KR101895949B1 - Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof - Google Patents

Abstract

The present invention provides an organic heterocyclic compound, an organic electronic device using the same, and an electronic device, which can improve the luminous efficiency, stability, and lifetime of the device.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound for an organic electronic device including an organic heteroaromatic compound, an organic heteroaromatic compound, an organic heteroaromatic compound, an organic heteroaromatic compound,

TECHNICAL FIELD The present invention relates to a compound including a heteroaromatic heterocycle, an organic electric device using the same, and an electronic device therefor.

Mr. Eastman Kodak of the 1980s. W. C. W. Tang et al. Have made organic electroluminescent devices using organic materials practical by developing laminated structure devices in which various roles are shared among various materials. They emit phosphors capable of transporting electrons and organic materials capable of transporting holes, and both charges are injected into the phosphor layer to emit light, so that a luminance of 1000 cd / m 2 or more can be obtained at a voltage of 10 V or less .

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 electric device using an organic light emitting phenomenon generally has a structure including an anode, an anode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic electronic device, the organic material layer is often formed of a multilayer structure composed of different materials, and may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

A material used as an organic material layer in an organic electric device may 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 phosphorescent material derived from singlet excited state of electrons and a phosphorescent material derived from the triplet excited state of electrons . Further, the light emitting material can be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural color depending on the luminescent color.

Particularly, various studies have been conducted on organic materials inserted into a hole transporting layer or a buffer layer for an excellent lifetime characteristic of an organic electric device. To this end, a high hole transporting property from an anode to an organic layer is given, A hole injection layer material having high uniformity and low crystallinity is required.

It is possible to delay penetration and diffusion of the metal oxide from the anode electrode (ITO), which is one of the causes of shortening the lifetime of the organic electronic device, and to stabilize the joule heating caused by driving the device, Lt; RTI ID = 0.0 > layer < / RTI > It is also reported that the low glass transition temperature of the hole transporting layer material significantly affects the lifetime of the device depending on the characteristics of the uniformity of the thin film surface collapsing during device operation. In addition, the deposition method is the mainstream in the formation of OLED devices, and a material that can withstand such a long time, that is, a material having high heat resistance characteristics, is required.

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 a 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, the desired wavelength light can be obtained depending on the type of the dopant used.

In order to sufficiently exhibit the excellent characteristics of the organic electroluminescent device described above, a material 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 is supported by a stable and efficient material However, stable and efficient development of an organic material layer for an organic electric device has not yet been sufficiently developed, and therefore development of a new material is continuously required.

Disclosure of the Invention An object of the present invention is to provide a compound containing an organic hetero ring capable of improving the light emitting efficiency, the low driving voltage, the color purity, and the lifetime of the device, and the organic electronic device using the compound and the electronic device.

The present invention provides a compound represented by the following formula (1) for solving the problems of the prior art described above and achieving the object of the present invention: high luminous efficiency, low driving voltage, color purity, stability and life of the device.

In Formula 1,

(1) R ₁ to R ₆ are hydrogen; heavy hydrogen; Tritium; A halogen group; A nitro group; A nitrile group; An amide group; A silane group; A condensed ring group of a C ₆ to C ₆₀ aromatic ring and a C ₄ to C ₆₀ aliphatic ring;

Of hydrogen, deuterium, halogen group, C ₁ ~ C ₆₀ alkyl group, C ₁ ~ C ₆₀ alkoxy group, C ₁ ~ C for ₆₀ alkyl amine group, C ₆ ~ C ₆₀ aryl amine group, C ₁ ~ C ₆₀ of An alkylthio group, an alkylthiophene group, a C ₆ to C ₆₀ arylthiophene group, a C ₂ to C ₆₀ alkenyl group, a C ₂ to C ₆₀ alkynyl group, a C ₃ to C ₆₀ cycloalkyl group, a C ₆ to C ₆₀ aryl A C ₆ to C ₆₀ aryl group substituted with deuterium, a C ₈ to C ₆₀ arylalkenyl group, a substituted or unsubstituted silane group, a substituted or unsubstituted boron group, a substituted or unsubstituted germanium group, and an aryl group, a substituted or unsubstituted C ₂ ~ C ₂₀ by at least one group selected from the group consisting of a heterocyclic-substituted or unsubstituted C ₆ ~ C ₆₀ of;

C ₁ ~ alkenyl group of the C ₂₀ alkyl group, C ₂ ~ C ₂₀ of, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ aryl group of C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with deuterium, C ₇ alkyl ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ of the hetero ring group, nitrile group and acetylene group unsubstituted or substituted with a substituent selected from the group consisting of C ₁ ~ C ₅₀ ;

A halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group , C ₈ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ of the heterocyclic group, the in nitrile group and acetylene group the group consisting of unsubstituted or substituted with substituent C ₂ ~ C An alkenyl group having 1 to ₄₀ carbon atoms;

Hydrogen, deuterium, halogen, CN, NO _2, C ₁ ~ C ₆₀ alkyl group, C ₁ ~ C ₆₀ alkoxy group, C ₁ ~ C ₆₀ alkyl amine group, C ₆ ~ C ₆₀ aryl amine group, C ₁ A C ₆ to C ₆₀ alkyl group, a C ₂ to C ₆₀ alkenyl group, a C ₂ to C ₆₀ alkynyl group, a C ₃ to C ₆₀ cycloalkyl group, a C ₆ to C ₆₀ aryl group, a C ₆ ~ C ₆₀ aryl group, a substituted or unsubstituted silane group, a substituted or unsubstituted boron group, a substituted or unsubstituted germanium group, and a substituted or unsubstituted from the group consisting of a heterocycle of the C ₂ ~ C ₂₀ ring A C ₂ to C ₆₀ heterocyclic group which is substituted or unsubstituted with one or more selected groups and contains at least one hetero atom selected from O, N, and S; And

One selected from the group consisting of a C ₁ to C ₆₀ alkyl group, a C ₂ to C ₆₀ alkenyl group, a C ₆ to C ₆₀ aryl group, a C ₂ to C ₂₀ heterocyclic group, and a C ₈ to C ₆₀ arylalkenyl group An amino group substituted or unsubstituted with the above groups; ≪ / RTI >

However, R ₄ to R ₆ Is a substituted or unsubstituted C ₆ to C ₆₀ aryl group, and when one of R ₄ to R ₆ is an aryl group, the other two groups are not hydrogen.

(2) X is S, O, Si (R ') (R "), N (R'), and wherein R 'to R" are hydrogen, deuterium, halogen group, C ₁ ~ alkyl group of C _60, C ₁ ~ C ₆₀ alkoxy group, C ₁ ~ C ₆₀ alkyl amine group, C ₆ ~ C ₆₀ aryl amine group, C ₁ ~ C ₆₀ alkyl thiophene group, C ₆ ~ C ₆₀ aryl thiophene group, C of ₂ ~ C ₆₀ alkenyl group, C ₂ ~ C ₆₀ alkynyl group, C ₃ ~ C ₆₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, a C ₆ ~ C ₆₀ substituted with a heavy hydrogen of the aryl group, a C ₈ ~ C ₆₀ arylalkenyl group, a substituted or unsubstituted silane group, a substituted or unsubstituted boron group, a substituted or unsubstituted germanium group, and a substituted or unsubstituted from the group consisting of a heterocycle of the C ₂ ~ C ₂₀ ring A C ₆ to C ₆₀ aryl group substituted or unsubstituted with at least one group selected; C alkyl group of ₁ ~ C _20, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ aryl group of C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with deuterium, C ₈ of alkyl ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ of the hetero ring group, nitrile group and acetylene group unsubstituted or substituted with a substituent selected from the group consisting of C ₁ ~ C ₅₀ ; Hydrogen, deuterium, a halogen, CN, NO _2, C ₁ ~ C ₆₀ alkyl group, C ₁ ~ C ₆₀ alkoxy group, C ₁ ~ C ₆₀ alkyl baby, C ₆ ~ C ₆₀ of the arylamine group, C ₁ ~ for C ₆₀ alkylthiophene group, C ₂ ~ alkenyl group of C _60, C ₂ ~ aryl group of C ₆₀ alkynyl group, C ₃ ~ C ₆₀ cycloalkyl group, C ₆ ~ C ₆₀ of, the C ₆ substituted with deuterium ~ C ₆₀ aryl group, a substituted or unsubstituted silane group, a substituted or unsubstituted boron group, a substituted or unsubstituted germanium group, and a substituted or unsubstituted C ₂ ~ C selected from the ₂₀ group consisting of a heterocyclic at least one group is a substituted or unsubstituted ring group O, N, a C ₂ ~ containing at least one hetero atom in the S C ₆₀ heterocyclic; And aromatic C ₆ to C ₆₀ aromatic rings and C ₄ to C ₆₀ aliphatic rings A condensed ring group ;

(3) l is an integer of 1 to 4, m is an integer of 1 to 3, and n is an integer of 1 to 5. On the other hand, when l, m, and n are an integer of 2 or more, a plurality of R ₁ , R ₂ , and R ₃ may be the same or different.

4, the R ₁ To R & lt; _{3 &} gt; may each be bonded to or reacted with adjacent groups to form a saturated or unsaturated ring. At this time, 'adjacent period' includes not only the substituent attached to the mother nucleus but also the mother nucleus itself. Accordingly, R ₁ to R ₄ may form a saturated or unsaturated ring by bonding or reacting with neighboring substituents, functional groups, carbon atoms included in the functional group forming the mother nucleus, or the like. A saturated or unsaturated ring is a concept including alicyclic, aromatic, heterocyclic, heterocyclic, and the like.

In the present specification, the term "aryl group" means a single ring or a heterocyclic aromatic group, and neighboring substituents include aromatic rings formed by bonding or participating in the reaction.

The term "heterocyclic group" refers to an aromatic or alicyclic monocyclic or heterocyclic ring containing a heteroatom in place of the ring forming carbon, and the adjacent substituent is a hetero Aromatic or alicyclic ring.

More specifically, the compound represented by Formula 1 may be represented by one of the following Chemical Formulas 2 to 8, wherein R ₁ to R ₆ , R ', R ", l, m and n are as defined in Chemical Formula 1 And o is an integer of 1 to 4.

More specifically, the above-mentioned formulas (1) to (8) may be one of the following compounds, but it is not limited thereto.

The compounds represented by Formula 1 may be one of the compounds shown above, but are not limited thereto. In this case, since it is practically difficult to exemplify all the compounds due to the wide range of substituents of the compounds represented by the formula (1), representative compounds are exemplarily described, but the compounds represented by the formula (1) can do.

In another aspect, the present invention provides an organic electronic device using the compound represented by the above formula and an electronic device including the organic electronic device.

The use of the heteroaromatic heterocyclic compound according to the present invention has the effect of greatly improving the device's high luminous efficiency, low driving voltage, color purity, and service life.

1 to 6 show examples of organic electroluminescent devices to which the compounds of the present invention can be applied.

Hereinafter, some embodiments of the present invention will be described in detail with reference to exemplary drawings.

It should be noted that, in adding reference numerals to the constituent elements of the drawings, the same constituent elements are denoted by the same reference symbols as possible even if they are shown in different drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected," "coupled," or "connected."

Hereinafter, preparation examples or synthesis examples of the compounds belonging to the formula 1 will be described. However, since the compounds belonging to the general formula (1) are numerous, some of the compounds belonging to the general formula (1) are exemplarily described. However, those skilled in the art will appreciate that those skilled in the art , A compound belonging to the present invention which is not illustrated can be prepared.

Typical Synthetic Method Example

The compounds of formulas 2, 4, 6 ( Product  1 to 3)

Sub 1 or Sub 2 or Sub 3 compound (1 equivalent), Sub 4 compound (1 equivalent), Pd ₂ (dba) ₃ (0.06-0.1 mmol), PPh ₃ (0.2 equivalent), NaO t- Bu (6 eq.) And toluene (10.5 mL / 1 mmol), and the reaction is allowed to proceed at 100 ° C. After completion of the reaction, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic matters were subjected to silicagel column and recrystallization to obtain final products 1, 2 and 3.

Sub  1 Synthetic method example:

Sub  1-1 Synthesis

The 4-bromo-1-iodo- 2-nitrobenzene, NaOH, Pd (PPh 3) 4 substitution after insert the 2L round the bottom flask was replaced by _{R 1 phenylboronic acid, THF, H} 2 O is dissolved in R ₂ in the order And the reaction is allowed to proceed at 80 DEG C for 24 hours. When the reaction is completed, the reaction mixture is extracted with methylene chloride, water, and brine, and the organic layer is dried with MgSO ₄ . The obtained organic layer was subjected to silicagel column (methylene chloride: hexane = 1: 3) to obtain Sub1-1.

Sub  1-2 Synthetic method

The obtained 1-1 triethylphosphate is added and the mixture is refluxed at 160 ° C to 165 ° C for 14 hours. After the reaction is completed, the remaining triethylphosphite is removed by distillation under reduced pressure, diluted with a mixed solvent of MeOH: H ₂ O = 1: 1, and the resulting solid is filtered. The resulting solid is washed with a mixed solvent of MeOH: H ₂ O = 1: 1 and petroleum ether. The solid was dissolved in methylene chloride, dried over MgSO ₄ , concentrated and silicagel column to obtain Sub 1-2. (petroleum ether: methylene chloride = 2: 1)

Sub  1-3 Synthetic method

Pd ₂ (dba) ₃ , PPh ₃ and NaO t -Bu were added after Sub 1 - 3 and Sub 1-4 were mixed in 2800 ml of toluene, and the mixture was refluxed at 100 ° C for 24 hours. After extracting with ether and water, the organic layer was dried with MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain Sub1.

Sub  2 Synthetic method example:

Sub  2-1 Synthetic method

After bromobenzene substituted with R ₁ was dissolved in DMF, bispinacoloborate was added to the catalyst in the order of PdCl ₂ (dppf) catalyst and KOAc, and the mixture was stirred for 24 hours to synthesize a borate compound. The resulting compound was purified by silica gel column and recrystallization Subsequently, Sub 2-1 was obtained as a borate compound.

Sub  2-2 Synthetic method

After dissolving 1 equivalent of Sub 2-1 and 5 equivalents of (5-bromo-2-iodophenyl) (methyl) sulfane substituted with R ₂ in THF, 1.1 equivalents of Tetrakis (triphenylphosphine) palladium and 2M aqueous sodium carbonate solution were added, The mixture was stirred at 70 占 폚 for 18 hours. After the reaction was completed, the reaction mixture was extracted with diethyl ether and water. The organic layer was dried and purified by silicagel column and recrystallization to obtain Sub 2-2.

Sub  2-3 Synthetic method

Sub 2-2 is dissolved in dichloromethane, 30% aqueous hydroxyperoxide solution and acetic acid are added, and the mixture is stirred at 30 ° C for 4 hours. After the reaction was completed, the reaction mixture was extracted with chloroform and water, and the organic layer was dried, and subjected to silicagel column and recrystallization to obtain Sub 2-3.

Sub  2 synthesis method

Add triflic acid to Sub 2-3 and stir at room temperature for 72 hours. When the reaction was complete, diethyl ether was added and the resulting white solid precipitate was filtered and dried to give 78% of Sub 2.

Sub  3 Synthetic method example:

After dibenzofuran substituted with R ₁ and R ₂ is dissolved in methylene chloride, 0.05 equivalents of BPO (Benzoyl peroxide) and NBS (N-bromosuccinimide) are slowly added thereto, followed by stirring at room temperature for 24 hours. After the reaction is completed, 5% HCl is added, water is added, the remaining NBS is removed, and the mixture is extracted with ether and water. The organic layer is dried with MgSO ₄ and concentrated. Subsequently, the resulting organic material was subjected to silicagel column and recrystallization to obtain Sub 3.

Examples of Sub 4 are as follows, but are not limited thereto.

Mass analysis results for the Sub 4-1 to 4-12 were as shown in Table 1 below.

Examples of the synthesis of the compounds of formulas 3, 5 and 7

(1 equivalent), Sub 8 compound (1 equivalent), Pd ₂ (dba) ₃ (0.06-0.1 mmol), PPh ₃ (0.2 equivalent), NaO t- Bu (6 eq.) And toluene (10.5 mL / 1 mmol), and the reaction is allowed to proceed at 100 ° C. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain final products 4, 5 and 6.

Sub  Synthesis Example 5:

Sub  5-1 Synthetic method

1-bromocarbazole substituted with R ₁ and R ₂ was dissolved in anhydrous THF, the temperature of the reaction was lowered to -78 ° C., n-BuLi (2.5 M in hexane) was slowly added dropwise and the reaction was stirred at 0 ° C. for 1 hour ≪ / RTI > Then, the temperature of the reaction was lowered to -78 ° C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. Water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated. The resulting product was separated by column chromatography to obtain the desired Sub 5-1.

Sub  5-2 Synthetic method

1-bromo-2-nitrobenzene, Pd ₂ (PPh ₃ ) ₄ and K ₂ CO ₃ substituted with Sub 5-1 and R ₃ obtained were dissolved in anhydrous THF and a small amount of water and refluxed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, the organic solvent was concentrated, and the resulting product was separated by column chromatography to obtain the desired Sub 5-2.

Sub  5 Synthetic method

The obtained Sub 5-2 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. When the reaction was completed, the solvent was removed by distillation under reduced pressure, and the concentrated product was separated by column chromatography to obtain the desired Sub 5.

Sub  6 Synthetic method example:

Sub  6-1 Synthetic method

4-bromodibenzothiophene substituted with R ₁ and R ₂ was dissolved in anhydrous THF, the temperature of the reaction was lowered to -78 ° C., n-BuLi (2.5 M in hexane) was slowly added dropwise, ≪ / RTI > Then, the temperature of the reaction was lowered to -78 ° C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. Water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, the organic solvent was concentrated, and the resulting product was separated by column chromatography to obtain the desired Sub 6-1.

Sub  6-2 Synthetic method

1-bromo-2-nitrobenzene, Pd ₂ (PPh ₃ ) ₄ and K ₂ CO ₃ substituted with Sub 6-1 and R ₃ were dissolved in anhydrous THF and a small amount of water and refluxed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, the organic solvent was concentrated, and the resulting product was separated by column chromatography to obtain the desired Sub 6-2.

Sub  6 Synthetic method

The resulting Sub 6-2 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the concentrated product was separated by column chromatography to obtain the desired Sub 6.

Sub  7 Synthetic method example:

Sub  7-1 Synthetic method

After 4-bromodibenzofuran substituted with R ₁ and R ₂ was dissolved in anhydrous THF, the reaction temperature was lowered to -78 ° C, n-BuLi (2.5 M in hexane) was slowly added dropwise, ≪ / RTI > Then, the temperature of the reaction was lowered to -78 ° C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. The water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, the organic solvent was concentrated, and the resulting product was separated by column chromatography to obtain the desired Sub 7-1.

Sub  7-2 Synthetic method

The obtained Sub 7-1 and 1-bromo-2-nitrobenzene, Pd ₂ (PPh ₃ ) ₄ and K ₂ CO ₃ substituted with R ₃ were dissolved in anhydrous THF and a small amount of water and refluxed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, the organic solvent was concentrated, and the resulting product was separated by column chromatography to obtain the desired Sub 7-2.

Sub  7 Synthetic method

The obtained Sub 7-2 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. When the reaction was completed, the solvent was removed by distillation under reduced pressure, and the concentrated product was separated by column chromatography to obtain the desired Sub 7.

Examples of Sub 8 are as follows, but are not limited thereto. Mass analysis results for Sub 8-1 to 8-7 are shown in Table 2.

Product  1-8 Synthetic Examples

(9.8 g, 20 mmol), N, 2,4-triphenylpyrimidin-5-amine (7.8 g, 24 mmol), Pd ₂ (dba) ₃ (0.06-0.1 mmol), PPh ₃ (0.2 eq.), NaO t- Bu (6 eq.) and toluene (10.5 mL / 1 mmol). After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 9.7 g (yield: 66%) of final product.

Product  2-12 Synthetic Example

(8.2 g, 20 mmol), 5-bromo-2,4-diphenylpyrimidine (7.5 g, 24 mmol), Pd ₂ (dba) ₃ (0.06-0.1 mmol), PPh ₃ ), NaO t- Bu (6 eq.), And toluene (10.5 mL / 1 mmol) were added thereto, followed by reaction at 100 ° C. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 8.4 g (yield: 64%) of final product.

Product  3-16 Synthetic Examples

To a round bottom flask was added 3-bromodibenzothiophene (5.3g, 20mmol) , N, 2,4,6-tetraphenylpyrimidin-5-amine (9.6g, 24mmol), Pd 2 (dba) 3 (0.06 ~ 0.1 mmol), PPh 3 ( 0.2 eq.), NaO t- Bu (6 eq.), And toluene (10.5 mL / 1 mmol). After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 7.1 g (yield: 61%) of final product.

Product  4-1 Synthetic Example

(5.5 g, 20 mmol), 5-bromo-2,4-diphenylpyrimidine (7.5 g, 24 mmol), Pd ₂ (dba) ₃ (0.06-0.1 mmol) and PPh ₃ ), NaO t- Bu (6 eq.), And toluene (10.5 mL / 1 mmol) were added thereto, followed by reaction at 100 ° C. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 6.8 g (yield: 68%) of final product.

Product  5-18 Synthetic Examples

To a round bottom flask was added 3-bromodibenzofuran (5.0g, 20mmol) , 2- (9H-carbazol-9-yl) -N, 4-diphenylpyrimidin-5-amine (10.0g, 24mmol), Pd 2 (dba) 3 (0.06 0.1 mmol), PPh ₃ (0.2 eq.), NaO t- Bu (6 eq.) And toluene (10.5 mL / 1 mmol). After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 7.2 g (yield: 62%) of final product.

Product  6-3 Example of synthesis

(5.5 g, 20 mmol), 5-bromo-2,4-diphenylpyrimidine (7.5 g, 24 mmol) and Pd ₂ (dba) ₃ (0.06 - 0.1 mmol), PPh ₃ (0.2 eq.), NaO t- Bu (6 eq.) And toluene (10.5 mL / 1 mmol). After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 6.5 g (yield: 64%) of final product.

Product  7-20 Synthetic Examples

(2.5 g, 20 mmol), 5-bromo-2- (dibenzo [b, d] thiophen-3-yl) -4-phenylpyrimidine (10.0 g, 24 mmol) and Pd ₂ (dba) were added to a round bottom flask. ₃ (0.06-0.1 mmol), PPh ₃ (0.2 eq.), NaO t- Bu (6 eq.) And toluene (10.5 mL / 1 mmol). After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 9.3 g (yield: 61%) of final product.

The results of mass spectrometry for the compounds 1-1 to 7-20 synthesized by the above-described synthesis method are shown in Table 3.

Meanwhile, although each of the substituents of the compounds represented by the formula (1) is broadly related to the synthesis examples of representative compounds, the compounds not exemplarily illustrated in the synthesis examples can also form a part of the present specification.

Further, by introducing various substituents into the core structure having the above structure, it is possible to synthesize a compound having the intrinsic characteristics of the substituent introduced. For example, by introducing a substituent used in a hole injecting layer material, a hole transporting layer material, a light emitting layer material, and an electron transporting layer material used in the production of an organic electronic device including the organic light emitting device into the above structure, Materials can be prepared.

The compounds according to the present invention can be used in various applications in organic electroluminescent devices depending on the kind and nature of substituent groups.

Since the compounds of the present invention are controllable by the core and the substituent, they can act as various layers other than phosphorescent or fluorescent light emitting host hosts.

The organic electroluminescent device of the present invention can be manufactured by a conventional method and material for producing an organic electroluminescent device, except that the above-described compounds are used to form one or more organic substance layers.

It is obvious that the same effects can be obtained even when the compounds of the present invention are used in other organic layers of an organic electroluminescent device, for example, a light-emission assisting layer, an electron injecting layer, an electron transporting layer, and a hole injecting layer.

Meanwhile, the compound of the present invention can be used in a soluble process. That is, the organic compound layer of the organic electronic device described later can be formed by a soluble process of the compound. That is, when the compound is used as an organic material layer, the organic material layer may be formed by a solution process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, Lt; RTI ID = 0.0 > a < / RTI > fewer layers.

Organic electric devices in which the compounds of the present invention can be used include, for example, organic electroluminescent devices (OLED), organic solar cells, organic photoconductor (OPC) drums, organic transistors (organic TFT)

The organic electroluminescent device (OLED) will be described as one example of organic electroluminescent devices to which the compounds of the present invention can be applied, but the present invention is not limited thereto and the above-described compounds may be applied to various organic electroluminescent devices.

According to another embodiment of the present invention, there is provided an organic electroluminescent device comprising a first electrode, a second electrode and an organic material layer disposed between the first electrode and the second electrode, wherein at least one of the organic material layers comprises the compound of the present invention to provide.

1 to 6 show examples of organic electroluminescent devices to which the compounds of the present invention can be applied.

The organic electroluminescent device according to another embodiment of the present invention can be manufactured by the same method as the organic electroluminescent device except that at least one layer of the organic compound layer including the hole injecting layer, the hole transporting layer, the light emitting layer, the electron transporting layer, Can be made with a structure known in the art using conventional manufacturing methods and materials in the art.

The structure of an organic electroluminescent device according to another embodiment of the present invention is illustrated in FIGS. 1 to 6, but is not limited to these structures. Reference numeral 101 denotes a substrate, 102 denotes an anode, 103 denotes a hole injection layer (HIL), 104 denotes a hole transport layer (HTL), 105 denotes a light emitting layer (EML), 106 denotes an electron injection layer (EIL) ETL), and 108 denotes a cathode.

The organic electroluminescent device has a hole blocking layer (HBL) for blocking the movement of holes, an electron blocking layer (EBL) for blocking the movement of electrons, a luminescent auxiliary layer for assisting or assisting luminescence and a protective layer It may be located. In the case of the protective layer, it may be formed to protect the organic layer at the uppermost layer or to protect the cathode.

At this time, the compound of the present invention may be included in at least one of organic compound layers including a hole injecting layer, a hole transporting layer, a light emitting layer, and an electron transporting layer.

Specifically, the compound of the present invention may be used as a substitute for one or more of a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer, a hole blocking layer, May be used. Of course, it can be used for more than two layers, not only one layer of the organic material layer.

In particular, it can be used as a hole injecting material, a hole transporting material, an electron injecting material, an electron transporting material, a light emitting material and a passivation (keping) material according to the compound of the present invention, It can be used as a dopant, and can be used as a hole injecting and hole transporting layer.

For example, the organic electroluminescent device according to another embodiment of the present invention may be formed by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, Oxide or an alloy thereof to form an anode, forming an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer and an electron injecting layer on the anode, depositing a material usable as a cathode thereon .

In addition to such a method, the organic material may be formed by sequentially depositing a negative electrode material, an organic material layer, and a positive electrode material on a substrate. The organic material layer may have a multi-layer structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, but is not limited thereto and may have a single layer structure.

In addition, the organic material layer may be formed by using a variety of polymer materials, not by vapor deposition, but by a solution process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, It can be manufactured in a small number of layers.

The organic electroluminescent device according to another embodiment of the present invention may be used in a soluble process such as a spin coating process or an ink jet process.

The substrate may be a silicon wafer, a quartz or glass plate, a metal plate, a plastic film, or a sheet.

An anode is placed on the substrate. Such an anode injects holes into the hole injection layer located thereon. The anode material may be a material having a large work function so that hole injection can be smoothly conducted into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of a metal and an oxide such as ZnO: Al or SnO2: Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline.

A hole injection layer is located on the anode. The conditions required for the material of the hole injection layer are that the hole injection efficiency from the anode is high and the injected holes must be efficiently transported. For this purpose, the ionization potential is small, the transparency to visible light is high, and the stability against holes is excellent.

As the hole injecting material, a hole can be injected from the anode at a low voltage. The highest occupied molecular orbital (HOMO) of the hole injecting material may be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene, quinacridone-based organic materials, perylene-based organic materials, Anthraquinone, polyaniline and a polythiophene-based conductive polymer, but are not limited thereto.

A hole transport layer is disposed on the hole injection layer. The hole transport layer transports holes from the hole injection layer to an organic light emitting layer disposed thereon, and has high hole mobility, stability to holes, and electrons. In addition to these general requirements, heat resistance to a device is required when it is applied for vehicle display, and it may be a material having a glass transition temperature (Tg) of 70 DEG C or more.

Materials satisfying such conditions include NPD (or NPB), spiro-arylamine compounds, perylene-arylamine compounds, azacycloheptatriene compounds, bis (diphenylvinylphenyl) anthracene, silicon germanium oxide Compounds, silicone-based arylamine compounds, and the like.

An organic light emitting layer is disposed on the hole transporting layer. The organic light emitting layer is a layer in which holes and electrons injected from the anode and the cathode respectively recombine to emit light, and the organic light emitting layer is made of a material having high quantum efficiency. The light emitting material may be a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and may be a material having good quantum efficiency for fluorescence or phosphorescence.

Materials or compounds that satisfy these conditions include Alq3 in the case of green, Balq (8-hydroxyquinoline beryllium salt) in the case of blue, DPVBi (4,4'-bis (2,2-diphenylethenyl) biphenyl series, Spiro material, Spiro-4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzoxazoyl) -phenolithium salt ), Bis (diphenylvinylphenylvinyl) benzene, aluminum-quinoline metal complexes, imidazoles, thiazole and oxazole metal complexes, and perylene and BczVBi (3,3 ' (1,1'-biphenyl) -4,4'-diyldi-2,1-ethenediyl] bis (9-ethyl) -9H-carbazole; DSA (distrylamine). In the case of red, the green luminescent material was doped with DCJTB ([2- (1,1-dimethylethyl) -6- [2- (2,3,6,7-tetrahydro-1,1,7,7-tetramethyl- -benzo (ij) quinolizin-9-yl) ethenyl] -4H-pyran-4-ylidene] -propanedinitrile).

Polymers such as a polyphenylene vinylene (PPV) -based polymer and polyfluorene may be used for the organic light emitting layer when the light emitting layer is formed using processes such as inkjet printing, roll coating and spin coating .

An electron transporting layer is disposed on the organic light emitting layer. Such an electron transporting layer requires a material capable of efficiently injecting electrons with a high electron injection efficiency from a cathode disposed thereon. For this purpose, it is required to be made of a material having high electron affinity, high electron transfer rate and excellent stability against electrons.

Specific examples of the electron transporting material satisfying such conditions include an Al complex of 8-hydroxyquinoline; Complexes containing Alq3; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.

An electron injection layer is deposited on the electron transport layer. The electron injection layer may be a metal complex compound such as Balq, Alq3, Be (bq) 2, Zn (BTZ) 2, Zn (phq) 2, PBD, spiro-PBD, TPBI or Tf-6P, boron compounds, and the like. At this time, the electron injection layer may be formed in a thickness range of 100 ANGSTROM to 300 ANGSTROM.

On the electron injection layer, a cathode is positioned. These cathodes serve to inject electrons. The material used for the cathode may be the material used for the anode and may be a metal having a low work function for efficient electron injection. Particularly suitable metals such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, silver, or their alloys may be used. Also, an electrode having a two-layer structure such as lithium fluoride and aluminum, lithium oxide and aluminum, strontium oxide and aluminum, etc., having a thickness of 100 μm or less may be used.

As described above, the compound of the present invention can be used as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material, which are suitable for the fluorescence of all colors such as red, green, It can be used as a host or dopant material of various colors.

The organic electroluminescent device according to the present invention may be of a top emission type, a back emission type, or a both-sided emission type, depending on the material used.

Meanwhile, the present invention includes a display device including the above-described organic electronic device and a terminal including a control unit for driving the display device. This terminal means a current or future wired or wireless communication terminal. The terminal according to the present invention may be a mobile communication terminal such as a mobile phone and includes all terminals such as a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.

Evaluation of manufacturing of organic electric device

An organic electroluminescent device was fabricated according to a conventional method using a compound obtained through synthesis as a luminescent host material in a light emitting layer. First, a film of copper phthalocyanine (hereinafter referred to as CuPc) was vacuum deposited on the ITO layer (anode) formed on a glass substrate to form a hole injection layer having a thickness of 10 nm. Subsequently, 4,4-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (hereinafter abbreviated as -NPD) was vapor-deposited as a hole transport compound on the film to a thickness of 30 nm to form a hole transport layer . (2-phenylpyridine) iridium (hereinafter referred to as " Ir (ppy) 3 ") as a phosphorescent Ir metal complex dopant was formed by depositing the above-described compound as a phosphorescent host material to form a hole transport layer, Flask). At this time, the concentration of Ir (ppy) 3 in the light emitting layer was 5 wt%. (2-methyl-8-quinolinolato) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm as a hole blocking layer, and electron injection Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was deposited to a thickness of 40 nm. Thereafter, LiF as an alkali metal halide was deposited to a thickness of 0.2 nm, Al was subsequently deposited to a thickness of 150 nm, and this Al / LiF was used as a cathode to produce an organic electroluminescent device.

Comparative Example

For comparison, an organic electroluminescent device having the same structure as that of the test example was fabricated using the compounds represented by the following formulas instead of the compound of the present invention as a luminescent host material.

The performance (driving voltage, current density, brightness, efficiency, lifetime, and color coordinates) of the organic electroluminescent device manufactured using the above-described compounds and the comparative examples as the light emitting host material are as shown in Table 4 below.

As can be seen from the above table, the material for an organic electroluminescence device of the present invention can be used as a light emitting host material, which can remarkably improve a low driving voltage, color purity, high luminous efficiency and service life.

In particular, when the present invention is compared with the comparative examples (2) and (3), it can be seen that the efficiency and lifetime are remarkably improved depending on the position of the nitrogen atom even if the substituent has similar substituents to the same core. That is, it was confirmed that compounds having nitrogen at the 4th and 6th positions of the present invention were significantly improved in efficiency and lifetime compared with the comparative compounds having nitrogen at positions 1 and 3 or nitrogen at positions 3 and 5 . As a result of Comparative Example (4) and Comparative Example (5), the compound of the present invention shows a better effect than a compound containing a linking group such as phenyl.

It is obvious that the same effects can be obtained even when the compounds of the present invention are used in other organic layers of an organic electroluminescent device such as a light emitting auxiliary layer, an electron injecting layer, an electron transporting layer, a hole transporting layer and a hole injecting layer.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention is not limited by these embodiments.

The scope of protection of the present invention should be construed according to the following claims, and all the techniques within the scope of the same should be construed as being included in the scope of the present invention.

Claims (9)

A compound represented by the following formula (1):
≪ Formula 1 >

In Formula 1,
R ₁ to R ₃ independently of one another are hydrogen; heavy hydrogen; A halogen group; A C ₆ to C ₆₀ aryl group; A C ₁ to C ₅₀ alkyl group; A C ₂ to C ₄₀ alkenyl group; Heterocyclic group of O, N, and C ₂ ~ containing at least one hetero atom in the C ₆₀ S; And an amine group substituted with an aryl group of C ₆ to C ₆₀ ; And R ₁ to R ₃ may be independently bonded to adjacent groups to form a saturated or unsaturated ring,
R ₄ to R ₆ independently of one another are hydrogen; heavy hydrogen; A C ₆ to C ₆₀ aryl group; And a C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from the group consisting of O, N, and S,
Provided that at least one of R ₁ to R ₃ is bonded to an adjacent group to form a ring and at least one of R ₄ to R ₆ is a substituted or unsubstituted C ₆ to C ₆₀ aryl group,
Except that when one of R ₄ to R ₆ is an aryl group, the remaining two groups are all hydrogen,
l is an integer of 1 to 4, m is an integer of 1 to 3, n is an integer of 1 to 5,
When l, m and n are each an integer of 2 or more, each R ₁ , each R ₂ , each R ₃ is the same or different,
X is O, Si (R ') (R ") or N (R'),
Wherein R 'and R "are each independently a C ₆ to C ₆₀ aryl group, a C ₁ to C ₅₀ alkyl group, and a C ₂ to C ₆₀ heterocyclic ring containing at least one hetero atom selected from O, N and S Group; < / RTI >
If the N (R ') R a' is an aryl group, it may be further substituted with an aryl group of C ₁ ~ C ₆₀ alkyl group or a C ₆ ~ C ₆₀ of. The method according to claim 1,
(1) is represented by the following general formula (3), (7) or (8):
&Lt; Formula 3 >< EMI ID =

Wherein R ₁ to R ₆ , R ', R ", l, m and n are the same as defined in claim 1, and o is an integer of 1 to 4. The method according to claim 1,
Wherein the compound of formula (I) is one of the following compounds:

. An organic electroluminescent device comprising a first electrode, a second electrode, and an organic layer formed between the first electrode and the second electrode,
Wherein the organic material layer comprises a compound according to any one of claims 1 to 3. 5. The method of claim 4,
Wherein the organic material layer is formed by a solution process. 5. The method of claim 4,
Wherein the organic material layer comprises at least one of a light emitting layer, a hole injecting layer, a hole transporting layer, an electron injecting layer, and an electron transporting layer. The method according to claim 6,
Wherein the compound is used as a host or dopant material of the light emitting layer. A display device including the organic electroluminescent device of claim 4; And
And a control unit for driving the display device. 9. The method of claim 8,
Wherein the organic electronic device is an organic electroluminescent device, an organic solar cell, an organophotoreceptor, or an organic transistor.

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