated hydrocarbon group, a cyano group, a nitro group, A trifluoromethyl group or a halogen atom,
Is an integer of 1 or more. [Formula 7] [However, in the general formula [IV], R ⁵³ and R ⁵⁵ are the same or different from each other, and are an aryl group represented by the following general formula (4). (However, in the general formula (4), R ⁶⁴ , R ⁶⁵ ,
R ⁶⁶ , R ⁶⁷ and R ⁶⁸ are the same or different groups, and each has a hydrogen atom or at least one of them having 1 carbon atom.
The above is a saturated or unsaturated hydrocarbon oxy group or hydrocarbon group. ), R ⁵² and R ⁵⁴ are the same or different groups, and are aryl groups represented by the following general formula (5). (However, in the general formula (5), R ⁶⁹ , R ⁷⁰ ,
R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ and R ⁷⁵ are the same or different groups, and each is a hydrogen atom, or at least one of them is a saturated or unsaturated hydrocarbon oxy group having 1 or more carbon atoms; It is a hydrogen group or a hydrocarbon amino group. ), R
⁵⁶ , R ⁵⁷ , R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² and R ⁶³ are the same or different groups, and at least one of them is a hydrogen atom, a saturated or unsaturated hydrocarbon group, A cyano group, a nitro group, a trifluoromethyl group or a halogen atom, and k is an integer of 1 or more. ] 2. The method according to claim 1, which is represented by the following general formula (6).
The bis (aminostyryl) stilbene-based compound described in (1). Embedded image [However, in the general formula (6), Ar ¹ , Ar ² ,
At least one of Ar ³ and Ar ⁴ has the following general formula (7), (8), (9), (10), (11), (1)
2) a group selected from aryl groups represented by (12 ′) or (12 ″), and the rest being unsubstituted aryl groups. (However, the general formulas (7), (8), (9), (1
0), (11), (12), (12 ') and (12 ")
In the above, R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² , R ⁸³ ,
R ⁸⁴ , R ⁸⁵ and R ⁸⁶ are a saturated or unsaturated hydrocarbon group having 1 or more carbon atoms, n is an integer of 0 to 5, and m is 0 to
3 is an integer, and 1 is an integer of 0 to 4. ), R ⁷⁶ and R ⁷⁷ are the same or different, and at least one of them is a hydrogen atom, a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. ] 3. The method according to claim 1, wherein said R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² , R
^83, R ^84, the carbon number of R ⁸⁵ and R ⁸⁶ is 1-6, bis (aminostyryl) stilbene compounds described in claim 2. 4. The following general formulas (13), (14) and (1)
5), (16), (17), (18), (19), (2)
The bis (aminostyryl) stilbene compound according to claim 1, which is represented by 0) or (21). Embedded image (However, in the general formula (13), R ⁸⁷ and R ^87
88 is the same or different and is a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. ) (However, in the general formula (14), R ⁸⁹ and R
⁹⁰ is the same or different saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. ) (However, in the general formula (15), R ⁹¹ , R ⁹² , R
⁹³ and R ⁹⁴ are the same or different and are each a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. ) (However, in the above general formula (16), R ⁹⁵ , R ⁹⁶ , R
⁹⁷ and R ⁹⁸ are the same or different and are each a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. ) (However, in the general formula (17), R ⁹⁹ and R ¹⁰⁰
Are the same or different saturated or unsaturated hydrocarbon groups having 1 to 6 carbon atoms. ) (However, in the general formula (18), R ¹⁰¹ and R
¹⁰² is the same or different and is a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. ) (However, in the general formula (19), R ¹⁰³ ,
R ¹⁰⁴ , R ¹⁰⁵ and R ¹⁰⁶ are the same or different and are each a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. ) (However, in the general formula (20), R ¹⁰⁷ ,
R ¹⁰⁸ , R ¹⁰⁹ and R ¹¹⁰ are the same or different and are each a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. ) (However, in the general formula (21), R ¹¹¹ and R
¹¹² is the same or different and is a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. ) 5. The following structural formulas (22) -1, (22)-
2, (22) -3, (22) -4, (22) -5, (2
2) -6, (22) -7, (22) -8, (22)-
9, (22) -10, (22) -11, (22) -12
Or the bis (aminostyryl) stilbene compound according to claim 1, represented by (22) -13. Embedded image 6. A compound represented by the following general formula [V] or [VI]
4- (N, N-diarylamino) benzaldehyde
At least one compound; diphosphine represented by the following general formula [VII]:
Sulfonic acid ester or diacid represented by the following general formula [VIII]
By condensing with a phosphonium salt,
Bis represented by general formulas (I), (II), (III) or (IV)
Bis (aminostyryl) stilbene compounds, bis
A method for producing an (aminostyryl) stilbene compound. Embedded image(However, in the general formulas [V] and [VI], R¹¹³
And R¹¹⁴Is the following R¹, R^Two, R¹⁸, R¹⁹,
R³⁵, R³⁶, R⁵²Or R⁵³Is an aryl group corresponding to
R¹¹⁵And R¹¹⁶Is the following R^Three, R^Four, R
²⁰, R^{twenty one}, R³⁷, R³⁸, R⁵⁴Or R⁵⁵Ally equivalent to
Group. )(However, in the general formulas [VII] and [VIII], R
¹¹⁷And R¹¹⁸Are the same or different
A hydrogen group;¹¹⁹, R¹²⁰, R¹²¹, R¹²², R
^{one two Three}, R¹²⁴, R¹²⁵And R¹²⁶Are respectively
R^Five, R⁶, R⁷, R⁸, R⁹, R^Ten, R¹¹, R¹², R
^{twenty two}, R^{twenty three}, R^{twenty four}, R^{twenty five}, R²⁶, R²⁷, R²⁸, R²⁹, R
³⁹, R⁴⁰, R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵, R⁴⁶,
R⁵⁶, R⁵⁷, R⁵⁸, R⁵⁹, R⁶⁰, R⁶¹, R⁶²Or R⁶³To
X is a halogen atom, and k is 1 or more.
Is the integer above. )[However, in the general formula [I], R¹And R^FourIs nothing
A substituted aryl group;^TwoAnd R^ThreeIs the following general formula
An aryl group represented by the formula (1):(However, in the general formula (1), R¹³, R¹⁴,
R^Fifteen, R¹⁶And R¹⁷Are the same or different groups.
And at least one of them is saturated with 1 or more carbon atoms or
An unsaturated hydrocarbonoxy or hydrocarbon group
You. ), R^Five, R⁶, R⁷, R⁸, R⁹, R^Ten, R¹¹Passing
And R¹²Are the same or different groups,
At least one of which is a hydrogen atom, a saturated or unsaturated hydrocarbon
Group, cyano group, nitro group, trifluoromethyl group or
And k is an integer of 1 or more. ][However, in the general formula [II], R¹⁸, R¹⁹, R²⁰
And R^{twenty one}Are the same or different groups, and
An aryl group represented by the general formula (2):(However, in the general formula (2), R³⁰, R³¹,
R³², R³³And R³⁴Are the same or different groups.
And at least one of them is saturated with 1 or more carbon atoms or
An unsaturated hydrocarbonoxy or hydrocarbon group
You. ), R^{twenty two}, R^{twenty three}, R^{twenty four}, R^{twenty five}, R²⁶, R²⁷, R²⁸Passing
And R²⁹Are the same or different groups,
At least one of which is a hydrogen atom, a saturated or unsaturated hydrocarbon
Group, cyano group, nitro group, trifluoromethyl group or
And k is an integer of 1 or more. [Formula 28][However, in the above general formula [III], R³⁵, R³⁶, R
³⁷And R³⁸Is at least one represented by the following general formula (3).
And the rest are unsubstituted aryl groups
And(However, in the general formula (3), R⁴⁷, R⁴⁸,
R⁴⁹, R⁵⁰And R⁵¹Are the same or different groups.
And at least one of them is saturated with 1 or more carbon atoms or
It is an unsaturated hydrocarbon amino group. ), R³⁹, R⁴⁰, R
⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵And R⁴⁶Are identical to each other
Are different groups, at least one of which is a hydrogen atom
, Saturated or unsaturated hydrocarbon group, cyano group, nitro
Group, trifluoromethyl group or halogen atom, k
Is an integer of 1 or more. [Chemical Formula 30][However, in the general formula [IV], R⁵³And R⁵⁴Are
Groups that are the same or different and are represented by the following general formula (4)
An aryl group represented by(However, in the general formula (4), R⁶⁴, R⁶⁵,
R⁶⁶, R⁶⁷And R⁶⁸Are the same or different groups.
And a hydrogen atom or at least one of them has 1 carbon atom
Above saturated or unsaturated hydrocarbon oxy group or hydrocarbon
Elementary group. ), R⁵²And R⁵⁴Are the same or different
An aryl group represented by the following general formula (5)
And(However, in the general formula (5), R⁶⁹, R⁷⁰,
R⁷¹, R⁷², R⁷³, R⁷⁴And R⁷⁵Are the same or different
A hydrogen atom or at least one of them
A saturated or unsaturated hydrocarbon oxy having one or more carbon atoms
Group, a hydrocarbon group, or a hydrocarbon amino group. ), R
⁵⁶, R⁵⁷, R⁵⁸, R⁵⁹, R⁶⁰, R⁶¹, R⁶²And R ⁶³Are
The same or different groups, at least
One of which is a hydrogen atom, a saturated or unsaturated hydrocarbon group,
Group, nitro group, trifluoromethyl group or halogen atom
And k is an integer of 1 or more. ] 7. The condensation is carried out by a Wittig-Horner (Wi
(ttig-Horner) reaction or Wittig reaction, and the diphosphonate and / or the diphosphonium is treated with a base in a solvent to generate a carbanion.
The method for producing a bis (aminostyryl) stilbene compound according to claim 6, wherein the compound is condensed with (N, N-diarylamino) benzaldehyde. 8. A method for obtaining a bis (aminostyryl) stilbene compound represented by the following general formula (6): [However, in the general formula (6), Ar ¹ , Ar ² ,
At least one of Ar ³ and Ar ⁴ has the following general formula (7), (8), (9), (10), (11), (1)
2) a group selected from aryl groups represented by (12 ′) or (12 ″), and the rest being unsubstituted aryl groups; (However, the general formulas (7), (8), (9), (1
0), (11), (12), (12 ') and (12 ")
In the above, R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² , R ⁸³ ,
R ⁸⁴ , R ⁸⁵ and R ⁸⁶ are a saturated or unsaturated hydrocarbon group having 1 or more carbon atoms, n is an integer of 0 to 5, and m is 0 to
3 is an integer, and 1 is an integer of 0 to 4. ), R ⁷⁶ and R ⁷⁷ are the same or different, and at least one of them is a hydrogen atom, a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. And 4- (N, N-diarylamino) represented by the following general formula (23) or (24).
At least one benzaldehyde; the above-mentioned general formula [VI
7. The method for producing a bis (aminostyryl) stilbene-based compound according to claim 6, wherein the diphosphonic acid ester represented by I] or the diphosphonium salt represented by the general formula [VIII] is condensed. Embedded image (However, in the general formulas (23) and (24), A
r ¹ , Ar ² , Ar ³ and Ar ⁴ are the same as described above. ) 9. The method for producing a bis (aminostyryl) stilbene compound according to claim 6, wherein R ¹¹⁷ and R ¹¹⁸ are each a saturated hydrocarbon group having 1 to 6 carbon atoms. 10. The method according to claim ⁸ , wherein said R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² ,
Method for producing R ^83, R ^84, and 1-6 carbon atoms in R ⁸⁵ and R ^86, bis (aminostyryl) stilbene compounds described in claim 8. 11. The following general formulas (13), (14) and (1)
5), (16), (17), (18), (19), (2)
The method for producing a bis (aminostyryl) stilbene-based compound according to claim 6, wherein the bis (aminostyryl) stilbene-based compound represented by (0) or (21) is obtained. Embedded image (However, in the general formula (13), R ⁸⁷ and R ^87
88 is the same or different and is a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. ) (However, in the general formula (14), R ⁸⁹ and R
⁹⁰ is the same or different saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. ) (However, in the general formula (15), R ⁹¹ , R ⁹² , R
⁹³ and R ⁹⁴ are the same or different and are each a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. ) (However, in the above general formula (16), R ⁹⁵ , R ⁹⁶ , R
⁹⁷ and R ⁹⁸ are the same or different and are each a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. ) (However, in the general formula (17), R ⁹⁹ and R ¹⁰⁰
Are the same or different saturated or unsaturated hydrocarbon groups having 1 to 6 carbon atoms. ) (However, in the general formula (18), R ¹⁰¹ and R
¹⁰² is the same or different and is a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. ) (However, in the general formula (19), R ¹⁰³ ,
R ¹⁰⁴ , R ¹⁰⁵ and R ¹⁰⁶ are the same or different and are each a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. ) (However, in the general formula (20), R ¹⁰⁷ ,
R ¹⁰⁸ , R ¹⁰⁹ and R ¹¹⁰ are the same or different and are each a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. ) (However, in the general formula (21), R ¹¹¹ and R
¹¹² is the same or different and is a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. ) 12. The following structural formulas (22) -1, (22)-
2, (22) -3, (22) -4, (22) -5, (2
2) -6, (22) -7, (22) -8, (22)-
9, (22) -10, (22) -11, (22) -12
Or the method for producing a bis (aminostyryl) stilbene-based compound according to claim 6, represented by (22) -13. Embedded image 13. A diphosphonic acid ester or diphosphonium salt represented by the following general formula [VII] or [VIII]. Embedded image (However, in the general formulas [VII] and [VIII], R
¹¹⁷ and R ¹¹⁸ are the same or different hydrocarbon groups, and R ¹¹⁹ , R ¹²⁰ , R ¹²¹ , R ¹²² , R
¹²³ , R ¹²⁴ , R ¹²⁵ and R ¹²⁶ are the same or different groups, and at least one of them is a hydrogen atom, a saturated or unsaturated hydrocarbon group, a cyano group, a nitro group, a trifluoromethyl group Or a halogen atom, X is a halogen atom, and k is an integer of 1 or more. ) 14. The method wherein R ¹¹⁷ and R ^{118 each} have 1 to 4 carbon atoms.
14. The diphosphonic ester or diphosphonium salt according to claim 13, which is a saturated hydrocarbon group. 15. The following general formulas (25), (26) and (2)
The diphosphonic acid ester or diphosphonium salt according to claim 13, which is represented by 7), (28), (29) or (30). Embedded image (However, the general formulas (25), (26), (27),
In (28), (29) and (30), R ¹¹⁷ , R
¹¹⁸ and X are the same as described above. ) 16. An aryl halide compound represented by the following general formula [IX] and a trialkyl phosphite or triphenylphosphine (PPh) represented by the following general formula [X]:
₃ ) to give the following general formula [VII]:
Or a method for producing a diphosphonic ester or a diphosphonium salt, which obtains the diphosphonic ester or the diphosphonium salt represented by [VIII]. Embedded image (However, in the general formula [IX], R ¹¹⁹ , R ¹²⁰ ,
R ¹²¹ , R ¹²² , R ¹²³ , R ¹²⁴ , R ¹²⁵ and R ¹²⁶ are the same or different groups, and at least one of them is a hydrogen atom, a saturated or unsaturated hydrocarbon group, a cyano group, A nitro group, a trifluoromethyl group or a halogen atom, X is a halogen atom, and k is 1
Is an integer greater than or equal to. ) General formula [X]: P (in OR ¹²⁷⁾ ₃ or P (OR ¹²⁸⁾ ₃ (where the general formula (X), R ¹²⁷ and R ¹²⁸
Are the same or different hydrocarbon groups. ) (However, in the general formulas [VII] and [VIII], R
¹¹⁷ and R ¹¹⁸ are the same or different hydrocarbon groups, and R ¹¹⁹ , R ¹²⁰ , R ¹²¹ , R ¹²² , R
¹²³ , ^R124 , ^R125 , ^R126 , X and k are the same as described above. ) 17. The method according to claim 17, wherein R ¹¹⁷ and R ^{118 each} have 1 to 6 carbon atoms.
The method for producing a diphosphonic ester or a diphosphonium salt according to claim 16, wherein the compound is a saturated hydrocarbon group. 18. The following general formulas (25), (26) and (2)
The method for producing a diphosphonic acid ester or diphosphonium salt according to claim 16, wherein the diphosphonic acid ester or diphosphonium salt represented by 7), (28), (29) or (30) is obtained. Embedded image (However, the general formulas (25), (26), (27),
In (28), (29) and (30), R ¹¹⁷ , R
¹¹⁸ and X are the same as described above. ) 19. An aryl halide compound represented by the following general formula [IX]. Embedded image (However, in the general formula [IX], R ¹¹⁹ , R ¹²⁰ ,
R ¹²¹ , R ¹²² , R ¹²³ , R ¹²⁴ , R ¹²⁵ and R ¹²⁶ are the same or different groups, and at least one of them is a hydrogen atom, a saturated or unsaturated hydrocarbon group, a cyano group, A nitro group, a trifluoromethyl group or a halogen atom, X is a halogen atom, and k is 1
Is an integer greater than or equal to. ) 20. A reaction between a stilbene compound represented by the following general formula [XI] and an N-halogenated succinimide represented by the following general formula [XII]:
A method for producing an aryl halide compound, wherein an aryl halide compound represented by the following general formula [IX] is obtained. Embedded image (However, in the general formula [XI], R ¹¹⁹ , R ¹²⁰ ,
R ¹²¹ , R ¹²² , R ¹²³ , R ¹²⁴ , R ¹²⁵ and R ¹²⁶ are the same or different groups, and at least one of them is a hydrogen atom, a saturated or unsaturated hydrocarbon group, a cyano group, A nitro group, a trifluoromethyl group or a halogen atom, X is a halogen atom, and k is 1
Is an integer greater than or equal to. ) (However, in the above general formula [XII], X is a halogen atom.) (However, in the general formula [IX], R ¹¹⁹ , R ¹²⁰ ,
R ¹²¹ , R ¹²² , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , X
And k are the same as described above. ) 21. An organic electroluminescent device in which an organic layer having a light emitting region is provided between an anode and a cathode, wherein the organic layer has the following general formula [I], [II], [III] or [IV] An organic electroluminescent device comprising at least one of the bis (aminostyryl) stilbene compounds represented by the formula (1) as an organic light emitting material. Embedded image [However, in the general formula [I], R ¹ and R ⁴ are an unsubstituted aryl group, and R ² and R ³ are an aryl group represented by the following general formula (1). (However, in the general formula (1), R ¹³ , R ¹⁴ ,
R ¹⁵ , R ¹⁶ and R ¹⁷ are the same or different groups, and at least one of them is a saturated or unsaturated hydrocarbon oxy group having 1 or more carbon atoms, or a hydrocarbon group. ), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are the same or different groups, and each represents a hydrogen atom, a saturated or unsaturated hydrocarbon group, A group selected from the group consisting of methyl groups, and k is an integer of 1 or more. [Formula 57] [However, in the general formula [II], R ¹⁸ , R ¹⁹ , R ²⁰
And R ²¹ are the same or different groups, and are aryl groups represented by the following general formula (2). (However, in the general formula (2), R ³⁰ , R ³¹ ,
R ³² , R ³³ and R ³⁴ are the same or different groups, and at least one of them is a saturated or unsaturated hydrocarbon oxy group having 1 or more carbon atoms, or a hydrocarbon group. ), R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ are the same or different groups, and each represents a hydrogen atom, a saturated or unsaturated hydrocarbon group, A group selected from the group consisting of methyl groups, and k is an integer of 1 or more. Embedded image [However, in the general formula [III], R ³⁵ , R ³⁶ , R
^At least one of ³⁷ and ^R38 is an aryl group represented by the following general formula (3), and the rest is an unsubstituted aryl group. (However, in the general formula (3), R ⁴⁷ , R ⁴⁸ ,
R ⁴⁹ , R ⁵⁰ and R ⁵¹ are the same or different groups, and at least one of them is a saturated or unsaturated hydrocarbon amino group having 1 or more carbon atoms. ), R ³⁹ , R ⁴⁰ , R
⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are the same or different groups and are selected from the group consisting of a hydrogen atom, a saturated or unsaturated hydrocarbon group and a trifluoromethyl group. And k is an integer of 1 or more. Embedded image [However, in the general formula [IV], R ⁵³ and R ⁵⁵ are the same or different from each other, and are an aryl group represented by the following general formula (4). (However, in the general formula (4), R ⁶⁴ , R ⁶⁵ ,
R ⁶⁶ , R ⁶⁷ and R ⁶⁸ are the same or different groups, and each has a hydrogen atom or at least one of them having 1 carbon atom.
The above is a saturated or unsaturated hydrocarbon oxy group or hydrocarbon group. ), R ⁵² and R ⁵⁴ are the same or different groups, and are aryl groups represented by the following general formula (5). (However, in the general formula (5), R ⁶⁹ , R ⁷⁰ ,
R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ and R ⁷⁵ are the same or different groups, and each is a hydrogen atom, or at least one of them is a saturated or unsaturated hydrocarbon oxy group having 1 or more carbon atoms; It is a hydrogen group or a hydrocarbon amino group. ), R
⁵⁶ , R ⁵⁷ , R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² and R ⁶³ are the same or different groups, and each represents a hydrogen atom, a saturated or unsaturated hydrocarbon group and a trifluoromethyl group. And k is an integer of 1 or more. ] 22. The bis (aminostyryl) stilbene-based compound is represented by the following general formula (6).
2. The organic electroluminescent device described in 1. above. Embedded image [However, in the general formula (6), Ar ¹ , Ar ² ,
At least one of Ar ³ and Ar ⁴ has the following general formula (7), (8), (9), (10), (11), (1)
2) a group selected from aryl groups represented by (12 ′) or (12 ″), and the rest being unsubstituted aryl groups; (However, the general formulas (7), (8), (9), (1
0), (11), (12), (12 ') and (12 ")
In the above, R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² , R ⁸³ ,
R ⁸⁴ , R ⁸⁵ and R ⁸⁶ are a saturated or unsaturated hydrocarbon group having 1 or more carbon atoms, n is an integer of 0 to 5, and m is 0 to
3 is an integer, and 1 is an integer of 0 to 4. ), R ⁷⁶ and R ⁷⁷ are the same or different, and at least one of them is a hydrogen atom, a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. ] 23. The method according to claim ²² , wherein R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² ,
The organic electroluminescent device according to claim 22, wherein R ⁸³ , R ⁸⁴ , R ⁸⁵ and R ⁸⁶ have 1 to 6 carbon atoms. 24. The bis (aminostyryl) stilbene compound represented by the following general formulas (13), (14) and (15)
Or the organic electroluminescent device according to claim 21, represented by (16). Embedded image (However, in the general formula (13), R ⁸⁷ and R ^87
88 is the same or different and is a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. ) (However, in the general formula (14), R ⁸⁹ and R
⁹⁰ is the same or different saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. ) (However, in the general formula (15), R ⁹¹ , R ⁹² , R
⁹³ and R ⁹⁴ are the same or different and are each a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. ) (However, in the above general formula (16), R ⁹⁵ , R ⁹⁶ , R
⁹⁷ and R ⁹⁸ are the same or different and are each a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. ) 25. The bis (aminostyryl) stilbene compound represented by the following structural formula (22) -1, (22) -2,
(22) -3, (22) -4, (22) -5, (22)
The organic electroluminescent device according to claim 21, represented by -6 or (22) -7. Embedded image 26. The organic layer has an organic laminated structure in which a hole transport layer and an electron transport layer are laminated, and the bis (aminostyryl) stilbene-based compound is used as a material for forming the hole transport layer. The organic electroluminescent device according to claim 21, wherein is used. 27. The organic layer has an organic laminated structure in which a hole transport layer and an electron transport layer are sequentially laminated, and the bis (aminostyryl) stilbene-based compound is used as a material for forming the electron transport layer. 22. is used.
2. The organic electroluminescent device described in 1. above. 28. The organic layer has an organic laminated structure in which a hole transport layer, a light emitting layer, and an electron transport layer are laminated,
22. The bis (aminostyryl) stilbene-based compound is used as a material for forming the light emitting layer.
2. The organic electroluminescent device described in 1. above.