KR20150136713A - Aromatic sulfone derivatives and Organic electroluminescent device comprising same - Google Patents

Abstract

The present invention relates to an organic material having an aromatic sulfonate derivative form and an organic electroluminescent device using the same. The organic electroluminescent device of the present invention can obtain short-wavelength light emitting in high efficiency and has improved lifespan properties.

Description

TECHNICAL FIELD The present invention relates to an aromatic sulfone derivative and an organic electroluminescent device comprising the same.

The present invention relates to a novel aromatic sulfonic derivative excellent in light emission efficiency and thermal stability, and an organic electroluminescent device exhibiting excellent efficiency characteristics by incorporating it into one or more organic layers.

Organic semiconductors are being developed for many types of electronic equipment applications. The organic electroluminescent device has a simple structure compared to other flat panel display devices such as a liquid crystal display (LCD), a plasma display panel (PDP), and a field emission display (FED) And has a high response speed and a low driving voltage, so that it is being actively developed to be used as a light source for a flat panel display such as a wall-mounted TV or a backlight of a display, a lighting, and a billboard.

In the organic electroluminescent device, when a direct current voltage is applied, holes injected from the anode recombine with electrons injected from the cathode to form an exciton, which is an electron-hole pair, and the energy of the exciton is transferred to the light emitting material .

In order to increase the efficiency and stability of the organic electroluminescent device, a low-voltage-driven organic electroluminescent device in which a laminated organic thin film is formed between two opposite electrodes by CW Tang of Eastman Kodak Co. (CW Tang, SA Vanslyke, Applied Physics Letters , Vol. 51, p. 913, 1987), studies on organic materials for multilayer thin film organic electroluminescent devices have been actively conducted.

In general, an organic electroluminescent device has a structure including a cathode (electron injection electrode), an anode (hole injection electrode), and at least one organic layer between the two electrodes. In this case, the organic electroluminescent device may include, as an organic layer, a hole injection layer (HIL), a hole transport layer (HTL), an electron transport layer (ETL), or an electron transport layer And may further include an electron injection layer (EIL), and may further include an electron blocking layer (EBL) or a hole blocking layer (HBL) on the light emitting property of the light emitting layer. The organic electroluminescent device including all of these organic layers has a stacked structure in the order of anode / hole injecting layer / hole transporting layer / electron blocking layer / light emitting layer / hole blocking layer / electron transporting layer / electron injecting layer / cathode.

When an electric field is applied to the organic electroluminescent device having such a structure, the holes injected from the anode and the electrons injected from the cathode are recombined to form an electron-hole pair exciton, Light is emitted as it is transmitted. The lifetime of the stacked organic electroluminescent device is related to the electrochemical stability and the thin film stability of the material.

For example, when a light emitting material having poor heat stability is used, crystallization of the material occurs at a high temperature or at a driving temperature, thereby shortening the lifetime of the device. An anthracene derivative has been used for a typical organic electroluminescence device as a light emitting layer, a hole transporting layer, an electron transporting layer, and the like. As a typical example, 9,10-di (naphthalen-2-yl) anthracene is used as a host material for a light emitting layer. However, it is easily crystallized as the temperature of the device rises, shortening the lifetime of the device. In order to overcome such shortcomings, various types of materials have been developed. However, until now, characteristics such as required luminous efficiency, driving stability, and life span are not sufficiently satisfied.

Accordingly, the inventors of the present invention have found that an aromatic sulfonium derivative can solve the above problems while studying a novel compound having excellent luminescent efficiency and thermal stability, thereby completing the present invention.

An object of the present invention is to provide an aromatic sulfonium derivative which is excellent in thermal stability and can emit light of a short purple-blue short wavelength with high efficiency, and an organic light emitting device including the aromatic sulfonium derivative in the organic layer.

In order to solve the above-mentioned problems, the present invention provides a compound represented by the following formula (1):

[Chemical Formula 1]

Wherein X is O or S,

L and M each independently represents a single bond, a substituted or unsubstituted C _{6 -50} arylene group, or a substituted or unsubstituted heteroarylene group having 5 to 50 nucleus atoms,

R ₁ to R ₅ may be one or more and are each independently selected from the group consisting of hydrogen, halogen, cyano, nitro, hydroxy, thio, phosphoryl, phosphinyl, carbonyl, amino, substituted or unsubstituted C ₁ to C ₅₀ alkyl, substituted or unsubstituted C _{2 -50} alkenyl, substituted or unsubstituted C _{2 -50} alkenyl, substituted or unsubstituted C _{3 -50} cycloalkyl , substituted or unsubstituted C _{5 - 50} cycloalkenyl, substituted or unsubstituted C _{5 -50} cyclo-alkynyl, substituted or unsubstituted C _{6 -50} aryl group or the number of nuclear atoms unsubstituted or substituted 5- to 50 heteroaryl, substituted or unsubstituted C _{5 -50} aryl-amino or a substituted or unsubstituted C _{1 -50} alkyl,

Optionally wherein L and M are unsubstituted or substituted by C _{1 -6} alkyl, amino, thio, phosphoryl, phosphine sulfinyl, carbonyl, silyl, borane yl, C _{1 -50} alkyl, C _{2 -50} alkenyl , C _{2 -50} alkynyl, C _1-50 alkoxy, C _{3 -50} cycloalkyl, C _{6 -50} aryl, nuclear atoms may be substituted by from 5 to 50 heteroaryl or C _{7 -50} aralkyl,

Optionally wherein R ₁ to R ₅ is C _{1 -6} alkyl substituted or unsubstituted amino, thio, phosphoryl, phosphine sulfinyl, carbonyl, silyl, borane yl, C _{1 -50} alkyl, C _{2 -50} alkenyl, C _{2 -50} alkynyl, C _{1 -50} alkyl, which may be substituted with C _{3 -50} cycloalkyl, C _{6 -50} aryl, nuclear atoms of 5 to 50 heteroaryl or C _{7 -50} aralkyl .

In the present invention, L and M each independently represent a single bond or may be a substituted or unsubstituted phenylene group.

That is, the compound of formula (1) may be a compound represented by any of the following formulas (1a) to (1d).

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

In the above general formulas (1a) to (1d), the definitions of R ₁ to R ₅ are as described above.

Hereinafter, the present invention will be described in detail.

The compound represented by the general formula (1) according to the present invention is a compound in which a phenylcarbazole group, a dibenzofuranyl group or a dibenzothiophenyl group is bonded or substituted, respectively, as aromatic groups in which a sulfone group is located at the center and the right and left sides of the above- It is characterized by its molecular design with asymmetric molecular structure.

As described above, due to the sulfone group located at the center, the solubility of the compound can be improved and the intramolecular bent structure can be formed. Therefore, the exciton is limited and the HOMO-LUMO energy level is lowered, You can give. In addition, the bending structure of the sulfone group can improve the thermal stability and the surface property by controlling the influence between the molecules.

Further, the compound represented by the formula (1) according to the present invention has an asymmetric molecular structure in which aromatic groups are respectively bonded or substituted to the right and left sides of the sulfonic group, and therefore the crystallization is difficult, And thus the thermal stability can also be improved.

In the present invention, it has been confirmed through experiments that the bending structure of the sulfone group can improve the thermal stability and surface properties by controlling the influence of the molecules. In addition, it has been confirmed through experiments that these characteristics of the sulfone group show higher luminous efficiency and luminance when a substance containing a sulfone group is applied to the device. Further, it has been confirmed through experiments that the asymmetric molecular structure of the present invention is difficult to crystallize, thereby preventing crystallization during film formation and thus improving thermal stability.

On the other hand, the amorphous thin film is formed into a crystalline form due to the temperature (usually less than 100 캜) which is raised at the time of driving the device, and the lifetime is drastically decreased. The thin film stability means the uniformity of the film and the interface stability with the other layer materials, and affects the driving stability (stable current density, etc.).

Heat resistance in OLED materials is related to melting point and glass transition temperature. This heat resistance is directly related to molecular firmness and molecular weight. That is, the higher the molecular weight, the better the heat resistance. Also, when a substituent capable of free rotation at a similar molecular weight or a molecule containing a linear aliphatic hydrocarbon substituent is introduced, the heat resistance tends to decrease. Therefore, the compound represented by the formula (1) according to the present invention is designed to minimize such deterioration in heat resistance.

The compound represented by the formula (1) according to the present invention has an advantage that the substituent for solubility enhancement can be introduced at a position irrelevant to the conjugation rather than directly connected to the core exhibiting light emission or OLED characteristics. When the substituents for solubility enhancement are directly connected to the aromatic core, OLED characteristics are generally poor. That is, when the substituents R ₁ to R ₅ in the above formula (1) are appropriately selected, the solubility of the compound represented by the formula (1) can be increased to improve the film proccesibility. For example, the solubility can be improved by controlling the length of an aliphatic substituent, and thus it can be applied to a wet film formation process such as ink jet or spin coating.

When the substituents R ₁ to R ₅ are appropriately selected, amorphous characteristics can be exerted more effectively, and breakage of the device due to crystallization caused by Joule heat generated when the organic light emitting device operates can be prevented have.

Representative examples of the compound of Formula 1 include the following compounds 1 to 24.

(1),

(2),

(One),

(2),

(3),

(4),

(3),

(4),

(5),

(6),

(5),

(6),

(7),

(8),

(7),

(8),

(9),

(10),

(9),

(10),

(11),

(12),

(11),

(12),

(13),

(13),

(14),

(14),

(15),

(15),

(16),

(16),

(17),

(18),

(17),

(18),

(19),

(20),

(19),

(20),

(21),

(22),

(21),

(22),

(23), 및

(24).

(23), and

(24).

The compound represented by Formula 1 may be applied to not only the light emitting layer but also the hole injecting layer, the hole transporting layer, the electron transporting layer, and the electron injecting layer depending on the type of the substituent to be introduced. A number of compounds which can act as a buffer between a hole injection, a hole transport, a hole blocking, a luminescence, an electron transport, an electron injection, and an anode and a hole injection layer are well known and are generally substituted or unsubstituted aromatic or hetero And an aromatic group.

The organic material capable of injecting holes facilitates the injection of holes from the anode, and has an appropriate ionization potential for injecting holes from the anode, a high interfacial adhesion to the anode, and a nonabsorbing property in the visible region , And examples of the substituent capable of injecting holes include metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene, quinacridone-based organic materials, perylene ) Organic materials, anthraquinone, and the like, but are not limited thereto.

Organic materials capable of transferring holes may have high hole mobility and preferably have a high LUMO level for electron blocking. For example, substituents capable of transferring holes include arylamine-based organic materials and the like. The present invention is not limited thereto. More specific examples include triarylamine derivatives, amines having a bulky aromatic group, starburst aromatic amines, amines having spirofluorene, cross-linked amines (e.g., crosslinked amine compounds.

The organic substance capable of electron transferring is a compound having an electron withdrawing group, and examples of the substituent capable of electron transfer include a functional group which attracts electrons by resonance such as a cyano group, oxadiazole or triazole Compounds, and the like, but are not limited thereto.

Also, as an example of the present invention, there is provided a process for producing a compound represented by the above formula (1a) as shown in the following reaction scheme 1. In the following Reaction Scheme 1, the definitions of R ₁ to R ₅ are as described above.

[Reaction Scheme 1]

Step 1 is a step of reacting a sulfone compound represented by Formula 1-1 with a phenylcarbazole compound represented by Formula 1-4 to prepare a compound represented by Formula 1-2. In the above step, it is preferable to first react the compound of Formula 1-4 with n-butyllithium and sulfur dioxide to obtain a lithium salt, and reacting the lithium salt with the compound of Formula 1-1 to obtain a compound of Formula 1-2. As the reaction solvent, tetrahydrofuran may be used.

Step 2 is a step of reacting a compound represented by Formula 1-2 with a compound represented by Formula 1-5 to prepare a compound represented by Formula 1a. In the above step, it is preferable to add palladium dichloride to the compounds of formulas 1-2, compounds of formulas 1-5 and potassium carbonate. As the reaction solvent, water, acetone or a mixed solvent thereof may be used.

Also, as an example of the present invention, there is provided a process for producing a compound represented by the above formula (1b) In the following Reaction Scheme 2, the definitions of R ₁ to R ₅ are as described above.

[Reaction Scheme 2]

In step 1, sodium sulfite and sodium hydrogencarbonate are added to a sulfonic compound represented by the formula (2-1) and reacted to prepare a compound represented by the formula (2-2). Water may be used as a reaction solvent.

Step 2 is a step of reacting a compound represented by Formula 2-2 with a phenylcarbazole compound represented by Formula 2-4 to prepare a compound represented by Formula 2-3. In the above step, it is preferable that the compound of the formula 2-2, the compound of the formula 2-4, and dimethylsulfoxide are reacted by adding copper acetic acid and potassium carbonate.

Step 3 is a step of reacting a compound represented by Formula 2-3 with a compound represented by Formula 1-5 to prepare a compound represented by Formula 1b. In the above step, it is preferable to add an aqueous solution of potassium carbonate and tetrakis (triphenylphosphine) palladium to the compound of Formula 2-3 and the compound of Formula 1-5. As the reaction solvent, tetrahydrofuran, water or a mixed solvent thereof may be used.

Also, as an example of the present invention, there is provided a process for producing a compound represented by the above formula (1c) as shown in Reaction Scheme 3 below. In the following Reaction Scheme 3, the definitions of R ₁ to R ₅ are as described above.

[Reaction Scheme 3]

Step 1 is a step of reacting a sulfone compound represented by formula (1-1) with a phenylcarbazole compound represented by formula (3-1) to prepare a compound represented by formula (3-2). In the above step, the compound of formula (3-1) is first reacted with n-butyl lithium and sulfur dioxide to obtain a lithium salt, and the lithium salt is reacted with the compound of formula (1-1) to obtain a compound of formula (3-2). As the reaction solvent, tetrahydrofuran may be used.

Step 2 is a step of reacting a compound represented by formula (3-2) with a compound represented by formula (1-5) to prepare a compound represented by formula (1c). In the above step, it is preferable to add palladium dichloride to the compound of Formula 3-2, the compound of Formula 1-5, and potassium carbonate to carry out the reaction. As the reaction solvent, water, acetone or a mixed solvent thereof may be used.

Further, the present invention provides a luminescent host or a dopant-containing composition for an organic electroluminescence device containing a compound represented by the formula (1), preferably any one of the above-mentioned compounds (1) to (24).

The present invention also provides an organic electroluminescence device comprising a compound represented by the formula (1), preferably any one of the compounds (1) to (24) in at least one organic layer. At this time, the organic layer essentially includes a light emitting layer and may include a hole injecting layer, a hole transporting layer, an electron injecting layer, an electron transporting layer, or a laminate thereof in addition to the light emitting layer.

The organic electroluminescent device of the present invention comprises a single layer or a multilayer organic layer containing a positive electrode, a negative electrode and at least one light emitting layer between the two electrodes, wherein at least one layer of the organic layer is a compound represented by the general formula (1) Preferably one or more of the compounds of the above-mentioned compounds 1 to 24. For example, a multilayer organic electroluminescent device is laminated from the bottom in a multilayer structure of a substrate, an anode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer and a cathode.

The substrate, the anode, and the cathode of the organic electroluminescent device according to the present invention are made of a material used in a conventional organic electroluminescent device, and any one of the hole injecting layer, the hole transporting layer, the light emitting layer, the electron transporting layer, 1, preferably any one or more of the above-mentioned compounds 1 to 24, or a mixture thereof.

Particularly, in the case of the light emitting layer, the compound represented by the formula (1) of the present invention, preferably the compounds (1) to (24) may be used alone or in combination of two or more, or a light emitting host material or a dopant ) Materials and may be used with other known light emitting dopant materials or host materials. When the compound represented by the formula (1), preferably the compound (1) to (24) is used as a single luminescent material or a host material, it may be added in an amount of 100 to 80% by weight relative to the light emitting layer. May be added in an amount of 0.01 to 20% by weight relative to the light emitting layer. Specific examples of the light emitting material, the host material or the dopant material which can be used in the light emitting layer together with the compound represented by the formula (1), preferably the compound (1) to the above-mentioned compound (24) include anthracene, naphthalene, phenanthrene, But are not limited to, naphthalene, naphthalene, naphthalene, naphthalene, naphthalene, naphthalene, naphthalene, naphthalene, There may be mentioned a metal complex such as chalcogenide, bisbenzoxazoline, bisstearyl, pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, benzoquinoline metal complex, imine, diphenylethylene, vinyl anthracene, diaminocarbazole, , Polymethine, melocyanine, imidazole chelated oxinoid compounds, quinacridone, rubrene, fluorescent dyes, and mixtures thereof. It is not. When a dopant material is selected, it is preferable to select a dopant having a bandgap equal to or less than the bandgap of the host material while having high efficiency of fluorescence or phosphorescence.

Each of the layers constituting the organic electroluminescent device may be formed by any of a conventional film forming method such as vacuum deposition, sputtering, plasma or ion plating, or a wet film forming method such as spin coating, immersion coating, . If the film thickness is too large, a high applied voltage is required to obtain a constant light output, which leads to deterioration of efficiency. When the film thickness is too thin, pin holes are generated and an electric field is applied A sufficient light emission luminance can not be obtained. A typical film thickness is preferably in the range of 5 nm to 10 mu m, more preferably in the range of 50 nm to 400 nm.

The organic electroluminescent device using the aromatic sulfonium derivative according to the present invention as an organic layer can achieve light emission of a short wavelength with high efficiency and improved thermal stability and exhibits improved lifetime characteristics.

Hereinafter, the present invention will be described in more detail with reference to Examples. These embodiments are only for describing the present invention more specifically, and the scope of the present invention is not limited by these examples.

Example  1: Preparation of compound 1

Compound 1 was prepared by the following reaction formula.

1) Synthesis of Substituents 1-4

Substituents 1-4 were prepared by the following synthetic method.

1-3 (5 g), palladium (0) diacetate (0.1 g), tri-tert-butylphosphine (0.3 g) and toluene (100 ml) were placed in a 250 ml three- Lt; / RTI > Potassium carbonate (7.2 g) and 3-bromocarbazole (6.3 g) were added to the mixed solution, followed by stirring at 80 ° C for 6 hours. After addition of water, the reaction mixture was extracted with ethyl acetate, the water was removed, and the resulting product was subjected to column separation using hexane to obtain 1.9 g of the Substituent 1-4.

2) Synthesis of intermediate 1-2

Was dissolved in 9- (3-bromo) phenylcarbazole (3.0 g) and tetrahydrofuran (50 ml) in a 250 ml three-necked round bottom flask, and the mixture was stirred at -78 ° C for 30 minutes. N-butyl lithium (4.1 ml) of 2.5 molar concentration was added to the mixed solution at -5 ° C. Sulfur dioxide diluted in tetrahydrofuran (20 ml) was slowly added at a very low temperature of -50 ° C and stirred for 15 minutes. The reaction temperature was gradually raised to room temperature, stirred for 1 hour, and the solvent was removed through a rotary evaporator, followed by vacuum drying. The dried lithium salt was mixed with the tetrahydrofuran solvent and the sulphuryl chloride solution was added at 0 < 0 > C. The reaction solution was stirred at room temperature for 1 hour and then all of the solvent was dried to obtain 3.5 g of the title intermediate 1-2.

3) Synthesis of Compound 1

2-dibenzofuran boronic acid (2.0 g), intermediate 1-2 (3.0 g) and potassium carbonate (2.6 g) were added to a 250 ml three-necked round bottom flask and nitrogen was blown at 0 ° C. To the reaction mixture was added a mixed solvent of acetone 3: water 1 (50 ml) and palladium dichloride (0.03 g), and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was dried under reduced pressure, and the reaction solution was separated by layer separation, and the organic layer was washed twice with water. The obtained organic layer was dried with magnesium sulfate and concentrated under reduced pressure to remove the solvent.

The material formed by concentration was subjected to column separation using dichloromethane and hexane to obtain 2.6 g of the title compound 1. < 1 >

(1H, d), 7.56 (1H, t), 7.61 (3H, m), 7.67 (1H, d), 7.88 ( 2H, d), 8.16 (1H, d), 8.27 (1H, s), 8.44 (1H, s) (200MHz 1 H-NMR chemical shift (δ), CDCl 3)

Example  2: Preparation of compound 5

Compound 5 was prepared by the following reaction scheme.

1) Synthesis of Substituent 2-4

Substituent 2-4 was prepared by the following synthesis method.

The intermediate 1-4 (3.0 g) was dissolved in purified tetrahydrofuran (60 ml) into a 100 ml three-necked round bottom flask, and stirred at -78 ° C for 30 minutes in an argon atmosphere. N-butyllithium (5.6 ml) of 2 molar concentration was slowly added dropwise to the mixed solution in the same atmosphere, followed by stirring for 1 hour. Triethylborate (2.3 ml) was slowly added dropwise to the reaction solution at the same temperature, and the mixture was stirred for 2 hours and then at room temperature for 12 hours. After completion of the reaction, water was added, and the mixture was stirred for 15 minutes. To the solution was added hydrochloric acid to pH 5 and stirred for 4 hours. After removing water from the solution obtained by extracting with ether, the resulting material was vacuum dried to obtain 2.2 g of the subject substituent 2-4.

2) Synthesis of intermediate 2-2

A thermometer was placed in a 500 ml three-neck round bottom flask, and sodium sulfite (33.8 g) and sodium hydrogencarbonate (22.9 g) were added. Distilled water (300 ml) was added and the mixture was heated to 70 to 80 ° C. The heat source was turned off and the mixture was stirred for 1 hour while adding a small amount of the compound 2-1 (20 ml). The mixed solution was agitated at 70 to 80 ° C for 3 hours, then, the heat source was removed, and the solution was slowly cooled to room temperature. The precipitate was washed with ethanol, filtered and the filtrate was dried under reduced pressure. After dissolving the dried material with high purity ethanol, the solution portion was dried under reduced pressure to obtain 39 g of Intermediate 2-2 which was a white solid in a salt form.

3) Synthesis of intermediate 2-3

Intermediate 2-2 (10 g), Substituent 2-4 (6.9 g) and dimethyl sulfoxide (200 ml) were added to a 500 ml three-necked round bottom flask and stirred for 15 minutes. Copper acetic acid (4.8 g) and potassium carbonate (6.6 g) were added in succession, followed by addition of 4 Å molecular filter (200 g) and stirring at room temperature for 16 hours. The reaction solution was filtered through a tightly packed celite layer, and an aqueous ammonium chloride solution was added thereto, followed by layer separation with ethyl acetate. The obtained organic layer was dried with magnesium sulfate and concentrated under reduced pressure to remove the solvent. The material formed by concentration was subjected to column separation using dichloromethane and hexane to obtain 7.3 g of the title intermediate 2-3.

4) Synthesis of Compound 5

Intermediate 2-3 (4 g) and Substituent 1-5 (2.1 g) were added to a 100 ml three-necked round bottom flask, and tetrahydrofuran (80 ml) was added thereto, followed by argon gas bubbling. Potassium carbonate aqueous solution (16 ml) diluted to 1 mol and tetrakis (triphenylphosphine) palladium (0) (0.18 g) were added to the reaction solution and refluxed for 12 hours. The reaction was terminated and extracted with dimethyl chloride and distilled water. The organic layer was separated, and the organic layer was dried over magnesium sulfate and concentrated under reduced pressure to remove the solvent. The dried material was dissolved in dichloromethane, filtered through tightly packed silica and activated carbon pad, and concentrated under reduced pressure. The material formed by concentration was subjected to column separation using dichloromethane and hexane to obtain 3.2 g of the title compound 5.

(2H, m), 7.31 (1H, t), 7.50 (1H, d), 7.63 (IH, d), 7.96 (IH, d), 8.01 (IH, d), 8.16 (IH, s), 8.23 1H, d) (200 MHz ¹ H-NMR chemical shift (?), CDCl ₃ )

Example  3: Preparation of compound 17

Compound 17 was prepared by the following reaction scheme.

1) Synthesis of Substituent 3-1

Substituent 3-1 was prepared by the following synthesis method.

Intermediate 1-5 (3g), 1-bromo-3-iodobenzene (3.8g), tetrahydrofuran (60ml), potassium carbonate (3g) and water (11ml) were added to a 100ml three- Respectively. Tetrakis (triphenylphosphine) palladium (0) (0.13 g) was added to the mixture, and the mixture was heated to 80 ° C. The reaction solution was layered to remove water, and the organic layer was washed twice with water. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to remove the solvent. The material produced by concentration was subjected to column separation using hexane to obtain 2.6 g of the title substituent 3-1.

2) Synthesis of intermediate 3-2

The title intermediate 3-2 was obtained in the same manner as in the synthesis of Intermediate 1-2, except that Substituent 3-1 was used instead of Substituent 1-4.

3) Synthesis of Compound 17

Compound 17 was obtained in the same manner as in the synthesis of Compound 1 except that Intermediate 3-2 was used instead of Intermediate 1-2.

D), 7.56 (1H, d), 7.64 (4H, m), 7.68 (2H, (IH, d), 7.76 (2H, d), 7.94 (IH, d), 8.00 (IH, s), 8.05 ^{1H, s) (200MHz 1 H} -NMR chemical shift (δ), CDCl 3)

Example  4 to 24: Preparation of compounds 2 to 4, compounds 6 to 16 and compounds 18 to 24

The following processes were carried out in the same manner as in the above Examples 1 to 3 except that the substituents and the intermediates were appropriately changed to obtain the following compounds 2 to 4, compounds 6 to 16 and compounds 18 to 24. NMR data of each example compound is shown below.

Compound 2

(2H, d), 7.56 (1H, t), 7.60 (1H, t), 7.09 (4H, m), 7.18 (3H, m), 7.89 ( 2H, m), 8.02 (1H, d), 8.17 (1H, d), 8.37 (1H, s) (200MHz 1 H-NMR chemical shift (δ), CDCl 3)

Compound 3

D), 7.88 (1H, d), 7.98 (2H, d), 7.08 (2H, t), 7.20 (2H, m), 7.98 ( 1H, d), 8.09 (1H, d), 8.16 (1H, d), 8.28 (1H, s), 8.70 (1H, s) (200MHz 1 H-NMR chemical shift (δ ), CDCl ₃₎

Compound 4

(1H, d), 7.06 (2H, t), 7.16 (2H, t), 7.29 (1H, d), 7.89 ( 2H, m), 7.93 (1H, d), 8.13 (1H, d), 8.18 (1H, d), 8.29 (1H, s) (200MHz 1 H-NMR chemical shift (δ ), CDCl ₃₎

Compound 6

(2H, m), 7.72 (1H, d), 7.72 (1H, d), 7.27 (2H, d), 7.93 ( 1H, d), 8.04 (1H, d), 8.22 (1H, d), 8.45 (1H, s), 8.48 (1H, s), 8.49 (1H, d) (200MHz 1 H-NMR chemical shift (δ) , CDCl 3)

Compound 7

(2H, t), 7.41 (2H, m), 7.63 (1H, t), 7.63 (1H, d), 7.97 ( 2H, m), 8.06 (1H, d), 8.11 (3H, m), 8.33 (1H, s), 8.36 (1H, s) (200MHz 1 H-NMR chemical shift (δ ), CDCl ₃₎

Compound 8

D), 7.73 (2H, d), 7.91 (2H, t), 7.17 (2H, t), 7.26 (IH, d), 7.96 (2H, m), 8.00 (IH, d), 8.04 (IH, d), 8.34 1H, d) (200 MHz ¹ H-NMR chemical shift (?), CDCl ₃ )

Compound 9

D), 7.66 (2H, d), 7.66 (2H, d), 7.70 (2H, (3H, m), 7.85 ( 2H, d), 7.96 (1H, d), 7.98 (1H, s), 8.14 (2H, d), 8.44 (1H, s) (200MHz 1 H-NMR chemical shift (δ ), CDCl ₃₎

Compound 10

(2H, t), 7.24 (2H, t), 7.31 (1H, t), 7.41 (1H, t), 7.48 (1H, d), 7.72 ( 2H, d), 7.83 (1H, d), 7.87 (2H, d), 8.02 (1H, s), 8.20 (2H, d), 8.24 (1H, d) (200MHz 1 H-NMR chemical shift (δ) , CDCl 3)

Compound 11

(1H, d), 7.15 (2H, t), 7.21 (2H, t), 7.40 (2H, m), 7.98 ( 1H, s), 8.05 (1H, d), 8.14 (3H, m), 8.71 (1H, s) (200MHz 1 H-NMR chemical shift (δ), CDCl 3)

Compound 12

,

,

(2H, m), 7.69 (1H, d), 7.73 (2H, t) (2H, d), 7.86 ( 2H, d), 7.91 (1H, d), 7.94 (2H, d), 8.02 (1H, s), 8.14 (2H, d), 8.45 (1H, d) (200MHz 1 H-NMR chemical shift (δ) , CDCl 3)

Compound 13

(1H, d), 7.16 (2H, t), 7.25 (3H, m), 7.31 (1H, t), 7.50 (2H, d), 7.80 (2H, d), 7.97 (1H, s), 8.05 ^{1H, s) (200MHz 1 H} -NMR chemical shift (δ), CDCl 3)

Compound 14

(1H, d), 7.16 (2H, t), 7.24 (2H, t), 7.32 (1H, t), 7.42 (1H, d), 7.79 ( 2H, d), 7.96 (1H, s), 8.05 (1H, d), 8.14 (2H, d), 8.25 (1H, d), 8.54 (1H, s) (200MHz 1 H-NMR chemical shift (δ) , CDCl 3)

Compound 15

D), 7.80 (2H, d), 7.92 (2H, d), 7.15 (2H, t), 7.24 (1H, d), 7.95 (1H, s), 7.98 (1H, d), 8.04 2H, s) (200 MHz ¹ H-NMR chemical shift (?), CDCl ₃ )

Compound 16

D), 7.77 (1H, d), 7.82 (2H, t), 7.16 (2H, t), 7.26 (2H, d), 7.94 ( 1H, d), 7.98 (1H, s), 8.01 (3H, m), 8.17 (2H, d), 8.22 (1H, d), 8.55 (1H, s) (200MHz 1 H-NMR chemical shift (δ) , CDCl 3)

Compound 18

(1H, d), 7.05 (1H, t), 7.18 (2H, t), 7.25 (2H, d), 7.83 ( 1H, d), 7.97 (1H, d), 8.17 (1H, s), 8.20 (1H, d), 8.25 (1H, d), 8.65 (1H, s) (200MHz 1 H-NMR chemical shift (δ) , CDCl 3)

Compound 19

(2H, d), 7.72 (2H, d), 7.82 (2H, t), 7.28 (2H, d), 7.98 (1H, s), 8.01 (1H, s), 8.05 ^{1H, s) (200MHz 1 H} -NMR chemical shift (δ), CDCl 3)

Compound 20

(2H, t), 7.37 (2H, m), 7.57 (3H, m), 7.63 (2H, d), 7.88 ( 1H, d), 8.05 (2H, d), 8.07 (1H, s), 8.13 (1H, d), 8.39 (1H, d), 8.55 (1H, s) (200MHz 1 H-NMR chemical shift (δ) , CDCl 3)

Compound 21

(2H, d), 7.74 (2H, d), 7.72 (2H, t), 7.249 (1H, t), 7.32 (2H, m), 7.97 (1H, d), 8.01 (1H, s), 8.03 (1H, d), 8.06 1H, s), 8.48 (1H , s) (200MHz 1 H-NMR chemical shift (δ), CDCl 3)

Compound 22

D), 7.59 (1H, d), 7.16 (1H, t), 7.23 (1H, t), 7.26 (1H, s), 8.07 (2H, t), 8.37 (1H, d), 7.76 1H, s), 8.43 (1H, s), 8.62 (1H, d) (200 MHz ¹ H-NMR chemical shift (?), CDCl ₃ )

Compound 23

D), 7.83 (1H, d), 7.92 (1H, d), 7.16 (2H, t), 7.25 (IH, d), 7.94 (4H, m), 8.12 (IH, d), 8.16 (IH, d), 8.26 ^{1H, s) (200MHz 1 H} -NMR chemical shift (δ), CDCl 3)

Compound 24

(2H, d), 7.75 (1H, d), 7.09 (2H, t), 7.13 (1H, d), 7.97 ( 4H, m), 8.02 (2H, t), 8.15 (1H, d), 8.54 (1H, s) (200MHz 1 H-NMR chemical shift (δ), CDCl 3)

Experimental Example

Experimental Example  One: Example  Preparation of organic electroluminescent device using compound 1

An ITO transparent electrode having a thickness of 100 nm was formed on a glass substrate having a size of 40 mm × 40 mm × 0.7 m, ultrasonically cleaned in a distillation shoe in which detergent was dissolved for 10 minutes, and repeatedly washed twice in distilled water for 10 minutes Respectively.

After the distilled water was washed, solvents such as isopropyl alcohol, acetone and methanol were sequentially ultrasonically washed and dried. After the wet refining, the substrate was dry-cleaned using oxygen / argon plasma, and then a glass substrate having a transparent electrode line was mounted on a substrate holder of a vacuum evaporation apparatus. On the surface of the ITO side on which the transparent electrode line was formed, DNTPD of a compound (N ¹ , N ^{1 '} - (biphenyl-4,4'-diyl) bis (N ¹ -phenyl-N ⁴ , N ⁴ -dim-tolylbenzene- Lt; RTI ID = 0.0 > vacuum / vacuum < / RTI >

(A)

(N ⁴ , N ^{4 '} -di (naphthalen-1-yl) -N ⁴ , N ^4' -diphenylbiphenyl-4,4 '-diamine was formed by vacuum deposition at 20 nm.

[Chemical Formula B]

(4- (4aH-carbazol-9 (4bH, 8aH, 9aH) -yl) phenyl, which is capable of preventing electrons from easily flowing into the hole transport layer on the layer of the compound of Formula (B) (9H-carbazol-9-yl) benzenamine) was vacuum-deposited to a thickness of 10 nm.

≪ RTI ID = 0.0 &

A compound represented by the following formula (D) as a blue dopant was mixed and vapor-deposited at a concentration of 5% together with the compound 1 of Example 1 as a light emitting host on the layer of the compound of the formula (C) to form a light emitting layer of 30 nm in thickness.

[Chemical Formula D]

A compound of the following formula (E) serving as an electron injecting and transporting layer was vacuum deposited on the light emitting layer to a thickness of 30 nm.

(E)

Lithium fluoride (LiF) with a thickness of 0.7 nm and aluminum with a thickness of 120 nm were sequentially deposited on the electron injection and transport layer to form a cathode. The resulting organic light emitting device was sagged at a voltage of 6 V, resulting in a current density of 0.063 mA / cm 2. At this time, the brightness of 24.27 cd / m 2 corresponding to x = 0.141 and y = 0.212 on the basis of 1931 CIE color coordinates A spectrum close to pure blue was observed and the efficiency was 38.5 cd / A.

Experimental Example  2: Preparation of Organic Electroluminescent Device Using Compound 2

An organic electroluminescent device was fabricated in the same manner as in Experimental Example 1, except that the compound 2 of Example 4 of the present invention was used as a luminescent host material instead of the compound of Example 1 of the present invention as a luminescent host material.

The organic EL device thus fabricated was measured at a voltage of 6 V and found to have a current density of 0.114 mA / cm 2. At this time, the luminance of 38.4 cd / m 2 corresponding to x = 0.143 and y = 0.223 on the basis of 1931 CIE color coordinates A spectrum close to pure blue was observed and the efficiency was 33.7 cd / A.

compare Experimental Example  One

An organic electroluminescent device was prepared in the same manner as in Experimental Example 1, except that the compound represented by the following formula (F) was used as a luminescent host material instead of the compound 1 of the present invention as a host material.

[Chemical Formula F]

The organic electroluminescent device manufactured as described above was measured at a voltage of 6 V and a current density of 0.15 mA / cm 2 was formed. The current density was 29 cd / m 2 corresponding to x = 0.146 and y = 0.239 on the basis of 1931 CIE color coordinates. A spectrum close to pure blue was observed and the efficiency was 19.3 cd / A.

Claims (7)

A compound represented by the following formula (1):
[Chemical Formula 1]

Wherein X is O or S,
L and M each independently represents a single bond, a substituted or unsubstituted C _{6 -50} arylene group, or a substituted or unsubstituted heteroarylene group having 5 to 50 nucleus atoms,
R ₁ to R ₅ may be one or more and are each independently selected from the group consisting of hydrogen, halogen, cyano, nitro, hydroxy, thio, phosphoryl, phosphinyl, carbonyl, amino, substituted or unsubstituted C ₁ to C ₅₀ alkyl, substituted or unsubstituted C _{2 -50} alkenyl, substituted or unsubstituted C _{2 -50} alkenyl, substituted or unsubstituted C _{3 -50} cycloalkyl , substituted or unsubstituted C _{5 - 50} cycloalkenyl, substituted or unsubstituted C _{5 -50} cyclo-alkynyl, substituted or unsubstituted C _{6 -50} aryl group or the number of nuclear atoms unsubstituted or substituted 5- to 50 heteroaryl, substituted or unsubstituted C _{5 -50} aryl-amino or a substituted or unsubstituted C _{1 -50} alkyl,
Optionally wherein L and M are unsubstituted or substituted by C _{1 -6} alkyl, amino, thio, phosphoryl, phosphine sulfinyl, carbonyl, silyl, borane yl, C _{1 -50} alkyl, C _{2 -50} alkenyl , C _{2 -50} alkynyl, C _1-50 alkoxy, C _{3 -50} cycloalkyl, C _{6 -50} aryl, nuclear atoms may be substituted by from 5 to 50 heteroaryl or C _{7 -50} aralkyl,
Optionally wherein R ₁ to R ₅ is C _{1 -6} alkyl substituted or unsubstituted amino, thio, phosphoryl, phosphine sulfinyl, carbonyl, silyl, borane yl, C _{1 -50} alkyl, C _{2 -50} alkenyl, C _{2 -50} alkynyl, C _{1 -50} alkyl, which may be substituted with C _{3 -50} cycloalkyl, C _{6 -50} aryl, nuclear atoms of 5 to 50 heteroaryl or C _{7 -50} aralkyl .
The compound according to claim 1, wherein L and M each independently represent a single bond or a substituted or unsubstituted phenylene group.
The compound according to claim 1, wherein the compound is

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

, And

≪ / RTI > is a compound selected from the group consisting of < RTI ID = 0.0 >
A light emitting host or a dopant-containing composition for an organic electroluminescence device containing the compound of any one of claims 1 to 3.
An organic electroluminescent device comprising an anode, a cathode, and an organic layer containing a compound of any one of claims 1 to 3 between the two electrodes.
The organic electroluminescent device according to claim 5, wherein the organic layer is a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, or a laminate thereof.
The organic electroluminescent device according to claim 5, wherein the compound of any one of claims 1 to 3 is used as a light emitting host material or a dopant material.