KR101779913B1 - Spiro compound and organic electroluminescent devices comprising the same - Google Patents

Abstract

The present invention relates to a novel spiro compound and an organic electroluminescent device including the spiro compound, and the organic electroluminescent device including the spiro compound according to the present invention has an excellent effect on luminance, color purity and lifetime characteristics.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a spiro compound and an organic electroluminescent device including the spiro compound.

TECHNICAL FIELD The present invention relates to a spiro compound and an organic electroluminescent device including the spiro compound, and more particularly, to a spiro compound and an organic electroluminescent device including the spiro compound having excellent brightness, color purity and lifetime.

In recent years, the demand for a flat display device having a small space occupation has been increasing due to the enlargement of a display device. The liquid crystal display, which is a typical flat display device, has an advantage of being lighter than a conventional CRT (cathode ray tube) angle is limited and a back light is necessarily required. On the other hand, an organic light emitting diode (OLED), which is a new flat display device, is a display using a self-luminous phenomenon, has a large viewing angle, is slimmer and smaller than a liquid crystal display, And in recent years, application to a full-color display or illumination 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 electroluminescent device using an organic light emitting phenomenon usually has a structure including an anode, an anode, and an organic material layer therebetween. Here, in order to enhance the efficiency and stability of the organic electroluminescent device, the organic material layer may have a multi-layer structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between the two electrodes in the structure of the organic electroluminescent device, holes are injected into the anode, electrons are injected into the organic layer, and excitons are formed when injected holes and electrons meet. When it falls back to the ground state, the light comes out. Such an organic electroluminescent device is known to have properties such as self-emission, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

A material used as an organic material layer in an organic electroluminescent device can be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions. The light emitting material may be classified into a polymer type and a low molecular type depending on the molecular weight and may be classified into a fluorescent material derived from singlet excited state of electrons and a phosphorescent material derived from the triplet excited state of electrons according to an emission mechanism . Further, the light emitting material can be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials necessary for realizing better natural color depending on the luminescent 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 is shifted to the wavelength band of the dopant, light of a desired wavelength can be obtained depending on the type of dopant used.

In order for the organic electroluminescent device to sufficiently exhibit the above-described excellent characteristics, materials constituting the organic material layer in the device, such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material are supported by a stable and efficient material However, the development of a stable and efficient organic material layer material for an organic electroluminescence device has not been sufficiently developed yet. Therefore, there is a continuing need in the art for the development of new materials.

Disclosure of Invention Technical Problem [8] The present invention provides a spiro compound having excellent luminescence brightness and color purity and having a long life span.

A second object of the present invention is to provide an organic electroluminescent device including the spiro compound.

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

In Formula 1,

R ₁ to R ₅ each independently represent a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted arylamino group having 6 to 40 carbon atoms, a substituted or unsubstituted aryloxy group having 3 to 40 carbon atoms, A substituted or unsubstituted aryl group, a substituted or 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, A substituted or unsubstituted aliphatic, aromatic, heteroaliphatic or heteroaromatic condensed ring,

A is C or Si,

L is a substituted or unsubstituted ethylene or ethenylene group having 2 carbon atoms,

Cy1 and Cy2 are each independently a substituted or unsubstituted 5- to 8-membered ring aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms.

In order to solve the second technical problem, the present invention provides a semiconductor device comprising: an anode; Cathode; And a layer including a spiro compound represented by Formula 1 interposed between the anode and the cathode.

The organic electroluminescent device including the spiro compound represented by the formula (1) in the organic material layer according to the present invention has excellent brightness, color purity and lifetime characteristics, and thus can be used for display and illumination.

1 is a schematic view of an organic electroluminescent device according to one embodiment of the present invention.
Description of the Related Art
10: substrate 20: anode
30: Hole injection layer 40: Hole transport layer
50: organic light emitting layer 60: electron transporting layer
70: electron injection layer 80: cathode

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

The spiro compound according to the present invention is characterized by being represented by the above formula (1).

In the spiro compounds according to the present invention, the substituents of the above formula (1) will be described more specifically.

delete

Specific examples of the alkyl group as the substituent used in the present invention include a methyl group, an ethyl group, a propyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isoamyl group, a hexyl group, a heptyl group, A halogen atom, a hydroxyl group, a nitro group, a cyano group, a trifluoromethyl group, a silyl group (in this case, a " alkylsilyl group "hereinafter), a substituted or unsubstituted amino group _{(-NH 2, -NH (R)} , -N (R ') (R''), where R, R' and R" are each independently a carbon number A hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms (for example, an alkyl group having 1 to 24 carbon atoms , An alkenyl group having 2 to 24 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, An aryl group having from 5 to 24 carbon atoms, an aryl group having from 5 to 24 carbon atoms, an arylalkyl group having from 6 to 24 carbon atoms, a heteroaryl group having from 3 to 24 carbon atoms, or a heteroarylalkyl group having from 3 to 24 carbon atoms.

Specific examples of the alkoxy group used as the substituent in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, isoamyloxy, And can be substituted with substituents similar to those in the case of the 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 as the substituent group used in the compound of the present invention include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, Examples of the aryl group include phenyl group, 4-methylbiphenyl group, 4-ethylbiphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, 1-naphthyl group, , Anthryl group, phenanthryl group, pyrenyl group, fluorenyl group, tetrahydronaphthyl group and the like, which may be substituted with the same substituents as those in the case of the alkyl group.

Specific examples of the heteroaryl group used as the substituent in the compound of the present invention include pyridinyl, pyrimidinyl, triazinyl, indolinyl, quinolinyl, pyrrolidinyl, piperidinyl, An oxazolyl group, an oxadiazolyl group, a benzoxazolyl group, a thiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a triazolyl group, an imidazolyl group, a benzoimidazole group, And at least one of the hydrogen atoms of the heteroaryl group may be substituted with the same substituent as the alkyl group.

In the present invention, the term "substituted or unsubstituted" refers to a group selected from the group consisting of deuterium, halogen, alkyl, alkenyl, alkoxy, aryl, arylalkyl, arylalkenyl, heteroaryl, Substituted or unsubstituted with at least one substituent selected from the group consisting of an acetylene group, a nitrile group and an acetylene group.

The spiro compound according to the present invention can be represented by any one of the following formulas (1-1) to (1-27).

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

[Chemical Formula 1-9]

[Chemical Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

[Chemical Formula 1-14]

[Chemical Formula 1-15]

[Chemical Formula 1-16]

[Formula 1-17]

[Chemical Formula 1-18]

[Chemical Formula 1-19]

[Chemical Formula 1-20]

[Formula 1-21]

[Formula 1-22]

[Formula 1-23]

[Formula 1-24]

[Chemical Formula 1-25]

[Chemical Formula 1-26]

[Chemical Formula 1-27]

In the above Formulas 1-1 to 1-27,

R ₁ to R ₅ , L and A are the same as defined in the above formula (1)

X ₁ to X ₄ are each independently C or N,

Z ₁ is NR ₅ or S,

Z ₂ and Z ₃ are each independently NR ₅ , S or O.

Specifically, the spiro compound according to the present invention may be any one of the compounds represented by Chemical Formulas 2 to 491 shown in Table 1 below.

[Table 1]

The production method of the spiro compound according to the present invention is specifically shown in the following Examples.

The present invention also relates to a fuel cell comprising an anode; Cathode; And a layer including a spiro compound represented by Formula 1 interposed between the anode and the cathode.

In this case, the layer containing the spiro compound is preferably a light emitting layer between the anode and the cathode, and a hole injecting layer, a hole transporting layer, an electron blocking layer, a hole blocking layer, an electron transporting layer and an electron injecting layer And at least one layer 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 0.5 nm to 500 nm, and 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 additionally stacked, and an electron transport layer (ETL) may be further stacked between the cathode and the organic emission layer. An electron donor molecule having a low ionization potential is used as the material of the hole transport layer. A diamine, triamine or tetraamine derivative having a basic skeleton of triphenylamine is used as the hole transport layer. It is widely used.

In the present invention, the material for the hole transport layer is not particularly limited as long as it is commonly used in the art. For example, N, N'-bis (3-methylphenyl) -N, N'- , 1-biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine (a-NPD).

A HIL (Hole Injection Layer) may be additionally deposited on the lower portion of the hole transport layer. The material for the hole injection layer is not particularly limited as long as it is commonly used in the art. For example, (4,4 ', 4 "-tri (N-carbazolyl) triphenylamine), m-MTDATA (4,4', 4" -tris- (3-methylphenylphenylamino) triphenylamine).

In addition, the electron transport layer used in the organic electroluminescent device according to the present invention can transport electrons supplied from the cathode smoothly to the organic luminescent layer and inhibit the movement of holes which are not bonded in the organic luminescent layer, . The material of the electron transport layer is not particularly limited as long as it is commonly used in the art. For example, oxadiazole derivative PBD, BMD, BND or Alq ₃ can be used.

Meanwhile, an electron injection layer (EIL) may be further formed on the electron transport layer to facilitate injection of electrons from the cathode to ultimately improve power efficiency. The electron injection layer material As long as it is commonly used in the art, it can be used without any particular limitation. For example, materials such as LiF, NaCl, CsF, Li ₂ O, and BaO can be used.

The organic electroluminescent device according to the present invention can be used for a display device, a display device, an element for a single color or a white light, and the like.

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

Referring to FIG. 1, the organic electroluminescent device of the present invention and its manufacturing method will be described as follows. First, an anode electrode material is coated on the substrate 10 to form an anode 20. Here, as the substrate 10, an organic substrate or a transparent plastic substrate which is excellent in transparency, surface smoothness, ease of handling, and waterproofness is used as a substrate used in a conventional organic EL device. As the material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) and the like which are transparent and excellent in conductivity are used.

A hole injection layer 30 is formed on the anode 20 by vacuum thermal deposition or spin coating. Subsequently, a hole transport layer 40 is formed by vacuum thermal deposition or spin coating on the hole transport layer 30 above the hole injection layer 30. 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 to form a thin film on the organic light emitting layer 50 can do. In the case where holes are injected into the cathode through the organic light-emitting layer, the lifetime and the efficiency of the device are reduced, and thus the hole blocking layer plays a role of preventing such a problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level . In this case, the hole blocking material to be used is not particularly limited, but it is required to have an ionization potential higher than that of the light emitting compound while having electron transporting ability. Typically, BAlq, BCP, TPBI and the like can be used.

After the electron transport layer 60 is deposited on the hole blocking layer by a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed, and a cathode forming metal is deposited on the electron injection layer 70 in a vacuum heat- And the cathode 80 is formed by vapor deposition to complete the organic EL device. Here, as the metal for forming the cathode, lithium, magnesium, aluminum, aluminum-lithium, calcium, magnesium-magnesium, Mg-Ag), and a transmissive cathode using ITO or IZO can be used to obtain a top light-emitting device.

According to another embodiment of the present invention, at least one layer selected from the hole injecting layer, the hole transporting layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transporting layer and the electron injecting layer is formed by a single molecular deposition method or a solution process And the organic electroluminescent device according to the present invention can be used for a display device, a display device, and a monochromatic or white illumination device.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited thereto.

< Example >

< Synthetic example  1> Preparation of the compound represented by the formula (2)

1) Synthesis of the compound represented by the formula 1-a

The compound represented by the formula (1-a) was synthesized by the following Reaction Scheme 1.

[Reaction Scheme 1]

50.0 g (0.295 mol) of diphenylamine and 38.10 ml (0.443 mol) of bromomethyl methyl ether were dissolved in 1,000 ml of tetrahydrofuran, and 44.85 g (0.443 mol) of triethylamine was slowly added dropwise to a 2,000 ml round bottom flask, After stirring for 5 hours in a nitrogen stream, the organic layer was separated using water and tetrahydrofuran, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography using hexane and tetrahydrofuran as eluent to obtain 53.3 g (84.6%).

2) Synthesis of the compound represented by the formula 1-b

A compound represented by the formula 1-b was synthesized by the following Reaction Scheme 2.

[Reaction Scheme 2]

10.0 g (0.047 mol) of the compound represented by the formula 1-a obtained from the reaction formula 1 was dissolved in 100 ml of tetrahydrofuran, and the mixture was stirred for 30 minutes in a nitrogen atmosphere. The temperature of the reaction mixture was lowered to -78 ° C and 1.6 mol 29.4 ml (0.047 mol) of n-butyllithium in hexane solution was added dropwise over 1 hour. After stirring at the same temperature for 1 hour, 9.8 g (0.047 mol) of dibenzosuberone was dissolved in 40 ml of tetrahydrofuran and slowly added dropwise. After stirring at the same temperature for 1 hour, the temperature was raised to room temperature and stirred for 5 hours. The organic layer was separated using ammonium chloride aqueous solution and ethyl ether, and the resulting solid was washed with ethanol and dried. The dried material was dispersed in 100 ml of acetic acid, 2 ml of concentrated sulfuric acid was slowly added dropwise, and the mixture was refluxed for 5 hours. The resulting solid was filtered off under reduced pressure, washed with water and ethanol, recrystallized using ethanol, and dried to obtain 14.4 g (85%) of a compound represented by the formula 1-b.

3) Synthesis of the compound represented by the formula 1-c

The compound represented by the formula 1-c was synthesized by the following Reaction Scheme 3.

[Reaction Scheme 3]

After making a nitrogen atmosphere in a 100 ml reactor, magnesium (3.36 g, 0.1384 mol), 40 ml of dry tetrahydrofuran and a small amount of iodine were added and stirred for 30 minutes. To this mixture was added dropwise 20 ml of a dry tetrahydrofuran solution of bromobenzene (19.2 g, 0.1216 mol) at 0 占 폚. After the dropwise addition, the mixture was heated and stirred at 65 DEG C for 2 hours. 2-diphenylamino-4,6-dichloro-1,3,5-triazine (18 g, 0.0568 mol) was dissolved in 100 ml of dry tetrahydrofuran, and the mixture of the 100 ml reactor was added dropwise at 0 占 폚. After dropwise addition, the mixture was stirred at room temperature for 12 hours. After completion of the reaction, 200 ml of 2N HCl was added. The organic layer was separated by layer separation, extracted with ethyl acetate and water, and neutralized. The organic layer was subjected to anhydrous treatment and then reduced in pressure to remove the organic solvent. 200 ml of hexane was added to 50 ml of EA, stirred and filtered to obtain 9.8 g of white solid 2,4-diphenyl-6-chloro-1,3,5-triazine (64.5%).

4) Synthesis of Compound Represented by Chemical Formula 2

The compound represented by the formula (2) was synthesized by the following Reaction Scheme 4.

[Reaction Scheme 4]

15.0 g (0.0417 mol) of the compound represented by the formula 1-b obtained from the reaction formula 2, 22.3 g (0.0835 mol) of the compound represented by the formula 1-c obtained from the reaction formula 3 and 11.5 g (0.0835 mol) of the potassium carbonate were added to a 250- 0.8 g (4.17 mmol) of copper iodide, 0.5 g (8.34 mmol) of copper and 300 ml of xylene were placed and refluxed for 2 days. After completion of the reaction, the reaction mixture was cooled to room temperature, and the organic layer was separated using water and ethyl acetate. The organic layer was separated and concentrated under reduced pressure. The residue was purified by column chromatography using hexane and ethyl acetate as eluent to obtain a solid. (45%).

_{^{1 H NMR (300MHz, CDCl 3}} ): δ 8.33 (d, 4H), 7.56 (t, 4H), 7.46 (t, 2H), 7.26 ~ 7.20 (m, 8H), 7.06 ~ 7.03 (m, 4H), 6.74 (t, 2H), 6.56 (m, 2H), 2.93 (s, 4H)

MS (MALDI-TOF): m / z 590.25 [M] &lt; + &

< Synthetic example  2> Preparation of the compound represented by the formula (109)

The compound represented by the formula (109) was synthesized by the following Reaction Scheme (5).

[Reaction Scheme 5]

(51.4%) of the compound represented by the formula (109) was synthesized except that 3-bromopyridine was used instead of the chlorodiphenyltriazine used in the reaction scheme 4.

_{^{1 H NMR (300MHz, CDCl 3}} ): δ 7.42 (t, 1H), 7.33 ~ 7.20 (m, 9H), 7.06 ~ 7.03 (m, 4H), 7.05 (t, 2H), 6.57 (d, 2H), 2.88 (s, 4H)

MS (MALDI-TOF): m / z 436.19 [M] &lt; + &

< Synthetic example  3> Synthesis of Compound Represented by Formula 113

1) Synthesis of Compound Represented by Formula 3-a

A compound represented by the general formula (3-a) was synthesized by the following Reaction Scheme (6).

[Reaction Scheme 6]

92.1 g (0.576 mol) of bromine and 28.17 g (0.0211 mol) of aluminum chloride were placed in a 250 ml round bottom flask and the external temperature was lowered to 0 캜. 20 g (0.096 mol) of dibenzosuberone was added dropwise to the above solution for 30 minutes. After the dropwise addition, the mixture was stirred for about 1 hour, and then the temperature was raised to room temperature. After completion of the reaction, the external temperature was lowered to 0 캜, and then 100 ml of water was slowly added dropwise. After extracting with 100 ml of methyl chloride, the organic layer was neutralized with aqueous sodium bicarbonate solution. The organic layer was dried (anhydrous), and the organic solvent was concentrated under reduced pressure. The solid was separated by column chromatography using hexane and dichloromethane as eluent to obtain 9 g (25%) of a compound represented by the formula 3-a Respectively.

2) Synthesis of the compound represented by the formula 3-b

The compound represented by the formula 3-b was synthesized according to the following Reaction Scheme 7.

[Reaction Scheme 7]

(0.0884 mol) of 2-bromoiodobenzene, 15.7 g (0.0928 mol) of diphenylamine, 0.4 g (1.768 mmol) of palladium acetate, 1.1 g (1.768 mmol) of biphenyl, 1.7 g , And 250 ml of toluene were placed, and the mixture was refluxed for 20 hours. After completion of the reaction, the reaction solution was filtered through celite, and the filtrate was concentrated under reduced pressure. The filtrate was separated by column chromatography using hexane and dichloromethane as eluent to obtain a solid. The solid was dried to obtain 17 g 67%).

3) Synthesis of the compound represented by the formula 3-c

The compound represented by the formula 3-c was synthesized by the following Reaction Scheme 8.

[Reaction Scheme 8]

10.0 g (0.0308 mol) of the compound represented by the formula 3-b obtained from the reaction formula 7 was dissolved in 100 ml of tetrahydrofuran, and the mixture was stirred for 30 minutes under a nitrogen atmosphere. The temperature of the reaction solution was lowered to -78 ° C and 1.6 mol 19.3 ml (0.0308 mol) of normal butyl lithium in hexane solution was added dropwise over 1 hour. After stirring at the same temperature for 1 hour, 11.3 g (0.0308 mol) of dibromobenzosuberone was dissolved in 50 ml of tetrahydrofuran and slowly added dropwise. After stirring at the same temperature for 1 hour, the temperature was raised to room temperature and stirred for 5 hours. The organic layer was separated using ammonium chloride aqueous solution and ethyl ether, and the resulting solid was washed with ethanol and dried. The dried material was dispersed in 100 ml of acetic acid, 2 ml of concentrated sulfuric acid was slowly added dropwise, and the mixture was refluxed for 5 hours. The resulting solid was filtered off under reduced pressure, washed with water and ethanol, recrystallized using ethanol, and dried to obtain 16.2 g (89%) of a compound represented by the formula 3-c.

4) Synthesis of Compound Represented by Formula 113

A compound represented by the formula (113) was synthesized by the following Reaction Scheme (9).

[Reaction Scheme 9]

7 g (0.0118 mol) of the compound represented by the formula 3-c, 3.6 g (0.0295 mol) of 3-pyridine boronic acid and 3.3 g (0.0236 mol) of potassium carbonate (K ₂ CO ₃ ) were added to a 100 ml round bottom flask, tetrakis (triphenylphosphine) palladium (Pd (PPh _{3) 4)} In the 0.5g (0.472mmol), 35mL of water, 56ml of toluene and 35mL of tetrahydrofuran and refluxed for 24 hours. After completion of the reaction, the reaction product was separated to remove the aqueous layer, and the organic layer was separated and concentrated under reduced pressure. The residue was separated by column chromatography using hexane and dichloromethane as eluent to obtain 4.5 g of the compound represented by Formula 113 65%).

_{^{1 H NMR (300MHz, CDCl 3}} ): δ 9.22 (s, 2H), 8.68 (d, 2H), 8.40 (d, 2H), 7.72 (s, 2H), 7.55 (t, 2H), 7.21 ~ 7.18 ( 4H), 6.48 (d, 2H), 2.87 (s, 4H), 6.87 (m,

MS (MALDI-TOF): m / z 587.26 [M] &lt; + &

< Synthetic example  4> Preparation of the compound represented by the general formula (105)

1) Synthesis of the compound represented by the formula 4-a

A compound represented by the formula 4-a was synthesized by the following Reaction Scheme 10.

[Reaction Scheme 10]

(0.12 mol) of carbazole, 68 g (0.24 mol) of 2-bromoiodobenzene, 33 g (0.24 mol) of potassium carbonate, 2.3 g (0.012 mol) of copper iodide, 1.5 g 400 ml of xylene was added and the mixture was refluxed for 2 days. After the completion of the reaction, the reaction mixture was cooled to room temperature, and the organic layer was separated using water and ethyl acetate. The organic layer was separated by column chromatography using hexane and ethyl acetate as eluent to obtain 15 g (39% ).

2) Synthesis of the compound represented by the formula 4-b

A compound represented by the formula 4-b was synthesized by the following Reaction Scheme 11.

[Reaction Scheme 11]

Except that the compound represented by the formula 4-a synthesized in the reaction scheme 10 was used instead of the compound represented by the formula 3-b used in the reaction scheme 8, to obtain 17.0 g of the compound represented by the formula 4-b (87%).

3) Synthesis of the compound represented by the formula 4-c

The compound represented by the formula 4-c was synthesized by the following Reaction Scheme 12.

[Reaction Scheme 12]

30 g (0.082 mol) of the compound represented by the formula 1-c obtained in the reaction formula 3, 25 g (0.0984 mol) of bis (pinacolato) diboron, 1.0 g (0.0016 mol) of PdCl ₂ (dppf) 12.4 g (0.164 mol) of acetate and 300 ml of toluene were added and refluxed for 20 hours. When the reaction is completed, the temperature is lowered to room temperature and extracted with toluene and water. The organic layer was concentrated under reduced pressure, and then subjected to column chromatography using hexane and methylene chloride as eluent to give 24.2 g (81%) of a compound represented by the formula 4-c.

4) Synthesis of compound represented by formula 105

The compound represented by the general formula (105) was synthesized according to the following Reaction Scheme (13).

[Reaction Scheme 13]

Instead of the compound represented by the formula 3-c used in the reaction scheme 9, the compound represented by the formula 4-b synthesized in the reaction scheme 11 and the compound represented by the formula 4-c synthesized in the scheme 12 instead of the 3-pyridine boronic acid (54%) of the compound represented by the general formula (105) was synthesized in the same manner as in Example 1,

_{^{1 H NMR (300MHz, CDCl 3}} ): δ 8.54 (d, 1H), 8.40 (d, 2H), 8.27 (d, 8H), 7.94 ~ 7.93 (m, 2H), 7.74 (s, 2H), 7.51 ( t, 8H), 7.40 ~ 7.17 (m, 14H), 2.91 ~ 2.86 (m, 4H)

MS (MALDI-TOF): m / z 895.34 [M] &lt; + &

< Synthetic example  5> Synthesis of Compound Represented by Formula 107

1) Synthesis of Compound Represented by Formula 5-a

A compound represented by the formula 5-a was synthesized by the following Reaction Scheme 14.

[Reaction Scheme 14]

24.0 g (38%) of the compound represented by the formula 5-a was prepared by the same procedure as described in the reaction scheme 10, except that indolocarbazole was used in place of the carbazole used in the reaction scheme 10.

2) Synthesis of the compound represented by the formula 5-b

The compound represented by the formula 5-b was synthesized according to the following Reaction Scheme 15.

[Reaction Scheme 15]

17.0 g (0.0464 mol) of 2,7-dibromodibenzosuberone, 21.3 g (0.1022 mol) of phosphorus pentachloride and 70 ml of phosphorus oxychloride were placed in a 500 ml round-bottomed flask and reacted at 100 ° C for 4 hours. After completion of the reaction, the mixture was cooled to room temperature, and then the reaction solution was slowly poured into a mixed solution of 80 ml of methyl chloride, 50 ml of methanol and 50 ml of water. An excess amount of water was added to the above solution, and the mixture was stirred for 12 hours. The filtered solid was washed with methanol. Methyl chloride, and the solution was boiled, cooled and filtered to obtain 7 g (yield: 44%) of a white solid of the compound represented by the formula (5-b).

3) Synthesis of the compound represented by the formula 5-c

The compound represented by the formula 5-c was synthesized by the following Reaction Scheme 16.

[Reaction Scheme 16]

A was used instead of the compound represented by the formula 4-a used in the reaction scheme 11 and the compound represented by the formula 5-a synthesized in the reaction scheme 15 was used instead of the compound represented by the formula 3-a, (85%) of the compound represented by the formula 5-c was synthesized in the same manner as in the synthesis of the compound represented by the formula 5-c.

4) Synthesis of Compound Represented by Formula 107

The compound represented by the formula (107) was synthesized by the following Reaction Scheme (17).

[Reaction Scheme 17]

Except that the compound represented by the formula 5-c synthesized in the reaction scheme 16 was used instead of the compound represented by the formula 4-b used in the reaction scheme 13 to obtain 7.2 g (37 %).

_{^{1 H NMR (300MHz, CDCl 3}} ): δ 8.55 (d, 1H), 8.36 (d, 1H), 8.28 (d, 8H), 8.12 (d, 1H), 7.94 (d, 1H), 7.79 (s, 2H), 6.90 (s, 2H), 7.60-7.22 (m, 28H)

MS (MALDI-TOF): m / z 1058.38 [M] &lt; + &

< Synthetic example  6> Preparation of the compound represented by the formula (108)

1) Synthesis of the compound represented by the formula 6-a

A compound represented by the formula 6-a was synthesized by the following Reaction Scheme 18.

[Reaction Scheme 18]

27.0 g (69%) of the compound represented by the formula 6-a was prepared, except that di (4-pyridyl) amine was used instead of the diphenylamine used in the reaction scheme 7.

2) Synthesis of the compound represented by the formula 6-b

The compound represented by the formula (6-b) was synthesized by the following reaction scheme (19).

[Reaction Scheme 19]

Except that dibromodibenzosubererone was used instead of dibromodibenzosuberone in place of dibromodibenzosuberone and the compound represented by the formula 6-a synthesized in the reaction scheme 14 instead of the compound represented by the formula 3-b used in the reaction scheme 8 , And 16.0 g (83%) of the compound represented by the formula (6-b) were synthesized in the same manner.

3) Synthesis of the compound represented by the formula (108)

The compound represented by the formula (108) was synthesized by the following Reaction Formula (20).

[Reaction Scheme 20]

Except that the compound represented by the formula 6-b synthesized in the reaction scheme 19 was used instead of the compound represented by the formula 3-c used in the reaction scheme 9 and 3-quinolidinol boronic acid was used instead of 3-pyridinoboronic acid, Synthesis was conducted in the same manner to prepare 12.0 g (78%) of a compound represented by the formula (108).

_{^{1 H NMR (300MHz, CDCl 3}} ): δ 8.87 (s, 2H), 8.48 ~ 8.43 (m, 5H), 8.26 (s, 1H), .92 (d, 2H), 7.79 (m, 2H), 7.76 (M, 6H), 6.69 (d, IH), 6.83 (d, IH), 6.51

MS (MALDI-TOF): m / z 689.26 [M] &lt; + &

< Synthetic example  7> Preparation of the compound represented by the formula (106)

1) Synthesis of the compound represented by the formula 7-a

A compound represented by the general formula (7-a) was synthesized by the following Reaction Scheme (21).

[Reaction Scheme 21]

Except that dibromodibenzosuberrone was used in place of the compound represented by the formula 3-c used in the reaction scheme 9 and phenylboronic acid was used instead of 3-pyridinoboronic acid to obtain the compound represented by the formula 7-a 17.0 g (72%) of the indicated compound was prepared.

2) Synthesis of the compound represented by the formula 7-b

The compound represented by the general formula (7-b) was synthesized according to the following reaction scheme (22).

[Reaction Scheme 22]

(84.7%) of the compound represented by the formula (7-b) except that the dibenzosuberone used in the reaction scheme 2 was replaced by the compound represented by the formula (7-a) .

3) Synthesis of Compound Represented by Formula 106

The compound represented by the formula (106) was synthesized according to the following reaction scheme (23).

[Reaction Scheme 23]

Except that the compound represented by the formula 7-b synthesized in the reaction scheme 22 was used instead of the compound represented by the formula 1-b used in the scheme 4 to obtain 64.0 g (43 %).

_{^{1 H NMR (300MHz, CDCl 3}} ): δ 8.29 (d, 4H), 7.79 (s, 2H), 7.52 ~ 7.44 (m, 20H), 7.02 ~ 6.99 (m, 6H), 6.69 (t, 2H), 6.51 (d, 2H)

MS (MALDI-TOF): m / z 740.29 [M] &lt; + &

< Synthetic example  8> Preparation of the compound represented by the formula (94)

1) Synthesis of Compound Represented by Formula 8-a

A compound represented by the formula 8-a was synthesized by the following Reaction Scheme 24.

[Reaction Scheme 24]

(0.183 mol) of 4-bromofluorene, 20.5 g (0.2196 mol) of aniline, 1.8 g (0.008 mol) of palladium acetate, 12.5 g (0.008 mol) of bicarbonate, sodium tertiary butoxide 35.2 g (0.366 mol) of triethylamine and 500 ml of toluene were placed and refluxed for 24 hours. After completion of the reaction, the mixture was filtered under reduced pressure, and hexane and methylene chloride were separated by column chromatography to obtain 36 g (69%) of the compound represented by the formula 8-a.

2) Synthesis of the compound represented by the formula 8-b

A compound represented by the formula 8-b was synthesized by the following Reaction Scheme 25.

[Reaction Scheme 25]

(81%) of the compound represented by the formula 8-b was synthesized except that the diphenylamine used in the reaction scheme 1 was replaced by the compound represented by the formula 8-a synthesized in the reaction scheme 24 Respectively.

3) Synthesis of the compound represented by the formula 8-c

The compound represented by the formula 8-c was synthesized according to the following Reaction Formula 26.

[Reaction Scheme 26]

Except that the compound represented by the formula 8-b synthesized in the reaction scheme 25 was used instead of the compound represented by the formula 1-a used in the scheme 2, to obtain 29.0 g of the compound represented by the formula 8-c (87%).

4) Synthesis of Compound Represented by Formula 94

The compound represented by the formula (94) was synthesized by the following reaction scheme (27).

[Reaction Scheme 27]

Instead of the compound represented by the formula 1-b used in Scheme 4, a compound represented by the formula 8-c synthesized in Scheme 26 and 3-bromo-N-phenylcarbazole were used instead of the compound represented by the formula 1-c (57%) of the compound represented by the general formula (94) were synthesized in the same manner as in the Synthesis Example.

_{^{1 H NMR (300MHz, CDCl 3}} ): δ 8.55 (d, 1H), 7.94 (d, 1H), 7.87 (. D 1H), 7.58 ~ 7.15 (m, 21H), 7.01 ~ 6.987 (m, 2H), 2H), 1.72 (s, 6H), 6.70 (m, 2H)

MS (MALDI-TOF): m / z 716.32 [M] &lt; + &

< Example  1 to 8> The organic electroluminescent device  Produce

The ITO glass was patterned to have a light emitting area of 2 mm x 2 mm and then cleaned. DNTPD (700Å) of ITO on the organic material so that after a then attached to a vacuum chamber base pressure was 1 × 10 ^-6 torr substrate, NPD (300Å), the compound + Ir (ppy) ₃ prepared according to the present invention ( Alq ₃ (350 Å), LiF (5 Å), and Al (1,000 Å).

[DNTPD]

[NPD]

[Ir (ppy) ₃ ]

[Alq ₃ ]

< Comparative Example  1>

The organic electroluminescent device for the comparative example was fabricated in the same manner except that CBP of the following structural formula was used in place of the compound manufactured by the invention in the device structures of Examples 1 to 8 above.

[CBP]

[Table 2]

From the results of Examples 1 to 8, Comparative Examples 1 and 2, it can be seen that the compound represented by Formula 1 according to the present invention has lower driving voltage and improved luminance as compared with CBP, which is a phosphorescence emitting material , A display element, a display element, an illumination, and the like.

Claims (11)

A spiro compound represented by any one of the following formulas (1-1) to (1-27):
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

[Chemical Formula 1-9]

[Chemical Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

[Chemical Formula 1-14]

[Chemical Formula 1-15]

[Chemical Formula 1-16]

[Formula 1-17]

[Chemical Formula 1-18]

[Chemical Formula 1-19]

[Chemical Formula 1-20]

[Formula 1-21]

[Formula 1-22]

[Formula 1-23]

[Formula 1-24]

[Chemical Formula 1-25]

[Chemical Formula 1-26]

[Chemical Formula 1-27]

In the above formulas 1-1 to 1-27,
A is C, L is an ethylene or ethenylene group having 2 carbon atoms, Z ₁ is NR ₅ or S, Z ₂ and Z ₃ are each independently NR ₅ , S or O, and X ₁ to X ₄ are Independently C or N,
R ₁ to R ₅ are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms, and adjacent groups are bonded to each other to form a substituted or unsubstituted aliphatic , Aromatic, heteroaliphatic or heteroaromatic rings. The method according to claim 1,
Wherein R ₁ to R ₅ are, except hydrogen, are each independently a heavy hydrogen, heteroaryl, C 1 -C 40 alkyl group, having 1 to 40 carbon atoms in the alkyl group, a C6-C40 aryl group, having 3 to 40 carbon atoms of the amino group , An aryl group having 6 to 40 carbon atoms, and a heteroaryl group having 3 to 40 carbon atoms. delete The method according to claim 1,
Wherein the spiro compound is any one of compounds represented by the following formulas (2) to (491)
[Table 1]

Anode;
Cathode; And
And a layer containing the spiro compound according to claim 1, interposed between the anode and the cathode. 6. The method of claim 5,
Wherein the layer containing the spiro compound is a light emitting layer between the anode and the cathode. The method according to claim 6,
And at least one layer selected from the group consisting of a hole injecting layer, a hole transporting layer, an electron blocking layer, a hole blocking layer, an electron transporting layer and an electron injecting layer is further interposed between the anode and the cathode. The method according to claim 6,
Wherein the thickness of the light emitting layer is 0.5 nm to 500 nm. The method according to claim 6,
Wherein the light emitting layer further comprises Ir (ppy) ₃ of the following structural formula:
[Ir (ppy) ₃ ]

8. The method of claim 7,
Wherein at least one layer selected from the group consisting of 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 molecular deposition method or a solution process. 6. The method of claim 5,
Wherein the organic electroluminescent device is used in a display device, a display device, or a device for monochromatic or white illumination.

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