KR20110106193A - Spiro compound and organic electroluminescent devices comprising the same - Google Patents

Abstract

The present invention relates to a novel spiro compound and an organic light emitting device comprising the same, the organic electroluminescent device comprising a spiro compound according to the present invention has an excellent effect of brightness, color purity and life characteristics.

Description

Spiro compounds and organic electroluminescent devices comprising same {SPIRO COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICES COMPRISING THE SAME}

The present invention relates to a spiro compound and an organic light emitting device including the same, and more particularly, to a spiro compound having excellent brightness, color purity and life characteristics and an organic light emitting device comprising the same.

Recently, as the size of the display device increases, the demand for a flat display device having a small space is increasing. A liquid crystal display, which is a typical flat display device, has a merit of being lighter than a conventional cathode ray tube (CRT). The disadvantage is that the angle is limited and the back light is necessary. In contrast, the organic light emitting diode (OLED), a new flat panel display device, is a display using a self-luminous phenomenon, and has a large viewing angle, can be thinner and shorter than a liquid crystal display, and has a fast response speed. In recent years, the application to full-color display or lighting is expected.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy.

An organic light emitting display device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. In this case, the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the anode and electrons are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. When it falls back to the ground, it glows. Such organic light emitting diodes are known to have characteristics such as self-luminous, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

Materials used as the organic material layer in the organic light emitting device may be classified into light emitting materials and charge transport materials such as hole injection materials, hole transport materials, electron transport materials, electron injection materials and the like depending on their function. The light emitting material may be classified into a polymer type and a low molecular type according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. . In addition, the light emitting material may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to achieve a better natural color according to the light emitting color.

On the other hand, when only one material is used as a light emitting material, there arises a problem that the maximum light emission wavelength shifts to a long wavelength due to intermolecular interaction, the color purity decreases, or the efficiency of the device decreases due to the light emission attenuating effect. A host / dopant system may be used as the light emitting material in order to increase the light emitting efficiency through the light emitting layer. When the dopant having a smaller energy band gap than the host forming the light emitting layer is mixed with a small amount of the light emitting layer, the excitons generated in the light emitting layer are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host shifts to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant to be used.

In order for the organic electroluminescent device to fully exhibit the above-mentioned excellent features, the organic layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc. is supported by a stable and efficient material Although this should be preceded, the development of a stable and efficient organic material layer for an organic light emitting device has not been made yet. Therefore, the development of new materials in the art continues to be required.

The technical problem to be achieved by the present invention is to provide a spiro compound having excellent luminance and color purity of blue and a long life.

The second technical problem to be achieved by the present invention is to provide an organic light emitting device comprising the spiro compound.

In order to achieve the first technical problem, the present invention provides a spiro compound represented by the following formula (1).

In Chemical Formula 1,

R 1 to R 19 each independently represent a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted arylamino group, a substituted or unsubstituted aryloxy group having 3 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or An unsubstituted heteroaryl group having 3 to 40 carbon atoms, a substituted or unsubstituted germanium group, a substituted or unsubstituted phosphorus, and a substituted or unsubstituted boron, and adjacent groups of R1 to R19 are bonded to each other to substitute or Condensed rings of unsubstituted aliphatic, aromatic, heteroaliphatic or heteroaromatic groups can be formed.

In order to solve the second technical problem, the present invention is an anode; Cathode; And it is interposed between the anode and the cathode, and provides an organic light emitting device having a layer comprising a spiro compound represented by the formula (1).

The organic light emitting display device including the spiro compound represented by Formula 1 according to the present invention in an organic material layer may be usefully used for display and lighting because of its excellent brightness, color purity, and lifespan.

1 is a schematic diagram of an organic light emitting display device according to an embodiment of the present invention.
<Description of the symbols for the main parts of the drawings>
10: substrate 20: anode
30: hole injection layer 40: hole transport layer
50: organic light emitting layer 60: electron transport layer
70: electron injection layer 80: cathode

Hereinafter, the present invention will be described in more detail.

Spiro compound according to the invention is characterized in that represented by the formula (1).

In the spiro compound according to the present invention, the substituents of the formula (1) will be described in more detail.

In Formula 1, the substituents are each independently a deuterium atom, a cyano group, a halogen atom, a hydroxy group, a nitro group, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an alkylamino group having 1 to 40 carbon atoms, and 6 to 40 carbon atoms. Arylamino group, C3-C40 heteroarylamino group, C1-C40 alkylsilyl group, C6-C40 arylsilyl group, C6-C40 aryl group, C3-C40 aryloxy group, C3 It may be substituted by one or more substituents selected from the group consisting of heteroaryl group, germanium group, phosphorus and boron of to 40, it may be further substituted by the substituent. The substituents may be bonded to each other to form a condensed ring of aliphatic, aromatic, heteroaliphatic or heteroaromatic.

Specific examples of the alkyl group which is a substituent used in the present invention include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, heptyl, octyl, A stearyl group, a trichloromethyl group, a trifluoromethyl group, and the like, and at least one hydrogen atom of the alkyl group may be a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, a trifluoromethyl group, or a silyl group (in this case, Alkylsilyl groups ", substituted or unsubstituted amino groups (-NH ₂ , -NH (R), -N (R ') (R''), wherein R, R' and R" are each independently carbon atoms An alkyl group of 1 to 24 (in this case referred to as an "alkylamino group"), an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group of 1 to 24 carbon atoms, a halogenated alkyl group of 1 to 24 carbon atoms , Alkenyl group having 2 to 24 carbon atoms, alkynyl group having 2 to 24 carbon atoms, 1 carbon atom It may be substituted with a heteroalkyl group of 24 to 24, an aryl group of 5 to 24 carbon atoms, an arylalkyl group of 6 to 24 carbon atoms, a heteroaryl group of 3 to 24 carbon atoms or a heteroarylalkyl group of 3 to 24 carbon atoms.

Specific examples of the alkoxy group which is a substituent used in the compound of the present invention include methoxy group, ethoxy group, propoxy group, isobutyloxy group, sec-butyloxy group, pentyloxy group, iso-amyloxy group, hexyloxy group and the like. These can be mentioned and can substitute by the same substituent as the case of the said alkyl group.

Specific examples of the halogen group which is a substituent used in the compound of the present invention include fluorine (F), chlorine (Cl), bromine (Br) and the like.

Specific examples of the aryl group which is a substituent used in the compound of the present invention are phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, o-biphenyl group, m-biphenyl group, p-ratio Phenyl group, 4-methylbiphenyl group, 4-ethylbiphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, 1-naphthyl group, 2-naphthyl group, 1-methylnaphthyl group, 2-methylnaphthyl group And an aromatic group such as an anthryl group, a phenanthryl group, a pyrenyl group, a fluorenyl group, a tetrahydronaphthyl group, and the like, and may be substituted with the same substituent as in the alkyl group.

Specific examples of the heteroaryl group which is a substituent used in the compound of the present invention include pyridinyl group, pyrimidinyl group, triazinyl group, indolinyl group, quinolinyl group, pyrrolidinyl group, piperidinyl group, morpholidinyl group, pipepe Radiinyl, carbazolyl, oxazolyl, oxdiazolyl, benzooxazolyl, chiazolyl, thiadiazolyl, benzothiazolyl, triazolyl, imidazolyl and benzoimidazole At least one hydrogen atom of the heteroaryl group may be substituted with the same substituent as in the alkyl group.

In the present invention, the term "substituted or unsubstituted" is deuterium, halogen, alkyl, alkenyl, alkoxy, aryl, arylalkyl, arylalkenyl, heteroaryl, carbazolyl, fluorenyl, Substituted or unsubstituted with one or more substituents selected from the group consisting of a nitrile group and an acetylene group.

Specifically, the spiro compound according to the present invention may be any one of the compounds represented by the following Chemical Formulas 2 to 358.

The method for preparing the spiro compound according to the present invention is shown in detail in the Examples to be described later.

In addition, the present invention is an anode; Cathode; And it is interposed between the anode and the cathode, and provides an organic light emitting device having a layer comprising a spiro compound represented by the formula (1).

At this time, the layer containing the spiro compound is preferably a light emitting layer between the anode and the cathode, and between the anode and the cathode as a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer and an electron injection layer It may further comprise one or more layers selected from the group consisting of.

In addition, according to another embodiment of the present invention, the thickness of the light emitting layer is preferably 0.5nm to 500nm, the light emitting layer may further include Ir (ppy) ₃ of the following structural formula.

[Ir (ppy) ₃ ]

As a specific example, a hole transport layer (HTL) may be further stacked, and an electron transport layer (ETL) may be further stacked between the cathode and the organic light emitting layer. The silver is stacked to facilitate the injection of holes from the anode, and the electron transport molecule having a small ionization potential is used as the material of the hole transport layer. A diamine, triamine or tetraamine derivative mainly based on triphenylamine is used. It is used a lot.

The present invention is not particularly limited as long as it is commonly used in the art as a material of the hole transport layer. For example, N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1 , 1-biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalen-1-yl) -N, N'-diphenyl benzidine (a-NPD) and the like can be used.

A hole injection layer (HIL) may be further stacked on the lower portion of the hole transport layer. The hole injection layer material may also be used without particular limitation as long as it is commonly used in the art. TCP (4,4'-4 "-tri (N-carbazolyl) triphenyl-amine), for example, copper phthalocyanine (CuPc) or starburst amines, m-MTDATA (4,4 ', 4" -tris- (3-methylphenylphenylamino) triphenylamine) etc. can be used.

In addition, the electron transport layer used in the organic electroluminescent device according to the present invention has the opportunity to recombine in the light emitting layer by smoothly transporting the electrons supplied from the cathode to the organic light emitting layer and suppressing the movement of holes not bonded in the organic light emitting layer. Serves to increase. The electron transport layer material may be used without particular limitation as long as it is commonly used in the art, and for example, oxadiazole derivatives such as PBD, BMD, BND or Alq ₃ may be used.

Meanwhile, an electron injection layer (EIL) may be further stacked on the electron transport layer to facilitate electron injection from the cathode and ultimately improve power efficiency. Also commonly used in the art may be used without particular limitation, for example, it may be used a material such as LiF, NaCl, CsF, Li ₂ O, BaO.

The organic light emitting display device according to the present invention can be used for a display device, a display device and a monochrome or white lighting device.

1 is a cross-sectional view showing the structure of an organic light emitting display device according to the present invention. The organic light emitting device according to the present invention includes an anode 20, a hole transport layer 40, an organic light emitting layer 50, an electron transport layer 60 and a cathode 80, and if necessary, the hole injection layer 30 and The electron injection layer 70 may be further included. In addition, an intermediate layer of one or two layers may be further formed, and a hole blocking layer or an electron blocking layer may be further formed.

Referring to Figure 1 with respect to the organic light emitting device and a manufacturing method of the present invention, as follows. First, the anode 20 is formed by coating an anode electrode material on the substrate 10. As the substrate 10, a substrate used in a conventional organic EL device is used. An organic substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling, and waterproofness is preferable. As the anode electrode material, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), and the like, which are transparent and have excellent conductivity, are used.

The hole injection layer 30 is formed by vacuum-heat deposition or spin coating of the hole injection layer material on the anode 20 electrode. Next, the hole transport layer 40 is formed by vacuum thermal evaporation or spin coating of the hole transport layer material on the hole injection layer 30. Subsequently, the organic light emitting layer 50 is stacked on the hole transport layer 40, and a hole blocking layer (not shown) is selectively formed on the organic light emitting layer 50 by a vacuum deposition method or a spin coating method. can do. The hole blocking layer prevents such a problem by using a material having a very low highest Occupied Molecular Orbital (HOMO) level because when the hole is introduced into the cathode through the organic light emitting layer is reduced the lifetime and efficiency of the device. . In this case, the hole blocking material to be used is not particularly limited, but should have an ionization potential higher than the light emitting compound while having an electron transport ability, and typically BAlq, BCP, TPBI, and the like may be used.

After the electron transport layer 60 is deposited on the hole blocking layer through a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed and a cathode forming metal is vacuum-heated on the electron injection layer 70. The organic EL device is completed by vapor deposition to form a cathode 80 electrode. The metal for forming the cathode may be lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lidium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver ( Mg-Ag), and the like, and a transmissive cathode using ITO and IZO can be used to obtain a front light emitting device.

According to another embodiment of the present invention, at least one layer selected from the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer and the electron injection layer is a single molecule deposition method or a solution process The organic light emitting display device according to the present invention may be used in display devices, display devices, and monochrome or white lighting devices.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto.

< Example >

< Synthetic example  1> Preparation of the compound represented by the formula (4)

1) Synthesis of Compound Represented by Chemical Formula 1-a

A compound represented by Chemical Formula 1-a was synthesized according to Scheme 1 below.

Scheme 1

In a 2,000 ml round bottom flask, 50.0 g (0.295 mol) of diphenylamine and 38.10 ml (0.443 mol) of bromomethylmethyl ether were dissolved in 1,000 ml of tetrahydrofuran, and 44.85 g (0.443 mol) of triethylamine was slowly added dropwise. After stirring for 5 hours under a stream of nitrogen, the organic layer was separated using water and tetrahydrofuran, concentrated under reduced pressure, and separated by column chromatography using hexane and tetrahydrofuran as a developing solvent. Compound 52.0g represented by Chemical Formula 1-a (82.5%) was prepared.

2) Synthesis of Compound Represented by Chemical Formula 1-b

The compound represented by Chemical Formula 1-b was synthesized by Reaction Scheme 2 below.

Scheme 2

50 g (0.167 mmol) of 3-bromobenz ansrone, 44.9 g (0.176 mmol) of bis (pinacolato) diboron, 3.9 g (4.8 mmol) of PdCl ₂ (dppf), 31.54 g of potassium acetate in a 1000 ml round bottom flask (0.321 mmol) was added, 500 ml of toluene was added, and the mixture was stirred under reflux for 12 hours. After the reaction was completed, after cooling to room temperature, the organic layer was separated, and then water was removed with magnesium sulfate. Dichloromethane and normal hexane were used as a developing solvent, separated by column chromatography, and then concentrated under reduced pressure. The concentrated material was dissolved in dichloromethane, recrystallized from hexane, filtered and dried to obtain 43 g (74.7%) of the compound represented by Chemical Formula 1-b.

3) Synthesis of Compound Represented by Chemical Formula 1-c

The compound represented by Chemical Formula 1-c was synthesized by Reaction Scheme 3 below.

Scheme 3

9 g (27.8 mmol) of 4-bromotriphenylamine in a 250 ml round bottom flask, 11.9 g (33.3 mmol) of the compound represented by Chemical Formula 1-b obtained in Scheme 2, and 0.64 g (0.6 mmol) of tetrakis triphenylphosphine palladium ) {Pd (pph ₃ ) ₄ }, 7.67 g (55.5 mmol) of potassium carbonate, 45 ml of toluene, 45 ml of 1,4-dioxane and 18 ml of water were added and stirred under reflux for 12 hours. After completion of the reaction, the mixture was cooled to room temperature, and the layers were separated and the aqueous layer was removed. Magnesium sulfate was added to the organic layer to remove water, and then concentrated under reduced pressure. Then, the mixture was separated by column chromatography using dichloromethane and normal hexane as a developing solvent, and then concentrated under reduced pressure. Recrystallization from dichloromethane and normal hexane gave 7.8 g (78.4%) of the compound represented by Chemical Formula 1-c.

4) Synthesis of Compound Represented by Chemical Formula 1-d

The compound represented by Chemical Formula 1-d was synthesized by Reaction Scheme 4 below.

Scheme 4

In a 250 ml round bottom flask, 3.5 g (16 mmol) of the compound represented by Chemical Formula 1-a obtained in Scheme 1 was dissolved in 70 ml of tetrahydrofuran, stirred for 30 minutes under nitrogen, and the reaction temperature was lowered to -78 ° C and 1.6 mol hexane. 19.5 ml (16 mmol) of normal butyllithium in the solution was added dropwise for 1 hour. After stirring at the same temperature for 1 hour, 7.8 g (16 mmol) of the compound represented by Chemical Formula 1-c were dissolved in 50 ml of tetrahydrofuran and slowly added dropwise thereto. After stirring for 1 hour at the same temperature, the temperature was raised to room temperature, and after stirring for 5 hours, the organic layer was separated using an aqueous ammonium chloride solution and ethyl ether, concentrated under reduced pressure, and the resulting solid was washed with ethanol and dried. The dried material was dispersed in 60 ml of acetic acid, slowly added dropwise 2 ml of concentrated sulfuric acid, and refluxed for 5 hours. The resulting solid was filtered under reduced pressure, washed with water and ethanol, recrystallized with ethanol and dried to prepare 5.7 g (64.9%) of the compound represented by Chemical Formula 1-d.

4) Synthesis of Compound Represented by Formula 4

The compound represented by Chemical Formula 4 was synthesized according to Scheme 5 below.

Scheme 5

0.3 g (13.0 mmol) of sodium hydride and 50 ml of anhydrous dimethylformamide were added to a 250 ml round bottom flask, and the mixture was cooled to 0 ° C. under a nitrogen atmosphere. 5.3 g (8 mmole) of the compound represented by Chemical Formula 1-d was slowly added thereto and stirred for 30 minutes. 4.1 g (15 mmol) of diphenylchlorotriazine was dissolved in 50 ml of anhydrous dimethylformamide and added dropwise thereto, and maintained at 0 ° C. After completion of the dropwise addition, the temperature was raised to room temperature and stirred for 12 hours. After the reaction was completed, filtered, washed with water, hexane, ethanol and dried to obtain 2.4g (37.0%) of the compound represented by the formula (4).

< Synthetic example  2> Preparation of the compound represented by the formula (6)

1) Synthesis of Compound Represented by Chemical Formula 2-a

The compound represented by Chemical Formula 2-a was synthesized according to Reaction Scheme 6 below.

Scheme 6

Except for using 3-bromo-9-phenyl carbazole instead of 4-bromotriphenylamine used in the Scheme 3 synthesized in the same manner to prepare 7.5g (67.5%) of the compound represented by the formula 2-a It was.

2) Synthesis of Compound Represented by Formula 2-b

To the compound represented by formula 2-b by the following scheme 7 was synthesized.

Scheme 7

Except for using the compound represented by the formula 2-a instead of the compound represented by Formula 1-c used in Scheme 4 to synthesize a compound 5.6g (66.0%) represented by the formula 2-b It was.

3) Synthesis of Compound Represented by Chemical Formula 6

The compound represented by Chemical Formula 6 was synthesized according to Scheme 8 below.

Scheme 8

Except for using the compound represented by the formula 2-b instead of the compound represented by Formula 1-d used in Scheme 5 was synthesized in the same manner to prepare a compound 2.8g (36.5%) represented by the formula (6).

< Synthetic example  3> Synthesis of Compound Represented by Formula 21

1) Synthesis of Compound Represented by Formula 3-a

A compound represented by Chemical Formula 3-a was synthesized by Reaction Scheme 9 below.

Scheme 9

10 g (31 mmol) 3-bromo-9-phenylcarbazole, 3.8 g (40.3 mmol) aniline, 0.5 g (0.6 mmol) Pd ₂ (dba) ₃ , BINAP 0.39 g (0.6 mmol), sodium in 250 ml round bottom flask 5.97 g (62 mmol) of tert-butoxide was added to 100 ml of toluene, and stirred at 90 ° C for 8 hours. After the reaction was completed, the mixture was filtered to remove sodium tert-butoxide, and the filtrate was concentrated under reduced pressure. Recrystallization with ethyl acetate and normal hexane gave 8.3g (74.7%) of the compound of formula 3-a.

2) Synthesis of Compound Represented by Formula 3-b

A compound represented by Chemical Formula 3-b was synthesized by Reaction Scheme 10 below.

Scheme 10

Compound 3 represented by Formula 3-a instead of 3-Bromo-9-phenylcarbazole used in Scheme 10 was synthesized in the same manner, except that 4-bromo iodobenzene was used instead of aniline. 10.7 g (73.1%) of the compound represented by -b was prepared.

3) Synthesis of Compound Represented by Chemical Formula 3-c

A compound represented by Chemical Formula 3-c was synthesized according to Scheme 11 below.

Scheme 11

Except for using the compound represented by the formula 3-b instead of 4-bromotriphenylamine used in Scheme 3 was synthesized in the same manner to prepare 8.0g (61.1%) of the compound represented by the formula 3-c. .

4) Synthesis of Compound Represented by Chemical Formula 3-d

The compound represented by Chemical Formula 3-d was synthesized by Reaction Scheme 12 below.

[Reaction Scheme 12]

5.2g (77.8%) of the compound represented by Chemical Formula 3-d was synthesized in the same manner except that the compound represented by Chemical Formula 3-c was used instead of the compound represented by Chemical Formula 1-c used in Scheme 4. It was.

5) Synthesis of Compound Represented by Formula 21

The compound represented by Chemical Formula 21 was synthesized according to Scheme 13 below.

Scheme 13

Except for using the compound represented by the formula 3-d instead of the compound represented by the formula 1-d used in Scheme 5 to synthesize 2.5g (37.2%) of the compound represented by the same method.

< Synthetic example  4> Synthesis of Compound Represented by Formula 101

1) Synthesis of Compound Represented by Chemical Formula 4-a

The compound represented by Chemical Formula 4-a was synthesized according to Scheme 14 below.

[Reaction Scheme 14]

Except for using diphenylchloro triazine in place of 4-bromotriphenylamine used in Scheme 3, 36.6g (76.4%) of a compound represented by the formula 4-a was prepared in the same manner.

2) Synthesis of Compound Represented by Formula 4-b

The compound represented by Chemical Formula 4-b was synthesized by Reaction Scheme 15 below.

[Reaction Scheme 15]

6.2g (58.4%) of a compound represented by Chemical Formula 4-b was synthesized in the same manner except that the compound represented by Chemical Formula 4-a was used instead of the compound represented by Chemical Formula 1-c used in Scheme 4. It was.

3) Synthesis of Compound Represented by Formula (101)

The compound represented by Chemical Formula 101 was synthesized by Reaction Scheme 16 below.

[Reaction Scheme 16]

The compound represented by the formula 4-b instead of the compound represented by the formula 1-d used in Scheme 5, 2,2 '-(5-bromo-1,3-phenylene) di instead of diphenylchlorotriazine Except for using pyridine it was synthesized in the same manner to prepare 2.3g (32.2%) of a compound represented by the formula (101).

< Synthetic example  5> Preparation of a compound represented by Formula 108

1) Synthesis of Compound Represented by Chemical Formula 5-a

Compound 5-a was synthesized according to Scheme 17 below.

[Reaction Scheme 17]

15.0 g (53 mmol) of 3-bromoiodobenzene, 9.1 g (53 mmol) of 1-naphthylboronic acid, 1.2 g (1 mmol) of tetrakistriphenylphosphine palladium (Pd [PPh ₃ ] ₄ ), in a 250 ml round bottom flask, 14.7 g (106 mmol) of potassium carbonate was added thereto, 75 ml of toluene, 75 ml of tetrahydrofuran, and 30 ml of water were added thereto, followed by stirring under reflux for 12 hours. After the reaction was completed, after cooling to room temperature, the organic layer was separated, and then water was removed with magnesium sulfate. Hexane was used as a developing solvent, separated by column chromatography, and then concentrated under reduced pressure. The concentrated material was dissolved in dichloromethane, recrystallized from normal hexane, filtered and dried to obtain 12 g (79.9%) of the compound represented by Chemical Formula 5-a.

2) Synthesis of Compound Represented by Chemical Formula 108

The compound represented by Chemical Formula 108 was synthesized according to Scheme 18 below.

[Reaction Scheme 18]

Compound 108 was synthesized in the same manner except for using the compound represented by formula 5-a instead of compound 2,2 '-(5-bromo-1,3-phenylene) dipyridine used in Scheme 16 to Formula 108 4.5 g (48.4%) of the compound was prepared.

< Synthetic example  6> Synthesis of Compound Represented by Chemical Formula 257

1) Synthesis of Compound Represented by Chemical Formula 6-a

The compound represented by Chemical Formula 6-a was synthesized according to Reaction Scheme 19 below.

Scheme 19

11.2g (75.4%) of a compound represented by Chemical Formula 6-a was prepared by synthesizing in the same manner except that 3-bromobenzanthrone was used instead of the compound represented by Chemical Formula 1-c used in Scheme 4. .

2) Synthesis of Compound Represented by Chemical Formula 6-b

The compound represented by Chemical Formula 6-b was synthesized by Reaction Scheme 20 below.

[Reaction Scheme 20]

The compound represented by Chemical Formula 6-a is used instead of the compound represented by Chemical Formula 1-d used in Scheme 5, except that 2-chloro-4,6-diphenylpyrimidine is used instead of diphenylchlorotriazine. Synthesis by the method to prepare a compound represented by the formula 6-b 6.5g (43.4%).

3) Synthesis of Compound Represented by Chemical Formula 257

The compound represented by Chemical Formula 257 was synthesized by Reaction Scheme 21 below.

Scheme 21

Compound represented by Chemical Formula 257, synthesized in the same manner except for using diphenylamine instead of 3-bromo-9-phenylcarbazole, a compound represented by the formula 6-b instead of aniline used in Scheme 10 3.4g (46.4%) was prepared.

< Example  1 to 6 Of organic light emitting device  Produce

The light emitting area of the ITO glass was patterned to have a size of 2 mm x 2 mm and then washed. After mounting the substrate in the vacuum chamber, the base pressure is 1 × 10 ^-6 torr and the organic material is placed on the ITO DNTPD (700 kPa), NPD (300 kPa), the compound + Ir (ppy) ₃ (prepared by the present invention) 10%) (300 mW), Alq ₃ (350 mW), LiF (5 mW), and Al (1,000 mW) were formed in this order and measured at 0.4 mA.

[DNTPD]

[NPD]

[Ir (ppy) ₃ ]

[Alq ₃ ]

< Comparative example  1>

An organic light emitting display device for a comparative example was manufactured in the same manner except for using CBP having the following structural formula instead of the compound prepared by the present invention in the device structure of Examples 1 to 6.

[CBP]

From the results of Examples 1 to 6, Comparative Example 1 and Table 1, the compound represented by the formula (1) according to the present invention exhibits excellent properties such as light emission characteristics compared to CBP used as a phosphorescent material, display device, It can be seen that it can be usefully used for display elements and lighting.

Claims (10)

Spiro compounds represented by the following formula (1):
[Formula 1]

In Chemical Formula 1,
R 1 to R 19 each independently represent a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted arylamino group, a substituted or unsubstituted aryloxy group having 3 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or An unsubstituted heteroaryl group having 3 to 40 carbon atoms, a substituted or unsubstituted germanium group, a substituted or unsubstituted phosphorus, and a substituted or unsubstituted boron, and adjacent groups of R1 to R19 are bonded to each other to substitute or Condensed rings of unsubstituted aliphatic, aromatic, heteroaliphatic or heteroaromatic groups can be formed. The method of claim 1,
R1 to R19 of Formula 1 are each independently a deuterium atom, cyano group, halogen atom, hydroxy group, nitro group, alkyl group of 1 to 40 carbon atoms, alkoxy group of 1 to 40 carbon atoms, alkylamino group of 1 to 40 carbon atoms, 6 carbon atoms Arylamino group of 40 to 40, heteroarylamino group of 3 to 40 carbon atoms, alkylsilyl group of 1 to 40 carbon atoms, arylsilyl group of 6 to 40 carbon atoms, aryl group of 6 to 40 carbon atoms, aryloxy group of 3 to 40 carbon atoms, Spiro compound, characterized in that substituted by one or more selected from the group consisting of a heteroaryl group, a germanium group, phosphorus and boron having 3 to 40 carbon atoms. The method of claim 1,
The spiro compound is one of the compounds represented by the following formula 2 to formula 358 Spiro compound, characterized in that:

Anode;
Cathode; And
An organic electroluminescent device having a layer interposed between the anode and the cathode and comprising a spiro compound according to any one of claims 1 to 3. The method of claim 4, wherein
The layer containing the spiro compound is an organic light emitting device, characterized in that the light emitting layer between the anode and the cathode. The method of claim 5,
An organic electroluminescent device further comprising at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer and an electron injection layer between the anode and the cathode. The method of claim 5,
The thickness of the light emitting layer is an organic light emitting device, characterized in that 0.5nm to 500nm. The method of claim 5,
The organic light emitting device, characterized in that the light emitting layer further comprises Ir (ppy) ₃ of the following structural formula:
[Ir (ppy) ₃ ]

The method of claim 6,
At least one layer selected from the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer and the electron injection layer is formed by a single molecule deposition method or a solution process. The method of claim 4, wherein
The organic electroluminescent device is an organic electroluminescent device, characterized in that used for a display device, a display device, or a device for monochrome or white illumination.

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