JP2002326965A - Spirofluorene compound, method for producing the same, intermediate for synthesizing the same, and organic electroluminescent element using the spirofluorene compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a spirofluorene compound suitable as an organic luminescent material which gives strong blue light emission, to provide a method for efficiently producing the compound, to provide an intermediate for synthesizing the compound, and to provide an organic electroluminescent element using the spirofluorene compound. SOLUTION: This spirofluorene compound is expressed by the general formula (1) [the benzo groups in the formula (1) may be each independently substituted and/or fused together].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a spirofluorene compound which is suitable as an organic light emitting material which emits blue light, a method for producing the same, a synthetic intermediate thereof, and an organic electroluminescence device using the spirofluorene compound. is there.

[0002]

2. Description of the Related Art In recent years, the importance of interfaces between humans and machines, including multimedia-oriented products, has been increasing in importance. In order for a human to operate a machine more comfortably and efficiently, it is necessary to extract the information of the machine to be operated without error, simply, instantly, and with a sufficient amount of information. Research on various display elements such as a display and the like has been conducted.

[0003] Further, with the miniaturization of machines, the demand for miniaturization and thinning of display elements is increasing daily.

For example, there has been a remarkable progress in miniaturization of laptop information processing devices, such as notebook personal computers and notebook word processors, which are integrated with display elements. Display innovation is also great.

[0005] Today, liquid crystal displays are used as interfaces for various products. Not only laptop information processing equipment, but also small TVs, clocks,
Products using a liquid crystal display such as a calculator as an interface are widely used in our daily lives.

[0006] These liquid crystal displays are characterized by the fact that liquid crystals are driven at low voltage and consume low power, so that they are widely used from small-sized display devices to large-capacity display devices. It has been studied as the center of display elements for interfacing.

[0007]

However, liquid crystal displays do not have self-luminous properties, and therefore require a backlight when used. The power consumed when driving the backlight requires a larger amount of power than the power consumed when driving the liquid crystal. Will be restricted.

Further, the liquid crystal display has a problem that it is not suitable for a large display device such as a large display because of a narrow viewing angle.

Further, since the liquid crystal display is a display method based on the alignment state of liquid crystal molecules, it is considered that there is a great problem that the contrast varies depending on the angle even within the viewing angle.

In consideration of the driving method, the active matrix method, which is one of the driving methods, shows a response speed sufficient to handle moving images. However, since a TFT (thin film transistor) driving circuit is used, pixel defects are reduced. This makes it difficult to increase the screen size.

The other driving method, the simple matrix method, is low in cost and relatively easy to enlarge the screen size, however, it does not have a sufficient response speed for handling moving images. There's a problem.

On the other hand, as a self-luminous display element,
Plasma display devices, inorganic electroluminescent devices, organic electroluminescent devices, and the like have been studied.

The plasma display element uses plasma emission in a low-pressure gas for display, and is suitable for increasing the size and capacity, but has problems in terms of thinning and cost. Further, since a high-voltage AC bias is required for driving, it is not suitable for a portable device.

As the inorganic electroluminescent device, a green light emitting display or the like has been commercialized. However, like the plasma display device, it is driven by AC bias and requires several hundred volts for driving. I have.

Further, by using an inorganic material, red (R), green (G), and blue (B) necessary for a color display can be obtained.
However, since an inorganic material is used as the light emitting material, it is difficult to control the emission wavelength and the like by molecular design and the like, and it is difficult to achieve full color.

On the other hand, the electroluminescence phenomenon caused by an organic compound is as follows.
It has been studied for a long time since the light-emitting phenomenon caused by carrier injection into an anthracene single crystal that emits strong fluorescence was discovered in the early 1960s.
Moreover, since it is a single crystal, it has been conducted as a basic research of carrier injection into an organic material.

However, in 1987 Eastman Kodak
Since Tang et al. Announced a stacked organic thin film electroluminescent device having an amorphous light emitting layer capable of low voltage driving and high luminance emission, red (R), green (G), and blue (B) have been used in various fields. Emission of three primary colors, stability, increased brightness, laminated structure,
Research and development of manufacturing methods and the like have been actively conducted.

The first advantage of the organic light emitting material is that the optical properties of the material can be controlled to some extent by molecular design. At present, various novel organic light emitting materials have been researched and developed by molecular design and the like. I have. Organic electroluminescent devices using these organic light-emitting materials as constituent materials have excellent features such as low-voltage direct current drive, thinness, and self-luminous properties. It is beginning to take place.

However, considering the practical use of the organic electroluminescent device, there are still problems in the reliability of the device such as chromaticity, luminous life and luminous efficiency, and it is necessary to solve those problems. However, this is a major factor in realizing a full-color display using an organic electroluminescent element.

In view of the above situation, an object of the present invention is to provide a spirofluorene compound suitable as a blue organic luminescent material exhibiting strong luminescence, a method for producing the compound with high efficiency, a synthetic intermediate thereof, and a synthetic intermediate thereof. An object of the present invention is to provide an organic electroluminescent device using a spirofluorene compound.

[0021]

Means for Solving the Problems According to the present invention, as a result of intensive studies to solve the above-mentioned problems, a spirofluorene compound represented by the following general formula (1) or (2) exhibits strong luminescence, The present inventors have found that the material can be used as a light emitting material, established a general and highly efficient manufacturing method thereof, and reached the present invention.

That is, the present invention relates to a spirofluorene compound represented by the following general formula (1).

Embedded image (However, in the general formula (1), the benzo groups may be substituted and / or fused independently of each other.)

The present invention also relates to a spirofluorene compound represented by the following general formula (2).

Embedded image [However, in the general formula (2), A ¹ , B ¹ , C ¹ ,
D ¹ , E ¹ and F ¹ may be the same or different from each other, and each independently represents a group represented by the following general formula:

Embedded image Is one of In the general formula (2) and the group, each R may be the same as or different from each other, and may be a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, An alkoxy group, an ester group, a hydroxyl group, a halogen atom, a cyano group, a nitro group, an alkylamino group, an aryl group, an arylamino group or an aryloxy group, wherein the aryl group is a substituted or unsubstituted phenyl group, biphenyl group , Triphenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-fluorenyl, 2-fluorenyl or 9-fluorenyl, and the like. The substituent is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amino group, an alkylamino group. Arylamino group, a cyano group, a nitro group, a hydroxyl group or a halogen atom. Further, W, X, Y and Z in the group are each independently a hydrogen atom, or a substituted or unsubstituted carbon atom having 6 to 6 carbon atoms.
30, and the substituents of W and X, and of Y and Z may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated 5- or 6-membered ring, wherein The substituent is an alkyl group having 1 to 6 carbon atoms, 6 to 30 carbon atoms.
Is an aryl group, an amino group, an alkylamino group, an arylamino group, a cyano group, a nitro group, a hydroxyl group or a halogen atom, and these substituents may be single or plurally substituted. Also, 1 in the above group is 1, 2 or 3,
m and n are integers of 0-6. Further, in the group, D represents -CR ¹ - a, or nitrogen, wherein R ¹ is a hydrogen atom or a straight-chain having 1 to 6 carbon atoms, branched or cyclic alkyl group, an aryl having 6 to 20 carbon atoms Represents a group, an amino group, an alkylamino group, an arylamino group, a cyano group, a nitro group, a hydroxyl group or a halogen atom, and these substituents may be single or plurally substituted. In the above group, E is-
O -, - S -, - NR 2 -, CR 3 R 4 -, - CH = CH
—, —CH ＝ N—, and R ² , R ³ , and R ⁴ may be the same or different from each other, and represent a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms. An aryl group having 6 to 20 carbon atoms, an amino group, an alkylamino group,
It represents an arylamino group, a cyano group, a nitro group, a hydroxyl group or a halogen atom, and these substituents may be single or plurally substituted. ]

The spirofluorene compound of the present invention has excellent thermal stability, provides good luminous efficiency, is extremely difficult to crystallize, and can form a uniform amorphous thin film. Further, when the spirofluorene compound of the present invention is used as a constituent material of the organic electroluminescent device, it is possible to realize a full color display such as a color display and to extend the life of the device.

The spirofluorene compound represented by the general formula (2) comprises at least one of pinacolato boron compounds represented by the following general formulas (3) to (9) and the following general formula (1)
By performing a coupling reaction with the bromo compound represented by 0) in the presence of a metal catalyst, the compound can be produced with high efficiency.

Embedded image [However, in the general formulas (3) to (9), each R
May be the same or different from each other, a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkoxy group, an ester group, a hydroxyl group,
A halogen atom, a cyano group, a nitro group, an alkylamino group, an aryl group, an arylamino group or an aryloxy group, wherein the aryl group is a substituted or unsubstituted phenyl group, biphenyl group, triphenyl group, 1-naphthyl Group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-fluorenyl group, 2
A fluorenyl group or a 9-fluorenyl group, wherein the substituent means an alkyl group having 1 to 6 carbon atoms,
An alkoxy group having 10 to 10, an aryl group having 6 to 30 carbon atoms,
It is an amino group, an alkylamino group, an arylamino group, a cyano group, a nitro group, a hydroxyl group or a halogen atom. W, X, Y and Z in the group are each independently a hydrogen atom or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituent of W and X, and a substituent of Y and Z May be bonded to each other to form a substituted or unsubstituted saturated or unsaturated 5- or 6-membered ring, wherein the substituent is
An alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amino group, an alkylamino group, an arylamino group,
A cyano group, a nitro group, a hydroxyl group or a halogen atom,
These substituents may be single or plurally substituted.
Also, 1 in the above group is 1, 2 or 3, and m and n are integers of 0 to 6. In the above group, D represents -CR ^1-
Or nitrogen, wherein R ¹ is a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, an amino group, an alkylamino group,
It represents an arylamino group, a cyano group, a nitro group, a hydroxyl group or a halogen atom, and these substituents may be single or plurally substituted. In the above groups, E is -O-, -S
^{-, - NR 2 -, CR} 3 R 4 -, - CH = CH -, - CH
R ² , R ³ , and R ⁴ may be the same or different from each other, and may be a hydrogen atom, a straight-chain, branched or cyclic alkyl group having 1 to 6 carbon atoms, To 20 aryl groups, amino groups, alkylamino groups, arylamino groups, cyano groups, nitro groups, hydroxyl groups or halogen atoms, and these substituents may be single or plurally substituted. ]

Embedded image [However, in the general formula (10), I ¹ , J ¹ ,
At least one of K ¹ , L ¹ , M ¹ and N ¹ is a halogen atom of bromine atom (Br) or iodine atom (I);
Each R may be the same or different from each other,
A hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkoxy group or an ester group,
A hydroxyl group, a halogen atom, a cyano group, a nitro group, an alkylamino group, an aryl group, an arylamino group or an aryloxy group, wherein the aryl group is a substituted or unsubstituted phenyl group, biphenyl group, triphenyl group,
-Naphthyl group, 2-naphthyl group, 1-anthryl group, 2
-Anthryl group, 9-anthryl group, 1-fluorenyl group, 2-fluorenyl group or 9-fluorenyl group and the like, wherein the substituent means an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 10 carbon atoms. Group, an aryl group having 6 to 30 carbon atoms, an amino group, an alkylamino group, an arylamino group, a cyano group, a nitro group, a hydroxyl group or a halogen atom. ]

The spirofluorene compound of the present invention is preferably represented by the following general formula (11).

Embedded image [However, in the general formula (11), A ² , B ² ,
C ² , D ² , E ² , and F ² may be the same or different from each other, and each independently represents a group represented by the following general formula:

Embedded image It is. In the general formula (11) and the group, each R may be the same or different from each other, and may be a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, An alkoxy group, an ester group, a hydroxyl group, a halogen atom, a cyano group, a nitro group, an alkylamino group, an aryl group, an arylamino group or an aryloxy group, wherein the aryl group is a substituted or unsubstituted phenyl group, biphenyl group , A triphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-fluorenyl group, a 2-fluorenyl group or a 9-fluorenyl group. The substituent means an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amino group, an alkyl group. Amino group, an arylamino group, a cyano group, a nitro group, a hydroxyl group or a halogen atom. Also, 1 in the above group is 1, 2 or 3, and m
And n are integers from 0 to 6. ]

The spirofluorene compound represented by the general formula (11) is obtained by dehydrochlorinating a tetrazole compound represented by the following general formula (12) and a carboxylic acid chloride compound represented by the following general formula (13). By condensing in the presence of an agent, efficient production can be achieved.

Embedded image [However, in the general formula (12), each R may be the same or different from each other, and may represent a hydrogen atom,
A straight-chain, branched or cyclic alkyl group having 20 carbon atoms, an alkoxy group, an ester group, a hydroxyl group, a halogen atom, a cyano group, a nitro group, an alkylamino group, an aryl group, an arylamino group or an aryloxy group;
The aryl group is a substituted or unsubstituted phenyl group, a biphenyl group, a triphenyl group, a 1-naphthyl group,
A 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-fluorenyl group, a 2-fluorenyl group, a 9-fluorenyl group, or the like, wherein the substituent has 1 to 6 carbon atoms. An alkyl group having 1 to 10 carbon atoms
An alkoxy group, an aryl group having 6 to 30 carbon atoms, an amino group, an alkylamino group, an arylamino group, a cyano group,
It is a nitro group, a hydroxyl group or a halogen atom. Also, 1 in the above group is 1, 2 or 3, and m and n are integers of 0 to 6. ]

Embedded image [However, in the general formula (13), I ² , J ² ,
At least one of K ² , L ² , M ^2, and N ² is a carboxylic acid chloride (—COCl) group, and each R may be the same or different, and includes a hydrogen atom,
A straight-chain, branched or cyclic alkyl group, alkoxy group or ester group having 20 to 20 carbon atoms, hydroxyl group, halogen atom, cyano group, nitro group, alkylamino group, aryl group, arylamino group or aryloxy group. And the aryl group is a substituted or unsubstituted phenyl group, biphenyl group, triphenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-fluorenyl. A 2-fluoroenyl group, a 9-fluorenyl group, or the like, wherein the substituent means an alkyl group having 1 to 6 carbon atoms,
0 alkoxy group, aryl group having 6 to 30 carbon atoms, amino group, alkylamino group, arylamino group, cyano group, nitro group, hydroxyl group or halogen atom. ]

More specifically, the spirofluorene compound of the present invention is preferably represented by the following general formula (14).

Embedded image [However, in the general formula (14), A ³ , B ³ ,
C ³ , D ³ , E ³ and F ³ may be the same or different from each other, and each independently represents a group represented by the following general formula:

Embedded image It is. In the general formula (14) and the group, each R may be the same as or different from each other, and may be a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, An alkoxy group, an ester group, a hydroxyl group, a halogen atom, a cyano group, a nitro group, an alkylamino group, an aryl group, an arylamino group or an aryloxy group, wherein the aryl group is a substituted or unsubstituted phenyl group, biphenyl group , Triphenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-fluorenyl, 2-fluorenyl or 9-fluorenyl, and the like. The substituent means an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amino group, an alkyl group. Amino group, an arylamino group, a cyano group, a nitro group, a hydroxyl group or a halogen atom. Also, 1 in the above group is 1, 2 or 3, and m
And n are integers from 0 to 6. ]

The spirofluorene compound represented by the general formula (14) is obtained by dehydrochlorinating a hydrazine compound represented by the following general formula (15) and a carboxylic acid chloride compound represented by the following general formula (17). The intermediate represented by the following general formula (18) produced by condensation in the presence of an agent and the following general formula (16) are efficiently produced by dehydration condensation in the presence of a strong acid or a dehydrating agent. can do.

Embedded image General formula (16): H ₂ NR [provided that, in the general formula (15) and the general formula (16), each R may be the same or different and each represents a hydrogen atom, 1 to 1 A straight chain having 20 carbon atoms,
A branched or cyclic alkyl group, an alkoxy group, an ester group, a hydroxyl group, a halogen atom, a cyano group, a nitro group, an alkylamino group, an aryl group, an arylamino group, or an aryloxy group; Substituted phenyl, biphenyl, triphenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-fluorenyl, 2-fluorenyl or 9-fluorenyl Wherein the substituent is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amino group, an alkylamino group, an arylamino group, It is a cyano group, a nitro group, a hydroxyl group or a halogen atom. In the general formula (15), 1 is 1, 2 or 3, and m and n are integers of 0 to 6. ]

Embedded image [However, in the general formula (17), I ³ , J ³ ,
At least one of K ³ , L ³ , M ³ and N ³ is a carboxylic acid chloride (—COCl) group, and each R may be the same or different from each other, and may be a hydrogen atom,
A straight-chain, branched or cyclic alkyl group, alkoxy group or ester group having 20 to 20 carbon atoms, hydroxyl group, halogen atom, cyano group, nitro group, alkylamino group, aryl group, arylamino group or aryloxy group. And the aryl group is a substituted or unsubstituted phenyl group, biphenyl group, triphenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-fluorenyl. A 2-fluoroenyl group, a 9-fluorenyl group, or the like, wherein the substituent means an alkyl group having 1 to 6 carbon atoms,
0 alkoxy group, aryl group having 6 to 30 carbon atoms, amino group, alkylamino group, arylamino group, cyano group, nitro group, hydroxyl group or halogen atom. ]

Embedded image [However, in the general formula (18), I ⁴ , J ⁴ ,
At least one of K ⁴ , L ⁴ , M ⁴ and N ⁴ is a group represented by the following general formula:

Embedded image [However, in the general formula (18) and the group, each R may be the same or different from each other, and may be a hydrogen atom,
A linear, branched or cyclic alkyl group, alkoxy group, ester group, hydroxyl group, halogen atom, cyano group, nitro group, alkylamino group, aryl group, arylamino group or aryloxy group having 1 to 20 carbon atoms. And the aryl group is a substituted or unsubstituted phenyl group, biphenyl group, triphenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1- A fluorenyl group, a 2-fluorenyl group, a 9-fluorenyl group, or the like, wherein the substituent means an alkyl group having 1 to 6 carbon atoms,
0 alkoxy group, aryl group having 6 to 30 carbon atoms, amino group, alkylamino group, arylamino group, cyano group, nitro group, hydroxyl group or halogen atom. Also,
L in the above group is 1, 2 or 3, and m and n are from 0 to 6
Is an integer. ]

Particularly preferred is a spirofluorene compound represented by the following general formula (19).

Embedded image [However, in the general formula (19), A ⁴ , B ⁴ ,
C ⁴ , D ⁴ , E ⁴ and F ⁴ may be the same or different from each other, and each independently represents a group represented by the following general formula:

Embedded image Is one of In the above groups, each R may be the same or different from each other, and may be a hydrogen atom,
A straight-chain, branched or cyclic alkyl group having 0 carbon atoms, an alkoxy group, an ester group, a hydroxyl group, a halogen atom, a cyano group, a nitro group, an alkylamino group, an aryl group, an arylamino group or an aryloxy group; The aryl group is a substituted or unsubstituted phenyl group,
Biphenyl group, triphenyl group, 1-naphthyl group, 2-
Naphthyl group, 1-anthryl group, 2-anthryl group, 9
-Anthryl group, 1-fluorenyl group, 2-fluorenyl group or 9-fluorenyl group and the like, wherein the substituent means an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a carbon atom having 6 carbon atoms. To 30 aryl groups, amino groups, alkylamino groups, arylamino groups, cyano groups, nitro groups, hydroxyl groups or halogen atoms. W, X, Y and Z in the group are each independently a hydrogen atom or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms;
The substituents of W and X, and the substituents of Y and Z may combine to form a substituted or unsubstituted saturated or unsaturated 5- or 6-membered ring, wherein the substituent has a carbon number of An alkyl group having 1 to 6, an aryl group having 6 to 30 carbon atoms, an amino group,
An alkylamino group, an arylamino group, a cyano group, a nitro group, a hydroxyl group, or a halogen atom, and these substituents may be single or plurally substituted. Also, 1 in the above group is 1, 2 or 3, and m and n are integers of 0 to 6. Further, in the group, D represents -CR ¹ - a, or nitrogen, wherein R ¹ is a hydrogen atom or a straight-chain having 1 to 6 carbon atoms, branched or cyclic alkyl group, an aryl having 6 to 20 carbon atoms Represents a group, an amino group, an alkylamino group, an arylamino group, a cyano group, a nitro group, a hydroxyl group or a halogen atom, and these substituents may be single or plurally substituted. In the above groups, E is -O-, -S-, -NR
^2- , CR ³ R ⁴ —, —CH ＝ CH—, —CH ＝ N—, and R ² , R ³ , and R ⁴ may be the same or different from each other, and represent a hydrogen atom or a carbon atom. A linear, branched or cyclic alkyl group of 1 to 6, an aryl group having 6 to 20 carbon atoms, an amino group, an alkylamino group, an arylamino group,
A cyano group, a nitro group, a hydroxyl group or a halogen atom,
These substituents may be single or plurally substituted. ]

The spirofluorene compound of the present invention is particularly preferably represented by the following general formula (20).

Embedded image [However, in the general formula (20), A ⁵ , B ⁵ ,
C ⁵ , D ⁵ , E ⁵ and F ⁵ may be the same or different from each other and are each independently a hydrogen atom or any of the following general formulas (abbreviations) L1 to L23. ]

Embedded image

The most preferred spirofluorene compounds of the present invention are those represented by the above-mentioned general formulas (abbreviations) L1 to L23, which have the meaning of the above-mentioned general formula (20) and are shown in the following Tables 1 to 3 Group.

[0033]

[Table 1]

[Table 2]

[Table 3]

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

That is, the general formulas (2), (11) and (1)
4) The above-mentioned general formula (1) used as a synthetic intermediate of a spirofluorene compound represented by (19) or (20)
0), (13), (17) or (18).

FIGS. 1 to 4 show an organic electroluminescent device (EL device) using a compound according to the present invention as an organic light emitting material.
Are respectively shown.

FIG. 1 shows a transmissive organic electroluminescent element A in which emitted light 20 passes through a cathode 3.
Observable from the side. FIG. 2 shows a reflective organic electroluminescent element B in which the reflected light from the cathode 3 is also obtained as the emitted light 20.

Referring to FIG. 1, reference numeral 1 denotes a substrate for forming an organic electroluminescent device, which may be made of glass, plastic, or another appropriate material. In addition, when the organic electroluminescent element is used in combination with another display element, the substrate can be shared. For example, when active matrix driving is performed, a TFT (Thin Film Transistors) can be used as the substrate. It is possible.
Reference numeral 2 denotes a transparent electrode (anode). For example, in the transmission type organic electroluminescent device A, a transparent electrode ITO (indium tin oxidized
e), IZO (Indium zinc oxide), SnO _{2 and the} like can be used. In the reflection type organic electroluminescent device B, Cr, Fe,
Co, Ni, Cu, Ta, W, Pt, Mo, Au and alloys thereof can be used.

Reference numeral 5 denotes an organic light emitting layer, which contains a compound according to 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 will be described later, 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 laminated can be used. Further, in order to improve the charge transporting performance in a range satisfying the object of the present invention, one or both of the hole transporting layer and the electron transporting layer has a structure in which thin films of a plurality of types of materials are stacked, or a plurality of types of materials. It does not prevent the use of a thin film having a mixed composition. Further, in order to improve the light emission performance, a structure in which this thin film is included in the hole transport layer or the electron transport layer, or both, using at least one kind of an abnormal fluorescent material may be used. In these cases, a thin film for controlling the transport of holes or electrons can be included in the layer structure in order to improve the luminous efficiency.

Since the compound according to the present invention has both electron transporting performance and hole transporting performance, it can be used as a light emitting layer also serving as an electron transporting layer or as a light emitting layer also serving as a hole transporting layer in a device. Can also be used. Further, it is also possible to adopt a configuration in which the compound according to the present invention is used as a light emitting layer and is sandwiched between an electron transporting layer and a hole transporting layer.

In FIGS. 1 and 2, reference numeral 3 denotes a cathode;
Examples of the electrode material include an alloy of an active metal such as Li, Mg, and Ca and a metal such as Ag, Al, and In, LiF, and Li.
O ₂ 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. On the other hand, in a reflection type organic electroluminescent device, the thickness of the cathode is reduced to maintain a high transmittance, and the anode is made of a material having a high reflectance, so that the organic electroluminescence is taken out to the cathode side. Can be. Further, reference numeral 4 in the drawing denotes a sealing / protecting layer, and its 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 the organic electroluminescent device according to the present invention, the organic layer has an organic laminated structure (single hetero structure) in which a hole transport layer and an electron transport layer are laminated, and The compound according to the present invention may be used as a material for forming the electron transport layer. 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 a compound according to the present invention is used as a material for forming the light emitting layer. May be used.

FIG. 3 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. 3, when the light-emitting layer is omitted, the light-emitting layer 20 emits light 20 having a predetermined wavelength from the interface between the hole transport layer 6 and the electron transport layer 7. These emitted lights are observed from the substrate 1 side.

FIG. 4 shows a light transmitting substrate 1, a light transmitting anode 2, an organic layer 5b composed of a hole transport layer 10, a light emitting layer 11, and an electron transport layer 12; Are sequentially laminated, and this laminated structure is sealed with a protective film 4 to form an organic electroluminescent device D having a double hetero structure.

In the organic electroluminescent device shown in FIG. 4, when a DC voltage is applied between the anode 2 and the cathode 3, holes injected from the anode 2 pass through the hole transport layer 10 and are The 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. 3 and 4 are arranged in a matrix. In addition, both elements C and D are:
Either a transmission type or a reflection type structure can be adopted.

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 film 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 contain the compound according to the present invention. The light emitting hole transport layer 6 or the electron transport layer 7 may be used. 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 according to the present invention, and the electron transport layer 12 are laminated, and various other laminated structures Can take. 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 transport layer 6, the electron transport layer 7, and the light-emitting layer 11 are layers composed of the compound according to the present invention. Alternatively, it may be formed by co-evaporation of the compound according to 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. However, 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 1 using at least one kind of fluorescent material is sandwiched between the hole transport layer and the electron transport layer. Alternatively, a structure in which this fluorescent material is contained in the hole transport layer or the electron transport layer, or both of them may be configured. In such a case, in order to improve the 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, Ca or the like and a metal such as Ag, Al, In or the like can be used, and a structure in which these metal layers 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.

Further, the protective film 4 functions as a sealing film, and the charge injection efficiency and the light emission efficiency can be improved by adopting a structure that covers the entire organic electrolysis device. If 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 destroy the element. However, in consideration of the 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. 5 shows an example of the configuration of a flat display using an organic electroluminescent device having a different type of stick. As shown, for example, in the case of a full color display, an organic layer 5 (5a, 5b) capable of emitting three primary colors of red (R), green (G) and blue (B) is provided between the cathode 3 and the anode 2. It is arranged in. 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. As this driving method, a simple matrix system or an active matrix system can be used.

That is, FIG. 5 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. 3 or FIG. 4)
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 time series, and emit light at the intersection. The EL element having such a configuration
The display of characters, signal course, can also be used as an image reproducing apparatus. Further, it is possible to form a multi-color or full-color all-solid-state flat panel display by arranging stripe patterns of the cathode 3 and the anode 2 for each color of red (R), green (G), and blue (B). Become.

[0057]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to the following Examples.

According to the following reaction formula, a spirofluorene compound [A] based on the present invention was produced. (1) Synthesis example of spirofluorene compound [A] (a) Compound [c]

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6,12-Dihydroindeno [1,2-b] f
luorene (synthesis method is J. Org. Chem., Vol. 56, 3, 1991, 1210-12
15.4 g (60.6 mmol) was dissolved in 300 ml of chlorobenzene, stirred at 50 for 30 minutes, and then NBS (N-bromosuccinimide, 27.0 g,
151.5 mmol) and a catalytic amount of AIBN were added in several portions, and the mixture was stirred at 120 ° C. for 4 hours. Thereafter, the solvent was distilled off under reduced pressure, and the residue was separated by silica gel chromatography (chloroform / hexane = 4/1). Then, 15.5 g (yield 45%) of compound [c] was obtained by recrystallization (chloroform / hexane). The obtained compound [c] (10.0 g, 17.5 mmol) was treated with acetic acid 20
After dissolving in 0 ml, 10 g of sodium acetate was added, and the mixture was heated under reflux for 5 hours. The reaction solution is returned to room temperature, and Na
After neutralization by adding ₂ CO ₃ , the organic layer was extracted, the solvent was distilled off, and the residue was separated by silica gel chromatography (chloroform / hexane = 5/1). Then, 4.10 g (yield 83%) of the compound [c] purified by recrystallization (chloroform / hexane) was obtained. Compound [c]
Was determined by FAB-MS spectrum measurement [FAB-MS: m / z 281 (M ⁺ )].

(B) Compound [A]

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Under a nitrogen atmosphere, 1.2 g of Mg shavings were first placed in 20 ml of dry diethyl ether. 2
-Bromobiphenyl (4.66 g, 20.0 mmol)
Was dissolved in 10 ml of dry diethyl ether, and about 5 ml of this solution was added to the previously prepared ether solution to start the Grignard reaction, and the remaining solution was added so as to boil gently. The compound [c] (5.52 g, 20.0 mmol) obtained as described above was dissolved in 15 ml of dry diethyl ether, added dropwise to the Grignard solution, and the mixture was boiled for 2 hours. After cooling the reaction mixture, the precipitate was filtered off with suction and washed with a little ether. The magnesium complex was hydrolyzed in an ammonium chloride solution. After stirring for 1 hour, the product [d] was suction filtered, washed with water and suction dried. Then acetic acid 1
After dissolving the product [d] in 00 ml, 0.1 ml of concentrated hydrochloric acid was added to the solution, the solution was boiled for several minutes, and the formed spirofluorene compound [A] was precipitated by adding water. After cooling, the product was filtered off with suction and washed with water. The dried product was further purified by recrystallization from ethanol. Thereby, compound [A] of a colorless crystal was obtained.
5.98 g (54% yield) was obtained. Compound [A] was identified by FAB-MS measurement [FAB-M].
S: m / z 553 (M ⁺ )].

(2) Synthesis Example of 2 ′, 2 ″ -Dibromospirofluorene Compound The spirofluorene compound [A] (2.77 g, 5.00 mmol) obtained as described above was dissolved in 10 ml of methylene chloride. After mixing with 2 mg of FeCl ₃ (anhydrous), 0.62 ml of bromine in 3 ml of methylene chloride (1
2.0 mmol) was added dropwise with stirring over 30 minutes. After 24 hours, the resulting solution was washed with saturated NaHCO ₃
The organic layer is washed with an aqueous solution and water to remove excess bromine.
After drying over Na ₂ SO ₄ , the solvent was evaporated. When the white residue was recrystallized from methanol, 2 ′, 2 ″ of colorless crystals were obtained.
-Dibromospirofluorene compound 2.03 g (yield 5
7%). The identification of the synthetic compound was performed by FAB-MS spectrum measurement [FAB-MS: m / z
712 (M ⁺ )].

For the 2,8,2 ', 2 "-tetrabromo compound and the 2,8,2', 7 ', 2", 7 "-hexabromo compound, different stoichiometric ratios are used to It could be manufactured in a similar manner.

(3) Synthesis Example of 2 ′, 2 ″ -Diacetyl Compound Anhydrous AlC was added to a solution of the spirofluorene compound [A] (4.54 g, 8.2 mmol) obtained as described above in 25 ml of anhydrous carbon disulfide. _3. After adding 7.20 g, acetyl chloride (2.30 g,
A solution of 16.4 g) in 5 ml of anhydrous carbon disulfide was gradually added dropwise, and the mixture was boiled under reflux for 2 hours. After distilling off the solvent under reduced pressure and mixing with 100 g of ice and 30 ml of hydrochloric acid under ice-cooling, the organic layer was extracted, and toluene / ethyl acetate (5: 5) was added.
Using 1), the crude organism was separated by silica gel chromatography. Thereafter, recrystallization (hexane / ethyl acetate) gave 4.34 g (83% yield) of a 2 ', 2 "-diacetylspirofluorene compound. The identity of the synthesized compound was determined by FAB-MS spectrum measurement [FA
B-MS: m / z 637 (M ^<+> )].

2,8,2 ′, 2 ″ -tetraacetylspirofluorene compound and 2,8,2 ′, 7 ′, 2 ″,
The 7 "-hexaacetylspirofluorene compound could be obtained as the main product in a manner similar to that described above by using different stoichiometric ratios.

(4) Synthesis Example of 2 ′, 2 ″ -dicarboxylic acid spirofluorene compound 2 ′, 2 ″ -diacetyl compound (4.24 g, 10.5 g)
mmol) in a dioxane solution (10 ml) was stirred under ice-cooling while a solution of 10.4 g of bromine in a dioxane solution (5 m
l) was mixed dropwise. Thereafter, the mixture was added dropwise to a sodium hydroxide aqueous solution (15 g / 40 ml) solution, and the mixture was further stirred at room temperature for 1 hour.
4 g / 30 ml). After acidification by addition of concentrated hydrochloric acid, the precipitated product was filtered and washed with a small amount of water. Recrystallization from ethanol gave 5.39 g (80% yield) of a spirofluorene 2 ', 2 "-dicarboxylate compound. The identity of the synthesized compound was determined by FAB-MS spectrum measurement [FAB-MS: m / z 641
(M ⁺ )].

2,8,2 ′, 2 ″ -spirofluorene tetracarboxylic acid compound and 2,8,2 ′, 7 ′,
The 2 ", 7" -spirofluorene hexacarboxylate compound could be obtained as the main product in a manner similar to that described above by using different stoichiometric ratios.

(5) Synthesis example of 2 ′, 2 ″ -dicarboxylic acid dichloride spirofluorene compound 2 ′, 2 ″ -dicarboxylic acid spirofluorene compound (4.60 g, 7.17 mmol) and DMF (dimethylformamide) 3 ml were mixed. After that, 46 ml of an excessive amount of thionyl chloride was gradually added dropwise, and the mixture was heated under reflux for 3 hours. Thereafter, unreacted thionyl chloride was distilled off under reduced pressure,
The residue was filtered, washed with hexane, and dried under reduced pressure to obtain 3.80 g (yield 82%) of 2 ', 2 "-dicarboxylic acid dichloride spirofluorene compound. The identity of the synthesized compound was determined by FAB-MS spectrum measurement. I went [F
AB-MS: m / z 650 (M ⁺ )].

2,8,2 ′, 2 ″ -tetracarboxylic acid dichloride spirofluorene compound and 2,8,2 ′,
The 7 ′, 2 ″, 7 ″ -hexacarboxylic acid dichloride spirofluorene compound was also obtained in the same manner as described above.

(6) Synthesis Example of 2 ', 2 "-diphenylspirofluorene Compound 2', 2" -dibromospirofluorene compound (3.0
0 g, 4.21 mmol) and phenylboric acid (1.03
g, 8.42 mmol), PdCl ₂ (dppf) 60
mg of THF and saturated sodium hydrogen carbonate solution 1
Slurried in a mixture with 0 ml. After the mixture was boiled under reflux for 24 hours while stirring vigorously, after cooling to room temperature, the solid was filtered off with suction, washed with water, dried under reduced pressure and 2.32 g of 2 ', 2 "-diphenylspirofluorene compound. (Yield: 78%) The synthesized compound was identified by FAB-MS spectrum measurement [FA
B-MS: m / z 705 (M ^<+> )].

(7) Synthesis example of 2 ', 2 "-di (biphenyl) spirofluorene compound 2', 2" -dibromospirofluorene compound (3.0
0 g, 4.21 mmol), biphenyl boric acid (1.67).
g, 8.42 mmol), PdCl ₂ (dppf) 60
mg was slurried in a mixture of 20 ml of THF (tetrahydrofuran) and 10 ml of a saturated aqueous sodium hydrogen carbonate solution. With vigorous stirring, the mixture is refluxed for 24 hours.
After boiling for an hour and cooling to room temperature, the solid is filtered off with suction, washed with water, dried under reduced pressure and 2.74 g of 2 ', 2 "-di (biphenyl) spirofluorene compound (yield 76).
%)was gotten. The identification of the synthetic compound was performed by FAB-MS spectrum measurement [FAB-MS: m / z 8.
57 (M ⁺ )].

(8) 2,8,2 ', 2 "-tetraphenyl
Synthesis Example of Ruspirofluorene Compound 2,8,2 ', 2 "-Tetrabromospirofluorenation
Compound (3.66 g, 4.21 mmol), phenyl boric acid
(2.05 g, 16.4 mmol), PdCl _Two(Dp
pf) 140 mg of THF and 40 ml of saturated sodium bicarbonate
A slurry was formed in a mixture with 20 ml of an aqueous solution of lithium.
The mixture is boiled under reflux for 24 hours with vigorous stirring.
After cooling to room temperature, the solid is filtered off with suction and washed with water.
And dried under reduced pressure to give 2,8,2 ', 2 "-tetraphenyl
2.67 g (74% yield) of spirofluorene compound was obtained.
Was done. The identity of the synthesized compound was determined by FAB-MS spectrum measurement.
[FAB-MS: m / z 857 (M
⁺)].

(9) Synthesis example of 2,8,2 ', 2 "-tetrakis (biphenyl) spirofluorene compound 2,8,2', 2" -tetrabromospirofluorene compound (3.66 g, 4.21 mmol) , Biphenyl boric acid (2.05 g, 16.4 mmol), PdCl ₂ (d
(ppf) 140 mg was slurried in a mixture of 40 ml THF and 20 ml saturated aqueous sodium bicarbonate. The mixture was boiled under reflux for 24 hours with vigorous stirring, and after cooling to room temperature, the solid was filtered off with suction, washed with water, dried under reduced pressure, and 2,8,2 ', 2 "-tetrakis (biphenyl). 2.67 g (74% yield) of a spirofluorene compound was obtained.
[FAB-MS: m /
z 1161 (M ^<+> )].

(10) 2, 8, 2 ', 7', 2 ", 7"
Synthesis example of -hexaphenylspirofluorene compound 2,8,2 ', 7', 2 ", 7" -hexabromospirofluorene compound (4.33 g, 4.21 mmol),
Phenyl boric acid (3.09 g, 25.3 mmol), Pd
140 mg of Cl ₂ (dppf) was slurried in a mixture of 40 ml of THF and 20 ml of saturated aqueous sodium hydrogen carbonate solution. While stirring vigorously, the mixture is refluxed for 2 hours.
After boiling for 4 hours and cooling to room temperature, the solid was filtered off with suction, washed with water and dried under reduced pressure to give 2,8,2 ', 7',
3.25 g (yield: 76%) of a 2 ″, 7 ″ -hexaphenylspirofluorene compound was obtained. Identification of the synthetic compound was performed by FAB-MS spectrum measurement [FA
B-MS: m / z 1009 (M ^<+> )].

(11) 2, 8, 2 ', 7', 2 ", 7"
Synthesis example of -hexa (biphenyl) spirofluorene compound 2,8,2 ', 7', 2 ", 7" -hexabromospirofluorene compound (4.33 g, 4.21 mmol),
Biphenyl boric acid (5.01 g, 25.3 mmol), P
140 mg of dCl ₂ (dppf) was slurried in a mixture of 40 ml of THF and 20 ml of a saturated aqueous sodium hydrogen carbonate solution. The mixture was boiled under reflux for 24 hours with vigorous stirring, then, after cooling to room temperature, the solid was filtered off with suction, washed with water, dried under reduced pressure, and dried with 2,8,2 ', 7',
4.20 g (68% yield) of 2 ″, 7 ″ -hexa (biphenyl) spirofluorene compound was obtained. Identification of the synthetic compound was performed by FAB-MS spectrum measurement [FAB-MS: m / z 1465 (M ⁺ )].

(12) 2 ′, 2 ″ -bis [5- (pt
-Butylphenyl) -1,3,4-oxadiazole-
Synthesis Example of 2-yl] -spirofluorene Compound 5- (4-t-butylphenyl) in a solution of 2 ′, 2 ″ -dicarboxylic acid dichloridespirofluorene compound (3.06 g, 4.5 mmol) in 10 ml of anhydrous pyridine. 20 ml of anhydrous pyridine of tetrazole (2.01 g, 11.0 mmol) was gradually added dropwise, and the mixture was heated under reflux for 3 hours under an inert gas atmosphere, cooled, added with 150 ml of water, and stirred for 2 hours. The precipitated oxadiazole compound was filtered, washed with water, and the crude product was separated by silica gel chromatography using chloroform / ethyl acetate (10: 1), followed by recrystallization (chloroform / hexane). 2), 2 "-
Bis [5- (pt-butylphenyl) -1,3,4-
1.87 g of [oxadiazol-2-yl] -spirofluorene compound was obtained. The compound was identified by FAB-MS measurement [FAB-MS: m / z 983].
(M ⁺ )].

(13) Synthesis Example 2 ′ of 2 ′, 2 ″ -bis [1-phenyl-5- (pt-butylphenyl) -1,3,4-triazol-2-yl] -spirofluorene compound Polyphosphoric acid 1 of 2,2 "-dicarboxylic acid dichloride spirofluorene compound (3.06 g, 4.5 mmol)
20 ml of NMP of 4-t-butylphenyl-benzoic acid hydrazide (2.17 g, 10.5 mmol) in a mixed solution of 0 ml / 20 ml of NMP (N-methylpyrrolidone)
Was gradually added dropwise, and the mixture was heated and refluxed for 3 hours under an inert gas atmosphere. Then, aniline (1.0 g, 10.5 mm
ol) was gradually added dropwise, and the mixture was heated and stirred at 175 ° C. for 30 hours. After cooling the reaction solution, 150 ml of water was added, and the mixture was stirred for 2 hours. The precipitate was filtered, washed with water, and then the crude product was separated by silica gel chromatography using chloroform / ethyl acetate (8: 1). did. After that, recrystallization (chloroform / hexane) gave 2 ′, 2 ″ -bis [1
-Phenyl-5- (pt-butylphenyl) -1,
1.87 g (yield: 42.2%) of 3,4-triazol-2-yl] -spirofluorene compound was obtained. The compound was identified by FAB-MS measurement [FAB-M
S: m / z 1133 (M ⁺ )].

(14) Synthesis example of 2 ′, 2 ″ -bis [(p-phenyl) styryl] spirofluorene compound 2 ′, 2 ″ -dibromospirofluorene compound (3.0
0 g, 4.21 mmol), 1-biphenyl-2-pinacolato boron ethene (3.09 g, 10.1 mmol)
l) and 140 mg of PdCl ₂ (dppf) in THF4
A slurry was prepared in a mixture of 0 ml and 20 ml of a saturated aqueous sodium hydrogen carbonate solution. The mixture was stirred for 20 hours while heating and refluxing under a nitrogen atmosphere. After cooling, the product is filtered, the precipitate is washed with water and dried. The organic layer was separated, and the aqueous layer was extracted with chloroform. Dry the combined organic layers over magnesium sulfate and evaporate the solvent to give the product. After dissolving in chloroform together with the previously filtered product and separating by-products with an alumina column, chloroform /
Recrystallized from hexane, 1.72 g of 2 ', 2 "-bis [(p-phenyl) styryl] spirofluorene compound
(Yield 45%) was obtained. The compound was identified by FAB-MS measurement [FAB-ms: m / z 909 (M
⁺ )].

(15) 2 ′, 2 ″ -bis (distyryl)
Synthesis Example of Spirofluorene Compound 2 ′, 2 ″ -dibromospirofluorene compound (3.0
0 g, 4.21 mmol), 1,1-diphenyl-2-
Pinacolate boron ethene (3.09 g, 10.1 mm
ol) and PdCl ₂ (dppf) 140mg in THF
Slurried in a mixture of 40 ml and 20 ml of saturated aqueous sodium bicarbonate solution. The mixture was stirred for 20 hours while heating and refluxing under a nitrogen atmosphere. After cooling, the product is filtered, the precipitate is washed with water and dried. The organic layer was separated, and the aqueous layer was extracted with chloroform. Dry the combined organic layers over magnesium sulfate and evaporate the solvent to give the product. The product was dissolved in chloroform together with the previously filtered product, and the by-product was separated by an alumina column, and then recrystallized from chloroform / hexane to give 2 ′, 2 ″ -bis (1,1).
-Diphenylvinyl) spirofluorene compound 1.46
g (38% yield). FAB-MS
[FAB-ms: m / z909 (M
⁺ )].

Example 1 In this example, among the spirofluorene compounds described in Table 1 above, a spiro-A2 compound was used as a light emitting material.
This is an example in which an organic electroluminescent device having a double hetero structure is manufactured.

First, in a vacuum evaporation apparatus, an anode made of ITO having a thickness of 100 nm and having a thickness of 30 nm formed on one surface was formed.
A × 30 nm glass substrate was set. As a vapor deposition mask, a metal mask having a plurality of 2.0 mm × 2.0 mm unit openings is disposed close to the substrate, and α of the following structural formula (1) is obtained by vacuum vapor deposition under a vacuum of 10 ⁻⁴ Pa or less.
-NPD (α-naphthylphenyldiamine) is, for example, 5
A film was formed as a hole transport layer to a thickness of 0 nm. The deposition rate was 0.1 nm / sec.

[0082]

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Further, a spirofluorene compound (spiro-A2) shown in Table 1 above was deposited as a light emitting material in contact with the hole transport layer. The thickness of the light emitting layer made of Spiro-A2 was also set to, for example, 30 nm, and the deposition rate was set to 0.2 nm / sec.

Further, Alq ₃ (tris (8-quinolinol) aluminum) having the following structural formula (2) was deposited as an electron transporting material in contact with the hole transporting layer. The thickness of the electron transport layer made of Alq ₃ was also set to, for example, 50 nm, and the deposition rate was set to 0.2 nm / sec.

[0085]

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The cathode material employs a laminated film of Mg and Ag,
This was also formed by vapor deposition to a thickness of, for example, 50 nm (Mg film) and 150 nm (Ag film) at a vapor deposition rate of 1 nm / sec to produce an organic electroluminescent device.

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 luminescent color was blue, and a spectrum having a luminescent peak at 430 nm was obtained as a result of spectral measurement. For spectrometry, a spectroscope using a photodiode array manufactured by Otsuka Electronics Co., Ltd. as a detector was used. When voltage-luminance measurement was performed, a luminance of 1200 cd / cm ² was obtained at 8 V.

After this organic electroluminescent device was manufactured, it was left under a nitrogen atmosphere for one month, but no device deterioration was observed. In addition, when forcedly degraded by continuously energizing the voltage value at an initial luminance of 300 cd / cm ² and continuously emitting light, it took 700 hours until the luminance was reduced by half.

Example 2 In this example, among the spirofluorene compounds described in Table 1 above, a spiro-A7 compound was used as a light emitting material.
This is an example in which an organic electroluminescent device having a double hetero structure is manufactured.

First, a 30 nm thick anode formed of ITO having a thickness of 100 nm was formed in a vacuum evaporation apparatus.
A × 30 nm glass substrate was set. As a vapor deposition mask, a metal mask having a plurality of 2.0 mm × 2.0 mm unit openings is arranged close to the substrate, and α of the above-mentioned structural formula (1) is obtained by vacuum vapor deposition under a vacuum of 10 ⁻⁴ Pa or less.
-NPD was deposited as a hole transport layer to a thickness of, for example, 50 nm. The deposition rate was 0.1 nm / sec.

Further, a spirofluorene compound (spiro-A7) shown in Table 1 above as a light emitting material was deposited in contact with the hole transport layer. The thickness of the light emitting layer made of Spiro-A7 was also set to, for example, 30 nm, and the deposition rate was set to 0.2 nm / sec.

Further, Alq ₃ of the above structural formula (2) was deposited as an electron transporting material in contact with the light emitting layer. The film thickness of Alq ₃ is, for example, 50 nm, and the deposition rate is 0.2 nm /
Seconds.

The cathode material employs a laminated film of Mg and Ag,
This was also formed by vapor deposition to a thickness of, for example, 50 nm (Mg film) and 150 nm (Ag film) at a vapor deposition rate of 1 nm / sec to produce an organic electroluminescent device.

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. It emitted a blue light, which was found by spectrometry (as in Example 1) to have a peak at 440 nm. When voltage-luminance measurement was performed, a luminance of 1500 cd / cm ² was obtained at 8 V.

After the fabrication of this organic electroluminescent device, the device was allowed to stand for one month in a nitrogen atmosphere, but no device degradation was observed. In addition, when forcedly degraded by applying a constant voltage at an initial luminance of 300 cd / cm ² and continuously emitting light, it took 1100 hours until the luminance was reduced by half.

Example 3 In this example, among the spirofluorene compounds described in Table 1 above, a spiro-A8 compound was used as a light emitting material.
This is an example in which an organic electroluminescent device having a double hetero structure is manufactured.

First, a 30 nm thick anode formed of ITO having a thickness of 100 nm was formed on one surface in a vacuum evaporation apparatus.
A × 30 nm glass substrate was set. As a vapor deposition mask, a metal mask having a plurality of 2.0 mm × 2.0 mm unit openings is arranged close to the substrate, and α of the above-mentioned structural formula (1) is formed by a vacuum vapor deposition method under a vacuum of 10 ⁻⁴ Pa or less.
-NPD was deposited as a hole transport layer to a thickness of, for example, 50 nm. The deposition rate was 0.1 nm / sec.

Further, a spirofluorene compound (spiro-A8) described in Table 1 above was deposited as a light emitting material in contact with the hole transport layer. The thickness of the light emitting layer made of Spiro-A8 was also set to, for example, 30 nm, and the deposition rate was set to 0.2 nm / sec.

Further, Alq ₃ of the above structural formula (2) was deposited as an electron transporting material in contact with the light emitting layer. The film thickness of Alq ₃ is, for example, 50 nm, and the deposition rate is 0.2 nm /
Seconds.

The cathode material employs a laminated film of Mg and Ag,
This was also formed by vapor deposition to a thickness of, for example, 50 nm (Mg film) and 150 nm (Ag film) at a vapor deposition rate of 1 nm / sec to produce an organic electroluminescent device.

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. It emitted blue light, which was found by spectrometry (as in Example 1) to have a peak at 440 nm. In addition, when voltage-luminance measurement was performed, luminance of 1600 cd / cm ² was obtained at 8 V.

After this organic electroluminescent device was manufactured, it was left under a nitrogen atmosphere for one month, but no device deterioration was observed. In addition, when forcedly degraded by applying a constant voltage at an initial luminance of 300 cd / cm ² and continuously emitting light, it took 2400 hours to reduce the luminance by half.

Example 4 In this example, among the spirofluorene compounds shown in Table 1 above, a spiro-A10 compound was used as a light emitting material to produce an organic electroluminescent device having a double hetero structure.

First, in a vacuum evaporation apparatus, an anode made of ITO having a thickness of 100 nm was formed on one surface with a thickness of 30 nm.
A × 30 nm glass substrate was set. As a vapor deposition mask, a metal mask having a plurality of 2.0 mm × 2.0 mm unit openings is arranged close to the substrate, and α of the above-mentioned structural formula (1) is obtained by vacuum vapor deposition under a vacuum of 10 ⁻⁴ Pa or less.
-NPD was deposited as a hole transport layer to a thickness of, for example, 50 nm. The deposition rate was 0.1 nm / sec.

Further, a spirofluorene compound (spiro-A10) shown in Table 1 above as a light emitting material was deposited in contact with the hole transport layer. The thickness of the light emitting layer made of Spiro-A10 is also, for example, 30 nm, and the deposition rate is 0.2 nm.
/ Sec.

Further, Alq ₃ of the above structural formula (2) was deposited as an electron transporting material in contact with the light emitting layer. The film thickness of Alq ₃ is, for example, 50 nm, and the deposition rate is 0.2 nm /
Seconds.

The cathode material employs a laminated film of Mg and Ag,
This was also formed by vapor deposition to a thickness of, for example, 50 nm (Mg film) and 150 nm (Ag film) at a vapor deposition rate of 1 nm / sec to produce an organic electroluminescent device.

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. It emitted a blue light, which was found by spectrometry (as in Example 1) to have a peak at 435 nm. When voltage-luminance measurement was performed, a luminance of 1500 cd / cm ² was obtained at 8 V.

After this organic electroluminescent device was prepared, it was left under a nitrogen atmosphere for one month, but no device deterioration was observed. In addition, when forcedly degraded by applying a constant voltage at an initial luminance of 300 cd / cm ² and continuously emitting light, it took 1700 hours until the luminance was reduced by half.

Example 5 In this example, among the spirofluorene compounds shown in Table 1 above, a compound of spiro-A11 was used as a light emitting material.
This is an example in which an organic electroluminescent device having a double hetero structure is manufactured.

First, in a vacuum evaporation apparatus, a 30 nm-thick anode made of ITO having a thickness of 100 nm was formed on one surface.
A × 30 nm glass substrate was set. As a vapor deposition mask, a metal mask having a plurality of 2.0 mm × 2.0 mm unit openings is arranged close to the substrate, and α of the above-mentioned structural formula (1) is formed by a vacuum vapor deposition method under a vacuum of 10 ⁻⁴ Pa or less.
-NPD was deposited as a hole transport layer to a thickness of, for example, 50 nm. The deposition rate was 0.1 nm / sec.

Further, a spirofluorene compound (spiro-A11) shown in Table 1 above as a light emitting material was deposited in contact with the hole transport layer. The thickness of the light-emitting layer made of Spiro-A11 is also, for example, 30 nm, and the deposition rate is 0.2 nm
/ Sec.

Further, Alq ₃ of the above structural formula (2) was deposited as an electron transporting material in contact with the light emitting layer. The film thickness of Alq ₃ is, for example, 50 nm, and the deposition rate is 0.2 nm /
Seconds.

The cathode material employs a laminated film of Mg and Ag,
This was also formed by vapor deposition to a thickness of, for example, 50 nm (Mg film) and 150 nm (Ag film) at a vapor deposition rate of 1 nm / sec to produce an organic electroluminescent device.

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. It emitted a blue light, which was found by spectrometry (as in Example 1) to have a peak at 430 nm. When voltage-luminance measurement was performed, luminance of 1000 cd / cm ² was obtained at 8 V.

After this organic electroluminescent device was manufactured, it was left in a nitrogen atmosphere for one month, but no device deterioration was observed. In addition, when forcedly degraded by applying a constant voltage at an initial luminance of 300 cd / cm ² and continuously emitting light, it took 800 hours until the luminance was reduced by half.

Example 6 In this example, an organic electroluminescent device having a double hetero structure was prepared by using a spiro-A13 compound among the spirofluorene compounds described in Table 1 as a light emitting material.

First, in a vacuum evaporation apparatus, an anode made of ITO having a thickness of 100 nm was formed on one surface with a thickness of 30 nm.
A × 30 nm glass substrate was set. As a vapor deposition mask, a metal mask having a plurality of 2.0 mm × 2.0 mm unit openings is arranged close to the substrate, and α of the above-mentioned structural formula (1) is formed by a vacuum vapor deposition method under a vacuum of 10 ⁻⁴ Pa or less.
-NPD was deposited as a hole transport layer to a thickness of, for example, 50 nm. The deposition rate was 0.1 nm / sec.

Further, a spirofluorene compound (spiro-A13) shown in Table 1 above as a light emitting material was deposited in contact with the hole transport layer. The thickness of the light-emitting layer made of Spiro-A13 is also, for example, 30 nm, and the deposition rate is 0.2 nm.
/ Sec.

Furthermore, Alq ₃ of the above structural formula (2) was deposited as an electron transporting material in contact with the light emitting layer. The film thickness of Alq ₃ is, for example, 50 nm, and the deposition rate is 0.2 nm /
Seconds.

As the cathode material, a laminated film of Mg and Ag is used.
This was also formed by vapor deposition to a thickness of, for example, 50 nm (Mg film) and 150 nm (Ag film) at a vapor deposition rate of 1 nm / sec to produce an organic electroluminescent device.

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. It emitted a blue light, which was found by spectrometry (as in Example 1) to have a peak at 430 nm. When voltage-luminance measurement was performed, a luminance of 1400 cd / cm ² was obtained at 8 V.

After this organic electroluminescent device was manufactured, it was left in a nitrogen atmosphere for one month, but no device deterioration was observed. In addition, when forcedly degraded by continuously energizing a voltage value at an initial luminance of 300 cd / cm ² and continuously emitting light, it took 850 hours until the luminance was reduced by half.

Example 7 In this example, among the spirofluorene compounds described in Table 3 above, a spiro-C2 compound was used as a light emitting material.
This is an example in which an organic electroluminescent device having a double hetero structure is manufactured.

First, in a vacuum deposition apparatus, a 30 nm thick anode formed of ITO having a thickness of 100 nm was formed on one surface.
A × 30 nm glass substrate was set. As a vapor deposition mask, a metal mask having a plurality of 2.0 mm × 2.0 mm unit openings is arranged close to the substrate, and α of the above-mentioned structural formula (1) is formed by a vacuum vapor deposition method under a vacuum of 10 ⁻⁴ Pa or less.
-NPD was deposited as a hole transport layer to a thickness of, for example, 50 nm. The deposition rate was 0.1 nm / sec.

Further, a spirofluorene compound (spiro-C2) described in Table 3 above as a light emitting material was deposited in contact with the hole transport layer. The thickness of the light emitting layer made of Spiro-C2 was also set to, for example, 30 nm, and the deposition rate was set to 0.2 nm / sec.

Further, Alq ₃ of the above structural formula (2) was deposited as an electron transporting material in contact with the light emitting layer. The film thickness of Alq ₃ is, for example, 50 nm, and the deposition rate is 0.2 nm /
Seconds.

As the cathode material, a laminated film of Mg and Ag is used.
This was also formed by vapor deposition to a thickness of, for example, 50 nm (Mg film) and 150 nm (Ag film) at a vapor deposition rate of 1 nm / sec to produce an organic electroluminescent device.

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. It emitted blue light, which was found by spectrometry (as in Example 1) to have a peak at 440 nm. When voltage-luminance measurement was performed, a luminance of 1200 cd / cm ² was obtained at 8 V.

After this organic electroluminescent device was manufactured, it was left for one month in a nitrogen atmosphere, but no device deterioration was observed. In addition, when forcedly degraded by applying a constant voltage at an initial luminance of 300 cd / cm ² and continuously emitting light, it took 1,000 hours until the luminance was reduced by half.

[0131]

The spirofluorene compound of the present invention is excellent in thermal stability, gives good luminous efficiency,
It is extremely difficult to crystallize, and a uniform amorphous thin film can be formed. 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. Furthermore, when the spirofluorene compound of the present invention is used as a constituent material of an organic electroluminescent device, it is possible to realize a full-color color display and the like and to extend the life of the device.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of a main part of an organic electroluminescent device according to the present invention.

FIG. 2 is a schematic sectional view of a main part of another organic electroluminescent device.

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

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

FIG. 5 is a configuration diagram of a full-color flat display using the organic electroluminescent element.

[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 transport layer, 11 light emitting layer, 12 electron transport 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) C09K 11/06 610 C09K 11/06 610 615 615 620 620 620 625 625 640 640 690 690 690 H05B 33/14 H05B 33 / 14 B 33/22 33/22 BD // C07D 215/30 C07D 215/30 249/02 249/02 271/10 271/10 (72) Inventor Shinichiro Tamura 7-35 Kitashinagawa 6-chome, Shinagawa-ku, Tokyo No. Sony Corporation F term (reference) 3K007 AB02 AB04 AB11 CA01 CB01 DA01 DB03 EB00 4C056 AA01 AB02 AC07 AD01 AE03 AF01 FA04 FB01 FC01 4H006 AA01 AA02 AB92 AC24 AC30 AC44 AC46 BA92 BJ50

Claims (16)

[Claims] 1. A spirofluorene compound represented by the following general formula (1). Embedded image (However, in the general formula (1), the benzo groups may be substituted and / or fused independently of each other.) 2. A spirofluorene compound represented by the following general formula (2). Embedded image [However, in the general formula (2), A ¹ , B ¹ , C ¹ ,
D ^1, E ¹ and F ¹ may be the being the same or different, each independently, a group represented by the following general formula: ## STR3 ## Is one of In the general formula (2) and the group, each R may be the same as or different from each other, and may be a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, An alkoxy group, an ester group, a hydroxyl group, a halogen atom, a cyano group, a nitro group, an alkylamino group, an aryl group, an arylamino group or an aryloxy group, wherein the aryl group is a substituted or unsubstituted phenyl group, biphenyl group , Triphenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-fluorenyl, 2-fluorenyl or 9-fluorenyl, and the like. The substituent is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amino group, an alkylamino group. Arylamino group, a cyano group, a nitro group, a hydroxyl group or a halogen atom. Further, W, X, Y and Z in the group are each independently a hydrogen atom, or a substituted or unsubstituted carbon atom having 6 to 6 carbon atoms.
30, and the substituents of W and X, and of Y and Z may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated 5- or 6-membered ring, wherein The substituent is an alkyl group having 1 to 6 carbon atoms, 6 to 30 carbon atoms.
Is an aryl group, an amino group, an alkylamino group, an arylamino group, a cyano group, a nitro group, a hydroxyl group or a halogen atom, and these substituents may be single or plurally substituted. Also, 1 in the above group is 1, 2 or 3,
m and n are integers of 0-6. Further, in the group, D represents -CR ¹ - a, or nitrogen, wherein R ¹ is a hydrogen atom or a straight-chain having 1 to 6 carbon atoms, branched or cyclic alkyl group, an aryl having 6 to 20 carbon atoms Represents a group, an amino group, an alkylamino group, an arylamino group, a cyano group, a nitro group, a hydroxyl group or a halogen atom, and these substituents may be single or plurally substituted. In the above group, E is-
O -, - S -, - NR 2 -, CR 3 R 4 -, - CH = CH
—, —CH ＝ N—, and R ² , R ³ , and R ⁴ may be the same or different from each other, and represent a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms. An aryl group having 6 to 20 carbon atoms, an amino group, an alkylamino group,
It represents an arylamino group, a cyano group, a nitro group, a hydroxyl group or a halogen atom, and these substituents may be single or plurally substituted. ] 3. A coupling between at least one pinacolate boron compound represented by the following general formulas (3) to (9) and a bromo compound represented by the following general formula (10) in the presence of a metal catalyst: A method for producing a spirofluorene compound, wherein a spirofluorene compound represented by the following general formula (2) is obtained by reacting: Embedded image [However, in the general formulas (3) to (9), each R
May be the same or different from each other, a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkoxy group, an ester group, a hydroxyl group,
A halogen atom, a cyano group, a nitro group, an alkylamino group, an aryl group, an arylamino group or an aryloxy group, wherein the aryl group is a substituted or unsubstituted phenyl group, biphenyl group, triphenyl group, 1-naphthyl Group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-fluorenyl group, 2
A fluorenyl group or a 9-fluorenyl group, wherein the substituent means an alkyl group having 1 to 6 carbon atoms,
An alkoxy group having 10 to 10, an aryl group having 6 to 30 carbon atoms,
It is an amino group, an alkylamino group, an arylamino group, a cyano group, a nitro group, a hydroxyl group or a halogen atom. W, X, Y and Z in the group are each independently a hydrogen atom or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituent of W and X, and a substituent of Y and Z May be bonded to each other to form a substituted or unsubstituted saturated or unsaturated 5- or 6-membered ring, wherein the substituent is
An alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amino group, an alkylamino group, an arylamino group,
A cyano group, a nitro group, a hydroxyl group or a halogen atom,
These substituents may be single or plurally substituted.
Also, 1 in the above group is 1, 2 or 3, and m and n are integers of 0 to 6. In the above group, D represents -CR ^1-
Or nitrogen, wherein R ¹ is a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, an amino group, an alkylamino group,
It represents an arylamino group, a cyano group, a nitro group, a hydroxyl group or a halogen atom, and these substituents may be single or plurally substituted. In the above groups, E is -O-, -S
^{-, - NR 2 -, CR} 3 R 4 -, - CH = CH -, - CH
R ² , R ³ , and R ⁴ may be the same or different from each other, and may be a hydrogen atom, a straight-chain, branched or cyclic alkyl group having 1 to 6 carbon atoms, To 20 aryl groups, amino groups, alkylamino groups, arylamino groups, cyano groups, nitro groups, hydroxyl groups or halogen atoms, and these substituents may be single or plurally substituted. ] [However, in the general formula (10), I ¹ , J ¹ ,
At least one of K ¹ , L ¹ , M ¹ and N ¹ is a halogen atom of bromine atom (Br) or iodine atom (I);
Each R may be the same or different from each other,
A hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkoxy group or an ester group,
A hydroxyl group, a halogen atom, a cyano group, a nitro group, an alkylamino group, an aryl group, an arylamino group or an aryloxy group, wherein the aryl group is a substituted or unsubstituted phenyl group, biphenyl group, triphenyl group,
-Naphthyl group, 2-naphthyl group, 1-anthryl group, 2
-Anthryl group, 9-anthryl group, 1-fluorenyl group, 2-fluorenyl group or 9-fluorenyl group and the like, wherein the substituent means an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 10 carbon atoms. Group, an aryl group having 6 to 30 carbon atoms, an amino group, an alkylamino group, an arylamino group, a cyano group, a nitro group, a hydroxyl group or a halogen atom. ] [However, in the general formula (2), A ¹ , B ¹ , C ¹ ,
D ¹ , E ¹ and F ¹ may be the same or different from each other, and each is independently a group represented by the following general formula: Is one of In the general formula (2) and the group, each R may be the same as or different from each other, and may be a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, An alkoxy group, an ester group, a hydroxyl group, a halogen atom, a cyano group, a nitro group, an alkylamino group, an aryl group, an arylamino group or an aryloxy group, wherein the aryl group is a substituted or unsubstituted phenyl group, biphenyl group , Triphenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-fluorenyl, 2-fluorenyl or 9-fluorenyl, and the like. The substituent is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amino group, an alkylamino group. Arylamino group, a cyano group, a nitro group, a hydroxyl group or a halogen atom. Further, W, X, Y and Z in the group are each independently a hydrogen atom, or a substituted or unsubstituted carbon atom having 6 to 6 carbon atoms.
30, and the substituents of W and X, and of Y and Z may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated 5- or 6-membered ring, wherein The substituent is an alkyl group having 1 to 6 carbon atoms, 6 to 30 carbon atoms.
Is an aryl group, an amino group, an alkylamino group, an arylamino group, a cyano group, a nitro group, a hydroxyl group or a halogen atom, and these substituents may be single or plurally substituted. Also, 1 in the above group is 1, 2 or 3,
m and n are integers of 0-6. Further, in the group, D represents -CR ¹ - a, or nitrogen, wherein R ¹ is a hydrogen atom or a straight-chain having 1 to 6 carbon atoms, branched or cyclic alkyl group, an aryl having 6 to 20 carbon atoms Represents a group, an amino group, an alkylamino group, an arylamino group, a cyano group, a nitro group, a hydroxyl group or a halogen atom, and these substituents may be single or plurally substituted. In the above group, E is-
O -, - S -, - NR 2 -, CR 3 R 4 -, - CH = CH
—, —CH ＝ N—, and R ² , R ³ , and R ⁴ may be the same or different from each other, and represent a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms. An aryl group having 6 to 20 carbon atoms, an amino group, an alkylamino group,
It represents an arylamino group, a cyano group, a nitro group, a hydroxyl group or a halogen atom, and these substituents may be single or plurally substituted. ] 4. The spirofluorene compound according to claim 2, represented by the following general formula (11). Embedded image [However, in the general formula (11), A ² , B ² ,
C ² , D ² , E ² , and F ² may be the same or different from each other, and each is independently a group represented by the following general formula: It is. In the general formula (11) and the group, each R may be the same or different from each other, and may be a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, An alkoxy group, an ester group, a hydroxyl group, a halogen atom, a cyano group, a nitro group, an alkylamino group, an aryl group, an arylamino group or an aryloxy group, wherein the aryl group is a substituted or unsubstituted phenyl group, biphenyl group , A triphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-fluorenyl group, a 2-fluorenyl group or a 9-fluorenyl group. The substituent means an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amino group, an alkyl group. Amino group, an arylamino group, a cyano group, a nitro group, a hydroxyl group or a halogen atom. Also, 1 in the above group is 1, 2 or 3, and m
And n are integers from 0 to 6. ] 5. The condensation of a tetrazole compound represented by the following general formula (12) with a carboxylic acid chloride compound represented by the following general formula (13) in the presence of a dehydrochlorinating agent: The method for producing a spirofluorene compound according to claim 3, wherein the spirofluorene compound represented by (11) is obtained. Embedded image [However, in the general formula (12), each R may be the same or different from each other, and may represent a hydrogen atom,
A straight-chain, branched or cyclic alkyl group having 20 carbon atoms, an alkoxy group, an ester group, a hydroxyl group, a halogen atom, a cyano group, a nitro group, an alkylamino group, an aryl group, an arylamino group or an aryloxy group;
The aryl group is a substituted or unsubstituted phenyl group, a biphenyl group, a triphenyl group, a 1-naphthyl group,
A 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-fluorenyl group, a 2-fluorenyl group, a 9-fluorenyl group, or the like, wherein the substituent has 1 to 6 carbon atoms. An alkyl group having 1 to 10 carbon atoms
An alkoxy group, an aryl group having 6 to 30 carbon atoms, an amino group, an alkylamino group, an arylamino group, a cyano group,
It is a nitro group, a hydroxyl group or a halogen atom. Also, 1 in the above group is 1, 2 or 3, and m and n are integers of 0 to 6. [Image Omitted] [However, in the general formula (13), I ² , J ² ,
At least one of K ² , L ² , M ^2, and N ² is a carboxylic acid chloride (—COCl) group, and each R may be the same or different, and includes a hydrogen atom,
A straight-chain, branched or cyclic alkyl group, alkoxy group or ester group having 20 to 20 carbon atoms, hydroxyl group, halogen atom, cyano group, nitro group, alkylamino group, aryl group, arylamino group or aryloxy group. And the aryl group is a substituted or unsubstituted phenyl group, biphenyl group, triphenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-fluorenyl. A 2-fluoroenyl group, a 9-fluorenyl group, or the like, wherein the substituent means an alkyl group having 1 to 6 carbon atoms,
0 alkoxy group, aryl group having 6 to 30 carbon atoms, amino group, alkylamino group, arylamino group, cyano group, nitro group, hydroxyl group or halogen atom. ] [However, in the general formula (11), A ² , B ² ,
C ² , D ² , E ² and F ² may be the same or different from each other, and each independently represents a group represented by the following general formula: It is. In the general formula (11) and the group, each R may be the same or different from each other, and may be a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, An alkoxy group, an ester group, a hydroxyl group, a halogen atom, a cyano group, a nitro group, an alkylamino group, an aryl group, an arylamino group or an aryloxy group, wherein the aryl group is a substituted or unsubstituted phenyl group, biphenyl group , A triphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-fluorenyl group, a 2-fluorenyl group or a 9-fluorenyl group. The substituent means an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amino group, an alkyl group. Amino group, an arylamino group, a cyano group, a nitro group, a hydroxyl group or a halogen atom. Also, 1 in the above group is 1, 2 or 3, and m
And n are integers from 0 to 6. ] 6. The spirofluorene compound according to claim 2, represented by the following general formula (14). Embedded image [However, in the general formula (14), A ³ , B ³ ,
C ³ , D ³ , E ³ and F ³ may be the same or different from each other, and each independently represents a group represented by the following general formula: It is. In the general formula (14) and the group, each R may be the same as or different from each other, and may be a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, An alkoxy group, an ester group, a hydroxyl group, a halogen atom, a cyano group, a nitro group, an alkylamino group, an aryl group, an arylamino group or an aryloxy group, wherein the aryl group is a substituted or unsubstituted phenyl group, biphenyl group , Triphenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-fluorenyl, 2-fluorenyl or 9-fluorenyl, and the like. The substituent means an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amino group, an alkyl group. Amino group, an arylamino group, a cyano group, a nitro group, a hydroxyl group or a halogen atom. Also, 1 in the above group is 1, 2 or 3, and m
And n are integers from 0 to 6. ] 7. The following general compound formed by condensing a hydrazine compound represented by the following general formula (15) and a carboxylic acid chloride compound represented by the following general formula (17) in the presence of a dehydrochlorinating agent: By subjecting the intermediate represented by the formula (18) and the following general formula (16) to dehydration condensation in the presence of a strong acid or a dehydrating agent, a spirofluorene compound represented by the following general formula (14) is obtained. A method for producing a spirofluorene compound according to claim 3. Embedded image General formula (16): H ₂ NR [provided that, in the general formula (15) and the general formula (16), each R may be the same or different and each represents a hydrogen atom, 1 to 1 A straight chain having 20 carbon atoms,
A branched or cyclic alkyl group, an alkoxy group, an ester group, a hydroxyl group, a halogen atom, a cyano group, a nitro group, an alkylamino group, an aryl group, an arylamino group, or an aryloxy group; Substituted phenyl, biphenyl, triphenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-fluorenyl, 2-fluorenyl or 9-fluorenyl Wherein the substituent is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amino group, an alkylamino group, an arylamino group, It is a cyano group, a nitro group, a hydroxyl group or a halogen atom. In the general formula (15), 1 is 1, 2 or 3, and m and n are integers of 0 to 6. Embedded image [However, in the general formula (17), I ³ , J ³ ,
At least one of K ³ , L ³ , M ³ and N ³ is a carboxylic acid chloride (—COCl) group, and each R may be the same or different from each other, and may be a hydrogen atom,
A straight-chain, branched or cyclic alkyl group, alkoxy group or ester group having 20 to 20 carbon atoms, hydroxyl group, halogen atom, cyano group, nitro group, alkylamino group, aryl group, arylamino group or aryloxy group. And the aryl group is a substituted or unsubstituted phenyl group, biphenyl group, triphenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-fluorenyl. A 2-fluoroenyl group, a 9-fluorenyl group, or the like, wherein the substituent means an alkyl group having 1 to 6 carbon atoms,
0 alkoxy group, aryl group having 6 to 30 carbon atoms, amino group, alkylamino group, arylamino group, cyano group, nitro group, hydroxyl group or halogen atom. [Image Omitted] [However, in the general formula (18), I ⁴ , J ⁴ ,
At least one of K ⁴ , L ⁴ , M ⁴ and N ⁴ is a group represented by the following general formula: [However, in the general formula (18) and the group, each R may be the same or different from each other, and may be a hydrogen atom,
A linear, branched or cyclic alkyl group, alkoxy group, ester group, hydroxyl group, halogen atom, cyano group, nitro group, alkylamino group, aryl group, arylamino group or aryloxy group having 1 to 20 carbon atoms. And the aryl group is a substituted or unsubstituted phenyl group, biphenyl group, triphenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1- A fluorenyl group, a 2-fluorenyl group, a 9-fluorenyl group, or the like, wherein the substituent means an alkyl group having 1 to 6 carbon atoms,
0 alkoxy group, aryl group having 6 to 30 carbon atoms, amino group, alkylamino group, arylamino group, cyano group, nitro group, hydroxyl group or halogen atom. Also,
L in the above group is 1, 2 or 3, and m and n are from 0 to 6
Is an integer. ] [However, in the general formula (14), A ³ , B ³ ,
C ³ , D ³ , E ³ and F ³ may be the same or different from each other, and each is independently a group represented by the following general formula: It is. In the general formula (14) and the group, each R may be the same as or different from each other, and may be a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, An alkoxy group, an ester group, a hydroxyl group, a halogen atom, a cyano group, a nitro group, an alkylamino group, an aryl group, an arylamino group or an aryloxy group, wherein the aryl group is a substituted or unsubstituted phenyl group, biphenyl group , Triphenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-fluorenyl, 2-fluorenyl or 9-fluorenyl, and the like. The substituent means an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amino group, an alkyl group. Amino group, an arylamino group, a cyano group, a nitro group, a hydroxyl group or a halogen atom. Also, 1 in the above group is 1, 2 or 3, and m
And n are integers from 0 to 6. ] 8. The spirofluorene compound according to claim 2, represented by the following general formula (19). Embedded image [However, in the general formula (19), A ⁴ , B ⁴ ,
C ⁴ , D ⁴ , E ⁴ and F ⁴ may be the same or different from each other, and each is independently a group represented by the following general formula: Is one of In the above groups, each R may be the same or different from each other, and may be a hydrogen atom,
A straight-chain, branched or cyclic alkyl group having 0 carbon atoms, an alkoxy group, an ester group, a hydroxyl group, a halogen atom, a cyano group, a nitro group, an alkylamino group, an aryl group, an arylamino group or an aryloxy group; The aryl group is a substituted or unsubstituted phenyl group,
Biphenyl group, triphenyl group, 1-naphthyl group, 2-
Naphthyl group, 1-anthryl group, 2-anthryl group, 9
-Anthryl group, 1-fluorenyl group, 2-fluorenyl group or 9-fluorenyl group and the like, wherein the substituent means an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a carbon atom having 6 carbon atoms. To 30 aryl groups, amino groups, alkylamino groups, arylamino groups, cyano groups, nitro groups, hydroxyl groups or halogen atoms. W, X, Y and Z in the group are each independently a hydrogen atom or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms;
The substituents of W and X, and the substituents of Y and Z may combine to form a substituted or unsubstituted saturated or unsaturated 5- or 6-membered ring, wherein the substituent has a carbon number of An alkyl group having 1 to 6, an aryl group having 6 to 30 carbon atoms, an amino group,
An alkylamino group, an arylamino group, a cyano group, a nitro group, a hydroxyl group, or a halogen atom, and these substituents may be single or plurally substituted. Also, 1 in the above group is 1, 2 or 3, and m and n are integers of 0 to 6. Further, in the group, D represents -CR ¹ - a, or nitrogen, wherein R ¹ is a hydrogen atom or a straight-chain having 1 to 6 carbon atoms, branched or cyclic alkyl group, an aryl having 6 to 20 carbon atoms Represents a group, an amino group, an alkylamino group, an arylamino group, a cyano group, a nitro group, a hydroxyl group or a halogen atom, and these substituents may be single or plurally substituted. In the above groups, E is -O-, -S-, -NR
^2- , CR ³ R ⁴ —, —CH ＝ CH—, —CH ＝ N—, and R ² , R ³ , and R ⁴ may be the same or different from each other, and represent a hydrogen atom or a carbon atom. A linear, branched or cyclic alkyl group of 1 to 6, an aryl group having 6 to 20 carbon atoms, an amino group, an alkylamino group, an arylamino group,
A cyano group, a nitro group, a hydroxyl group or a halogen atom,
These substituents may be single or plurally substituted. ] 9. The spirofluorene compound according to claim 2, represented by the following general formula (20). Embedded image [However, in the general formula (20), A ⁵ , B ⁵ ,
C ⁵ , D ⁵ , E ⁵ and F ⁵ may be the same or different from each other and are each independently a hydrogen atom or any of the following general formulas (abbreviations) L1 to L23. ] 10. The general formula (10) according to claim 3,
The general formula (13) described in claim 5, the general formula (17) described in claim 7, or the general formula (1) described in claim 7
A synthetic intermediate represented by 8). 11. An organic electroluminescent device in which an organic layer having a light emitting region is provided between an anode and a cathode, wherein the spirofluorene compound represented by the general formula (1) according to claim 1 comprises An organic electroluminescent element, which is contained in an organic layer. 12. An organic electroluminescent device in which an organic layer having a light emitting region is provided between an anode and a cathode, wherein the spirofluorene compound represented by the general formula (2) according to claim 2 comprises: An organic electroluminescent element, which is contained in an organic layer. 13. The general formula (11) according to claim 4,
The general formula (14) described in claim 6, the general formula (19) described in claim 8, or the general formula (2) described in claim 9
The organic electroluminescent device according to claim 10, wherein a spirofluorene compound represented by 0) is used. 14. The organic layer has an organic laminated structure in which a hole transport layer and an electron transport layer are laminated, and the spirofluorene compound is used as a material for forming the hole transport layer. The organic electroluminescent device according to claim 9. 15. The organic layer has an organic laminated structure in which a hole transport layer and an electron transport layer are sequentially laminated, and the spirofluorene compound is used as a material for forming the electron transport layer. The organic electroluminescent device according to claim 9. 16. 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,
The organic electroluminescent device according to claim 9, wherein the spirofluorene compound is used as a material for forming the light emitting layer.