KR102346943B1 - Bis phenyl pyrazine derivatives organic light emitting compound and organic electroluminescent device including the same - Google Patents

Abstract

상기 비스 페닐 피라진 유도체 유기화합물은 유기 전계발광 소자에 포함시 적절한 에너지 준위, 전기 화학적 안정성 및 열적 안정성등을 모두 우수하게 만족시킬 수 있다.A bisphenyl pyrazine derivative organic compound represented by the following formula (a) is provided.
[Formula a]

When the bisphenyl pyrazine derivative organic compound is included in an organic electroluminescent device, it is possible to excellently satisfy all of the appropriate energy level, electrochemical stability and thermal stability.

Description

Bis phenyl pyrazine derivatives organic light emitting compound and organic electroluminescent device including the same

It relates to a bisphenyl pyrazine derivative organic light emitting compound and an organic electroluminescent device comprising the same.

BACKGROUND ART An electroluminescence device (EL device) is a self-emission type display device, and has advantages of a fast response speed and a wide viewing angle. [Appl. Phys. Lett. 51, 913, 1987].

The most important factor that determines the luminous efficiency in an organic electroluminescent device is a luminescent material. Among luminescent materials, a phosphorescent material can theoretically improve luminous efficiency by 4 times compared to a fluorescent material. Until now, iridium (III) complex-based and carbazole-based materials are widely known as phosphorescent materials, and new phosphorescent materials are being studied recently.

The principle of organic electroluminescence is that when a voltage is applied between the two electrodes when there is an organic thin film layer between the cathode and the anode, electrons and holes are injected into the organic thin film layer from the cathode and the anode, respectively. Electrons and holes injected into the organic thin film layer recombine to form excitons, and the excitons fall back to the ground state and emit light. An organic electroluminescent device using this principle is generally a cathode and an anode and an organic thin film layer positioned therebetween, for example, an organic thin film layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer.

Materials used in organic electroluminescent devices are mostly pure organic substances or complex compounds formed by complexing organic substances with metals, and can be used as hole injection materials, hole transport materials, light emitting materials, electron transport materials, electron injection materials, etc. can be distinguished. Here, as the hole injection material or the hole transport material, an organic material having a p-type property, that is, an organic material that is easily oxidized and has an electrochemically stable state during oxidation is mainly used. On the other hand, as an electron injection material or an electron transport material, an organic material having an n-type property, that is, an organic material that is easily reduced and has an electrochemically stable state during reduction is mainly used. As the light emitting layer material, a material having both p-type and n-type properties, that is, a material having a stable form in both oxidation and reduction states, is preferable. desirable. Accordingly, there is a demand in the art for the development of a new organic material satisfying the above requirements.

One embodiment of the present invention provides a bisphenyl pyrazine derivative organic light emitting compound having an appropriate energy level, electrochemical stability and thermal stability.

In one embodiment of the present invention, there is provided a bisphenyl pyrazine derivative organic light emitting compound represented by the following formula (a).

<Formula a>

In the above formula (a),

Ar ₁ is C1~ C60 alkyl group, C1~ C60 alkyloxy group, substituted or unsubstituted C6~ C60 aryl group, C5~ C60 aryloxy group, substituted or unsubstituted C3~ C60 N, O, A heteroaryl group containing S and Si, a C6~ C60 arylalkyl group, or a C3~ C60 cycloalkyl group, wherein _{the substituent when Ar 1} is substituted is deuterium, a cyano group, a nitrile group, a halogen group, a C1-C30 It is one selected from the group consisting of an alkyl group, a C1~ C30 alkyloxy group, a C6~ C60 aryl group, a C5~ C60 heteroaryl group, and combinations thereof,

L ₁ is a single bond, or includes substituted or unsubstituted C6~ C40 arylene, substituted or unsubstituted C10~ C40 condensed arylene, substituted or unsubstituted C5~ C40 N, O, S and Si is one selected from the group consisting of heteroarylene and combinations thereof; When L ₁ is substituted, the substituents are hydrogen, deuterium, a C1 to C40 alkyl group, a C1 to C40 alkyloxy group, a C6 to C40 aryl group, a C5 to C40 aryloxy group, a C5 to C40 heteroaryl group. and one selected from the group consisting of combinations thereof,

R ₁ and R ₂ are each independently hydrogen, deuterium, cyano group, nitrile group, halogen group, hydroxyl group, C1-C40 alkyl group, C1-C40 alkyloxy group, substituted or unsubstituted C6-C40 of an aryl group, a C5~ C40 aryloxy group, a substituted or unsubstituted C3~ C40 heteroaryl group including N, O, S and Si, a C6~ C40 arylalkyl group or a C3~ C40 cycloalkyl group, When the R ₁ and R ₂ are substituted, the substituent is hydrogen, deuterium, a cyano group, a nitrile group, a halogen group, a C1 to C40 alkyl group or a C6 to C40 aryl group, a C5 to C40 heteroaryl group, and combinations thereof is one selected from the group consisting of,

m and n are each independently an integer of 0-5.

Specifically, Ar ₁ may be any one compound selected from the group consisting of the following.

Wherein m and n are each independently an integer of 0 to 5,

X is C(R ₄ )(R ₅ ), Si(R ₄ )(R ₅ ), N(R ₆ ), S or O,

Z is S or O;

R ₃ is hydrogen, deuterium, cyano group, nitrile group, halogen group, hydroxyl group, C1~ C40 alkyl group, C1~ C40 alkyloxy group, substituted or unsubstituted C6~ C40 aryl group, C5~ C40 It is one selected from the group consisting of an aryloxy group, a substituted or unsubstituted C3~ C40 heteroaryl group including N, O, S and Si, a C6~ C40 arylalkyl group, or a C3~ C40 cycloalkyl group,

When Ar ₁ includes a plurality of R ₃ , each R ₃ is the same as or different from each other, and adjacent groups may be bonded to each other to form an aromatic ring together with the carbon bonded thereto,

o is an integer from 0 to 7,

p is an integer from 0 to 4,

q is an integer from 0 to 3,

r is an integer from 0 to 6,

s is an integer from 0 to 9,

t is an integer from 0 to 8,

The R ₄ and R ₅ are each independently, a C1~ C40 alkyl group, a C1~ C40 alkyloxy group, a substituted or unsubstituted C6~ C40 aryl group, a substituted or unsubstituted C3~ C40 N, O , S and a heteroaryl group containing Si, a C6~ C40 arylalkyl group or a C3~ C40 cycloalkyl group is one selected from the group consisting of,

The R ₄ and R ₅ may combine with each other to form a spiro compound together with the fluorene to which they are bonded,

Wherein R ₆ is a C1~ C40 alkyl group, a C1~ C40 alkyloxy group, a substituted or unsubstituted C6~ C40 aryl group, a substituted or unsubstituted C3~ C40 N, O, S and a hetero containing Si One selected from the group consisting of an aryl group, a C6-C40 arylalkyl group, or a C3-C40 cycloalkyl group, and combinations thereof.

Specifically, R ₁ and R ₂ may each independently be any one compound selected from the group consisting of:

Specifically, the L may be any one compound selected from the group consisting of:

The organic light emitting compound provides a bisphenyl pyrazine derivative organic light emitting compound used as a material for a light emitting layer, a hole blocking layer, an electron transport layer, or an electron injection layer among materials for an organic light emitting device.

In another embodiment of the present invention, in the organic electroluminescent device in which at least one organic thin film layer is sandwiched between the cathode and the anode, the organic thin film layer has a multilayer structure including at least one light emitting layer and an electron transport region, and the organic At least one layer in the thin film layer provides an organic electroluminescent device comprising the bisphenyl pyrazine derivative organic light emitting compound alone or a mixture of two or more.

The electron transport region is interposed between the cathode and the light emitting layer, and an electron injection layer, an electron transport layer, an organic electroluminescent device comprising at least one of a functional layer having an electron injection function and an electron transport function at the same time, a buffer layer and a hole blocking layer provides

At least one layer selected from the layers formed between the cathode and the anode provides an organic electroluminescent device formed by a vacuum deposition process or a solution process.

The bisphenyl pyrazine derivative organic light emitting compound can excellently satisfy all of the conditions required for materials usable in the organic electroluminescent device, such as an appropriate energy level, electrochemical stability and thermal stability, and depending on the substituent, the organic electroluminescent device It can play various roles required in

1 is a lifespan characteristic evaluation graph showing measurement results for organic electroluminescent devices prepared in Examples 4, 5, 6, 7, and Comparative Examples 1 and 2;
2 is a lifespan characteristic evaluation graph showing the measurement results of the organic electroluminescent devices prepared in Examples 12, 13, 14, 15 and Comparative Examples 1 and 2;
3 is a lifespan characteristic evaluation graph showing the measurement results of the organic electroluminescent devices prepared in Examples 22 to 25 and Comparative Examples 3 and 4;

Hereinafter, embodiments of the present invention will be described in detail. However, this is provided as an example, and the present invention is not limited thereto, and the present invention is only defined by the scope of the claims to be described later.

In the present specification, "substituted" means, unless otherwise defined, a C1-C12 alkyl group, an amino group, a nitrile group, a C3-C7 cycloalkyl group, a C2-C12 alkenyl group, a C3-C7 cycloalkenyl group, C2 -C50 alkynyl group, C5-C50 cycloalkynyl group, cyano group, C1-C12 alkoxy group, C6-C60 aryl group, and C7-C60 arylalkyl group substituted with a substituent selected from the group consisting of and combinations thereof including cases where

In the present specification, "combination thereof" means that, unless otherwise defined, two or more substituents are bonded to a linking group, or two or more substituents are condensed and bonded.

As used herein, unless otherwise defined, "hetero" means including a hetero atom in one compound or a substituent, and the hetero atom is one selected from the group consisting of N, O, S, P, and combinations thereof. can be For example, it may mean a case in which 1 to 3 hetero atoms are included in the one compound or substituent, and the remainder is carbon.

In one embodiment of the present invention, there is provided a novel bisphenyl pyrazine derivative organic light emitting compound represented by the following formula (a).

<Formula a>

In the above formula (a),

Ar ₁ is C1~ C60 alkyl group, C1~ C60 alkyloxy group, substituted or unsubstituted C6~ C60 aryl group, C5~ C60 aryloxy group, substituted or unsubstituted C3~ C60 N, O, A heteroaryl group containing S and Si, a C6~ C60 arylalkyl group, or a C3~ C60 cycloalkyl group, wherein _{the substituent when Ar 1} is substituted is deuterium, a cyano group, a nitrile group, a halogen group, a C1-C30 It is one selected from the group consisting of an alkyl group, a C1~ C30 alkyloxy group, a C6~ C60 aryl group, a C5~ C60 heteroaryl group, and combinations thereof,

L ₁ is a single bond, or includes substituted or unsubstituted C6~ C40 arylene, substituted or unsubstituted C10~ C40 condensed arylene, substituted or unsubstituted C5~ C40 N, O, S and Si is one selected from the group consisting of heteroarylene and combinations thereof; When L ₁ is substituted, the substituents are hydrogen, deuterium, a C1 to C40 alkyl group, a C1 to C40 alkyloxy group, a C6 to C40 aryl group, a C5 to C40 aryloxy group, a C5 to C40 heteroaryl group. and one selected from the group consisting of combinations thereof,

R ₁ and R ₂ are each independently hydrogen, deuterium, cyano group, nitrile group, halogen group, hydroxyl group, C1-C40 alkyl group, C1-C40 alkyloxy group, substituted or unsubstituted C6-C40 of an aryl group, a C5~ C40 aryloxy group, a substituted or unsubstituted C3~ C40 heteroaryl group including N, O, S and Si, a C6~ C40 arylalkyl group or a C3~ C40 cycloalkyl group, When the R ₁ and R ₂ are substituted, the substituent is hydrogen, deuterium, a cyano group, a nitrile group, a halogen group, a C1 to C40 alkyl group or a C6 to C40 aryl group, a C5 to C40 heteroaryl group, and combinations thereof is one selected from the group consisting of,

m and n are each independently an integer of 0-5.

Specifically, Ar ₁ may be any one compound selected from the group consisting of the following.

Wherein m and n are each independently an integer of 0 to 5,

X is C(R ₄ )(R ₅ ), Si(R ₄ )(R ₅ ), N(R ₆ ), S or O,

Z is S or O;

R ₃ is hydrogen, deuterium, cyano group, nitrile group, halogen group, hydroxyl group, C1~ C40 alkyl group, C1~ C40 alkyloxy group, substituted or unsubstituted C6~ C40 aryl group, C5~ C40 It is one selected from the group consisting of an aryloxy group, a substituted or unsubstituted C3~ C40 heteroaryl group including N, O, S and Si, a C6~ C40 arylalkyl group, or a C3~ C40 cycloalkyl group,

When Ar ₁ includes a plurality of R ₃ , each R ₃ is the same as or different from each other, and adjacent groups may be bonded to each other to form an aromatic ring together with the carbon bonded thereto,

o is an integer from 0 to 7,

p is an integer from 0 to 4,

q is an integer from 0 to 3,

r is an integer from 0 to 6,

s is an integer from 0 to 9,

t is an integer from 0 to 8,

The R ₄ and R ₅ are each independently a C1~ C40 alkyl group, a C1~ C40 alkyloxy group, a substituted or unsubstituted C6~ C40 aryl group, a substituted or unsubstituted C3~ C40 N, O, It is one selected from the group consisting of a heteroaryl group including S and Si, a C6~ C40 arylalkyl group or a C3~ C40 cycloalkyl group,

The R ₄ and R ₅ may combine with each other to form a spiro compound together with the fluorene to which they are bonded,

Wherein R ₆ is a C1~ C40 alkyl group, a C1~ C40 alkyloxy group, a substituted or unsubstituted C6~ C40 aryl group, a substituted or unsubstituted C3~ C40 N, O, S and a hetero containing Si One selected from the group consisting of an aryl group, a C6-C40 arylalkyl group, or a C3-C40 cycloalkyl group, and combinations thereof.

Specifically, R ₁ and R ₂ may each independently be any one compound selected from the group consisting of the following.

Specifically, L ₁ may be any one compound selected from the group consisting of:

For example, the bisphenyl pyrazine derivative organic light emitting compound may be any one of compounds 1 to 339 shown in Table 1 below.

[Table 1]

The bisphenyl pyrazine derivative organic light emitting compound may be used as a material for an emission layer, a hole blocking layer, an electron transport layer, or an electron injection layer among materials for an organic light emitting device.

In another embodiment of the present invention, in the organic electroluminescent device in which at least one organic thin film layer is sandwiched between a cathode and an anode, the organic thin film layer has a multilayer structure including at least one light emitting layer and an electron transport region, and the organic At least one layer in the thin film layer provides an organic electroluminescent device comprising the bisphenyl pyrazine derivative organic compound alone or a mixture of two or more.

The electron transport region is interposed between the cathode and the light emitting layer, and may include at least one of an electron injection layer, an electron transport layer, a functional layer having an electron injection function and an electron transport function at the same time, a buffer layer, and a hole blocking layer, which It may be appropriately selected depending on the required use.

At least one layer selected from the layers formed between the cathode and the anode provides an organic electroluminescent device comprising a vacuum deposition process or a solution process.

The detailed description of the bisphenyl pyrazine derivative organic light emitting compound represented by Formula (a) included in the organic thin film layer is the same as described above.

Hereinafter, Examples and Comparative Examples of the present invention will be described. The following examples are only examples of the present invention, and the present invention is not limited to the following examples.

(Example)

Hereinafter, although reaction examples and comparative examples are specifically illustrated, the present invention is not limited to the following reaction examples and examples. In the following reaction examples, intermediate compounds are indicated by adding a serial number to the number of the final product. For example, compound 1 is denoted as compound [1], and an intermediate compound of the compound is denoted as [1-1] or the like. In the present specification, the number of the compound is indicated by the compound number described in Table 1 above. For example, a compound indicated by '1' in Table 1 is indicated as 'Compound 1'.

[Synthesis Example 1] Preparation of compound [1]

Scheme 1

Preparation of intermediate compound [1-1]

1,3-dibromo-5-methoxybenzene 100g (376mmol), bispinacolatodiboron 238.7g (940mmol), potassium acetate 110.7g (1128mmol), [1,1'- 5.5 g (7.5 mmol) of bis (diphenylphosphino) ferrocene] palladium (II) dichloride and 1 L of 1,4-dioxane are added, and the mixture is stirred under reflux overnight. After completion of the reaction, the mixture was extracted with dichloromethane and distilled water, and the organic layer was treated with anhydrous magnesium sulfate and concentrated under reduced pressure. It was separated and purified by silica gel chromatography using ethyl acetate and hexane to prepare 92.2 g (68%) of the intermediate compound [1-1] as a white solid.

Preparation of intermediate compound [1-2]

Intermediate compound [1-1] 92.2g (256mmol), 2-bromo-5-phenylpyrazine 132.4g (563mmol), tetrakis(triphenylphosphine)palladium 5.9g (5.1mmol) in a 3L reaction flask under nitrogen atmosphere Then, 1.4L of 1,4-dioxane was added and the temperature was raised. At 60 ^o C, 384 ml of 2M aqueous potassium carbonate solution was added, and the mixture was stirred under reflux for 4 hours. After completion of the reaction, the precipitated solid was filtered and recrystallized using toluene to prepare 56.8 g (53%) of the white solid of the desired intermediate compound [1-2].

Preparation of intermediate compound [1-3]

56.8 g (136 mmol) of the intermediate compound [1-2] and 394.2 g (3.4 mol) of pyridine hydrochloride were added to a 3L reaction flask under a nitrogen atmosphere, and the mixture was stirred under reflux overnight. After completion of the reaction, extraction was performed with tetrahydrofuran and distilled water, and the organic layer was treated with anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. 51.3 g (94%) of the intermediate compound [1-3] as an off-white solid was prepared by recrystallization from tetrahydrofuran and hexane.

Preparation of intermediate compound [1-4]

51.3 g (127 mmol) of intermediate compound [1-3], 1 L of dichloromethane, and 20.7 ml (254 mmol) of pyridine are added to a 3 L reaction flask under a nitrogen atmosphere and stirred. 31.2ml (190mmol) of anhydrous trifluoromethanesulfone was slowly added dropwise at 0 ^{o C, and the mixture was stirred at room temperature overnight.} After completion of the reaction, 1 L of distilled water was added for extraction, and the organic layer was treated with anhydrous magnesium sulfate and then concentrated under reduced pressure. Recrystallization was performed using toluene to prepare 48.3 g (71%) of the intermediate compound [1-4] as a white solid.

Preparation of compound [1]

Intermediate compound [1-4] 10g (18.7mmol), 4-biphenylboronic acid 4.4g (22.4mmol), tetrakis(triphenylphosphine)palladium 0.4g (0.4mmol), toluene in a 500ml reaction flask under nitrogen atmosphere 200ml is added and the temperature is raised. At 60 ^o C, 18.7 ml of a 2M aqueous potassium carbonate solution and 18 ml of ethanol were added, and the mixture was stirred under reflux for 4 hours. After completion of the reaction, the precipitated solid was filtered and recrystallized using methanol and toluene to prepare 6.5 g (65%) of the target compound [1] as a white solid.

[Synthesis Example 2] Preparation of compound [18]

Scheme 2

Preparation of compound [18]

In the preparation of compound [1], 5.1 g (61%) of the target compound [18] as a white solid was prepared in the same manner except that 2-naphthyl boronic acid was used instead of 4-biphenylboronic acid.

[Synthesis Example 3] Preparation of compound [22]

Scheme 3

Preparation of compound [22]

7.4 g of the target compound [22] as a white solid synthesized in the same manner except that (4-(naphthalen-1-yl)phenyl)boronic acid was used instead of 4-biphenylboronic acid in the preparation of compound [1] (55%) was prepared.

[Synthesis Example 4] Preparation of compound [32]

Scheme 4

Preparation of intermediate compound [32-1]

In a 250 ml reaction flask under nitrogen atmosphere, 5 g (27.5 mmol) of 4-bromobenzonitrile, 5.9 g (28.8 mmol) of 4-chloro-1-naphthyl boronic acid, 0.6 g (0.5 mmol) of tetrakis (triphenylphosphine) palladium ), 1,4-dioxane 75ml is added and the temperature is raised. 27.5 ml of 2M potassium carbonate aqueous solution was added at 60 ^o C, and the mixture was stirred under reflux for 3 hours. It was extracted with ethyl acetate and distilled water, and the organic layer was treated with anhydrous magnesium sulfate and concentrated under reduced pressure. 6.1 g (84%) of the intermediate compound [32-1] as a white solid was prepared by separation and purification by silica gel chromatography using dichloromethane and hexane.

Preparation of intermediate compound [32-2]

In a 250ml reaction flask under nitrogen atmosphere, 6.1g (23.1mmol) of intermediate compound [32-1], 7.6g (30mmol) of bispinacolatodiboron, 6.7g (69.3mmol) of potassium acetate, 0.1g (0.5mmol) of palladium acetate, 0.4g (0.9mmol) of XPOS and 120ml of tetrahydrofuran are added, and the mixture is stirred under reflux overnight. After completion of the reaction, the mixture was extracted with dichloromethane and distilled water, and the organic layer was treated with anhydrous magnesium sulfate and concentrated under reduced pressure. It was separated and purified by silica gel chromatography using ethyl acetate and hexane to prepare 6.5 g (79%) of the intermediate compound [32-2] as a white solid.

Preparation of compound [32]

In the preparation of compound [1], 5.5 g (49%) of the target compound [32] as a white solid was prepared by synthesizing in the same manner except that the intermediate compound [32-2] was used instead of 4-biphenylboronic acid. .

[Synthesis Example 5] Preparation of compound [36]

Scheme 5

Preparation of compound [36]

In the production of the compound [1] 4-boronic acid instead of 4- (pyridin-3-yl), and the target compound as a white solid by synthesis by the same method [36] 5.9g (60, except for using phenylboronic acid %) was prepared.

[Synthesis Example 6] Preparation of compound [48]

Scheme 6

Preparation of intermediate compound [48-1]

In the preparation of the intermediate compound [32-2], 4-bromo-2,6-diphenylpyrimidine was used instead of the intermediate compound [32-1], and synthesized in the same manner as a white solid target intermediate compound [ 48-1] 7.2 g (87%) was prepared.

Preparation of compound [48]

8.2 g (66%) of the target compound [48] as a white solid was prepared by synthesizing in the same manner except that the intermediate compound [48-1] was used instead of 4-biphenylboronic acid in the preparation of compound [1] .

[Synthesis Example 7] Preparation of compound [54]

Scheme 7

Preparation of compound [54]

In the preparation of compound [1], 5.4 g (72%) of the target compound [54] as a white solid was prepared in the same manner except that quinoline-6-boronic acid was used instead of 4-biphenylboronic acid.

[Synthesis Example 8] Preparation of compound [67]

Scheme 8

Preparation of intermediate compound [67-1]

In the preparation of the intermediate compound [32-1], 2-bromo-4-phenylquinazoline instead of 4-bromobenzonitrile and (4-chlorophenyl)boronic acid instead of 4-chloro-1-naphthylboronic acid 4.6 g (83%) of the target intermediate compound [67-1] as a white solid was prepared by synthesizing in the same manner except that it was used.

Preparation of intermediate compound [67-2]

5.4 g of the target intermediate compound [67-2] as a white solid synthesized in the same manner except for using the intermediate compound [67-1] instead of the intermediate compound [32-1] in the synthesis of the intermediate compound [32-2] (91%) was prepared.

Preparation of compound [67]

5.3 g (60%) of the target compound [67] as a white solid was prepared by synthesizing in the same manner except that the intermediate compound [67-2] was used instead of 4-biphenylboronic acid in the preparation of compound [1] .

[Synthesis Example 9] Preparation of compound [89]

Scheme 9

Preparation of intermediate compound [89-1]

9-phenanthrene boronic acid 10g (45.0mmol), 3-bromo-5-chlorophenol 9.3g (45.0mmol), tetrakis(triphenylphosphine)palladium 0.5g (0.4mmol) in a 250ml reaction flask under nitrogen atmosphere , 100ml of 1,4-dioxane is added and the temperature is raised. At 60 ^o C, 33.7 ml of 2M aqueous potassium carbonate solution was added and stirred under reflux overnight. After completion of the reaction, extraction was performed with ethyl acetate and distilled water, and the organic layer was treated with anhydrous magnesium sulfate and concentrated under reduced pressure. 11.6 g (85%) of the intermediate compound [89-1] as a white solid was prepared by separation and purification by silica gel chromatography using dichloromethane and hexane.

Preparation of intermediate compound [89-2]

In a nitrogen atmosphere, 11.6 g (38.3 mmol) of intermediate compound [89-1], 232 ml of dichloromethane, and 6.3 ml (76.6 mmol) of pyridine were added to a 1L reaction flask and stirred. 9.5ml (57.5mmol) of anhydrous trifluoromethanesulfone was slowly added dropwise at 0 ^{o C, and the mixture was stirred at room temperature overnight.} After completion of the reaction, 400 ml of distilled water was added for extraction, and the organic layer was treated with anhydrous magnesium sulfate and then filtered with silica. The filtrate was concentrated under reduced pressure to prepare 16.2 g (97%) of the intermediate compound [89-2] as a pale yellow solid.

Preparation of intermediate compound [89-3]

Intermediate compound [89-2] 16.2g (37.1mmol), (2,6-dimethylpyridin-3-yl)boronic acid 6.2g (40.8mmol), tetrakis(triphenylphosphine) in a 1L reaction flask under nitrogen atmosphere 1.7 g (1.5 mmol) of palladium and 325 ml of toluene are added and the temperature is raised. At 60 ^o C, 74.2 ml of 2M aqueous potassium carbonate solution and 74.2 ml of ethanol were added and stirred under reflux for 4 hours. After completion of the reaction, extraction was performed with ethyl acetate and distilled water, and the organic layer was treated with anhydrous magnesium sulfate and then concentrated under reduced pressure. 13.6 g (93%) of the target intermediate compound [89-3] as a white solid was prepared by separation and purification by silica gel chromatography using ethyl acetate and hexane.

Preparation of intermediate compound [89-4]

The intermediate compound [32-2] prepared from the intermediate compound [32-1] The objective intermediate compound as a white solid which was synthesized in the same manner except that instead of using the intermediate compound [89-3] [89-4] 14.0g of (84%) was prepared.

Preparation of compound [89]

14.8 g (69%) of the target compound [89] as a white solid was prepared by synthesizing in the same manner except that the intermediate compound [89-4] was used instead of 4-biphenylboronic acid in the preparation of compound [1] .

[Synthesis Example 10] Preparation of compound [103]

Scheme 10

Preparation of intermediate compound [103-1]

In the preparation of the intermediate compound [32-1], 3-bromo-9,9-dimethyl-9H-fluorene instead of 4-bromobenzonitrile, 4-chloro-1-naphthyl boronic acid instead of (3-chloro 10.2 g (91%) of the target intermediate compound [103-1] as a white solid was prepared by synthesizing in the same manner except that phenyl) boronic acid was used.

Preparation of intermediate compound [103-2]

11.1 g of the target intermediate compound [103-2] as a white solid synthesized in the same manner except for using the intermediate compound [103-1] instead of the intermediate compound [32-1] in the preparation of the intermediate compound [32-2] (84%) was prepared.

Preparation of compound [103]

11.9 g (60%) of the target compound [103] as a white solid was prepared by synthesizing in the same manner except that the intermediate compound [103-2] was used instead of 4-biphenylboronic acid in the preparation of compound [1] .

[Synthesis Example 11] Preparation of compound [117]

Scheme 11

Preparation of compound [117]

In the preparation of compound [1], the target compound [117 as a white solid was synthesized in the same manner except that (9,9-diphenyl-fluoren-4-yl)boronic acid was used instead of 4-biphenylboronic acid. ] 8.1 g (71%) was prepared.

[Synthesis Example 12] Preparation of compound [128]

Scheme 12

Preparation of intermediate compound [128-1]

(5,5-dimethyl-5H-dibenzo[b,d]silol-3-yl)boronic acid 5g (19.7mmol), 3,5-dibromo-1,1'- in a 250ml reaction flask under nitrogen atmosphere Biphenyl 6.1g (19.7mmol), tetrakis(triphenylphosphine)palladium 0.5g (0.4mmol), and 1,4-dioxane 50ml were added and the temperature was raised. 19.7 ml of 2M potassium carbonate aqueous solution was added at 60 ^o C, and the mixture was stirred under reflux for 3 hours. After completion of the reaction, the mixture was extracted with dichloromethane and distilled water, and the organic layer was treated with anhydrous magnesium sulfate and concentrated under reduced pressure. 5.6 g (65%) of the intermediate compound [128-1] as a white solid was prepared by separation and purification by silica gel chromatography using dichloromethane and hexane.

Preparation of intermediate compound [128-2]

The compound [32-2] prepared from the intermediate compound [32-1] instead of the intermediate compound [128-1] and 5.7g purpose is the intermediate compound [128-2] as a white solid by synthesis by the same method except for using the ( 91%) was prepared.

Preparation of compound [128]

5.4 g (62%) of the target compound [128] as a white solid was prepared by synthesizing in the same manner except that the intermediate compound [128-2] was used instead of 4-biphenylboronic acid in the preparation of compound [1] .

[Synthesis Example 13] Preparation of compound [147]

Scheme 13

Preparation of intermediate compound [147-1]

(6-phenyldibenzo[b,d]furan-4 instead of (5,5-dimethyl-5H-dibenzo[b,d]silol-3-yl)boronic acid in the preparation of the intermediate compound [128-1] -yl) boronic acid was synthesized in the same manner except that 1,4-dibromobenzene was used instead of 3,5-dibromo-1,1'-biphenyl, and the target intermediate compound as a white solid [147] -1] 3.8 g (55%) was prepared.

Preparation of intermediate compound [147-2]

4.0 g of the target intermediate compound [147-2] as a white solid synthesized in the same manner except for using the intermediate compound [147-1] instead of the intermediate compound [32-1] in the preparation of the intermediate compound [32-2] (95%) was prepared.

Preparation of compound [147]

In the preparation of compound [1], 4.5 g (70%) of the target compound [147] as a white solid was prepared by synthesizing in the same manner except that the intermediate compound [147-2] was used instead of 4-biphenylboronic acid. .

[Synthesis Example 14] Preparation of compound [162]

Scheme 14

Preparation of intermediate compound [162-1]

In the preparation of the intermediate compound [128-1] (5,5-dimethyl-5H-dibenzo[b,d]silol-3-yl)boronic acid instead of (dibenzo[b,d]thiophen3-yl) Boronic acid was synthesized in the same way except that 2,6-dibromopyridin-4-ol was used instead of 3,5-dibromo-1,1'-biphenyl, and the target intermediate compound as a white solid [ 162-1] 9.5 g (61%) was prepared.

Preparation of intermediate compound [162-2]

Intermediate compound [162-1] 9.5g (26.7mmol), phenylboronic acid 3.9g (32.0mmol), tetrakis(triphenylphosphine)palladium 0.6g (0.5mmol), 1,4 in a 250ml reaction flask under nitrogen atmosphere -Add 95ml of dioxane and raise the temperature. 26.7 ml of 2M potassium carbonate aqueous solution was added at 60 ^{o C, and the mixture was stirred under reflux overnight.} After completion of the reaction, the mixture was extracted with dichloromethane and distilled water, and the organic layer was treated with anhydrous magnesium sulfate and concentrated under reduced pressure. 6.3 g (67%) of the intermediate compound [162-2] as a white solid was prepared by separation and purification by silica gel chromatography using ethyl acetate and hexane.

Preparation of intermediate compound [162-3]

6.8 g of the target intermediate compound [162-3] as a white solid synthesized in the same manner except that the intermediate compound [162-2] was used instead of the intermediate compound [89-1] in the preparation of the intermediate compound [89-2] (79%) was prepared.

Preparation of intermediate compound [162-4]

5.9 g of the target intermediate compound [162-4] as a white solid synthesized in the same manner except for using the intermediate compound [162-3] instead of the intermediate compound [32-1] in the preparation of the intermediate compound [32-2] (90%) was prepared.

Preparation of compound [162]

In the preparation of compound [1], 5.5 g (60%) of the target compound [162] as a white solid was prepared by synthesizing in the same manner except that the intermediate compound [162-4] was used instead of 4-biphenylboronic acid. .

[Synthesis Example 15] Preparation of compound [177]

Scheme 15

Preparation of intermediate compound [177-1]

In the preparation of the intermediate compound [32-2], 3-(4-bromophenyl)-9-phenyl-9H-carbazole was used instead of the intermediate compound [32-1], synthesized in the same manner as a white solid 5.1 g (92%) of the target intermediate compound [177-1] was prepared.

Preparation of compound [177]

In the preparation of compound [1], 6.3 g (78%) of the target compound [177] as a white solid was prepared by synthesizing in the same manner except that the intermediate compound [177-1] was used instead of 4-biphenylboronic acid. .

[Synthesis Example 16] Preparation of compound [193]

Scheme 16

Preparation of intermediate compound [193-1]

25g (138mmol) of 9H-fluoren-9-one, 52.2g (554mmol) of phenol, 120g (693mmol) of 3-bromophenol, 66.7g (693mmol) of methanesulfonic acid in a 1L reaction flask under nitrogen atmosphere, and 152 ^o C. Stir overnight. After completion of the reaction, 300 ml of ethanol was added and the precipitated solid was filtered. It was separated and purified by silica gel chromatography using ethyl acetate and hexane to prepare 12.1 g (21%) of the intermediate compound [193-1] as a white solid.

Preparation of intermediate compound [193-2]

Except for using the intermediate compound [193-1] instead of 4-bromobenzonitrile and (4-chlorophenyl)boronic acid instead of 4-chloro-1-naphthylboronic acid in the preparation of the intermediate compound [32-1] and synthesized in the same manner to prepare 11.1 g (85%) of the target intermediate compound [193-2] as a white solid.

Preparation of intermediate compound [193-3]

12.0 g of the target intermediate compound [193-3] as a white solid synthesized in the same manner except for using the intermediate compound [193-2] instead of the intermediate compound [32-1] in the preparation of the intermediate compound [32-2] (90%) was prepared.

Preparation of compound [193]

13.0 g (73%) of the target compound [193] as a white solid was prepared by synthesizing in the same manner except that the intermediate compound [193-3] was used instead of 4-biphenylboronic acid in the preparation of compound [1] .

[Synthesis Example 17] Preparation of compound [199]

Scheme 17

Preparation of intermediate compound [199-1]

In the preparation of the intermediate compound [32-2], the intermediate compound [32-1] was synthesized in the same manner except that 2-bromospiro [fluorene-9,9'-xanthene] was used instead of the intermediate compound [32-1]. 5.2 g (93%) of the intermediate compound [199-1] was prepared.

Preparation of compound [199]

5.3 g (65%) of the target compound [199] as a white solid was prepared by synthesizing in the same manner except that the intermediate compound [199-1] was used instead of 4-biphenylboronic acid in the preparation of compound [1] .

[Synthesis Example 18] Preparation of compound [213]

Scheme 18

Preparation of intermediate compound [213-1]

5g (23.5mmol) of 9H-thioxanthen-9-one and 100ml of tetrahydrofuran were added to a 250ml reaction flask under a nitrogen atmosphere and stirred. After the reaction ^{was cooled to -78 o} C, 9.8 ml of n-BuLi (2.5M in hexanes) was slowly added dropwise. After stirring for 30 minutes, 7.3 g (23.5 mmol) of 2,2'-dibromo-1,1'-biphenyl was added and stirred at room temperature. The resulting solid was filtered, an excess aqueous solution of sulfuric acid was added, and the mixture was stirred under reflux. After completion of the reaction, 100 ml of ethanol was added and the precipitated solid was filtered. 4.6 g (46%) of the intermediate compound [213-1] as a pale yellow solid was prepared by separation and purification by silica gel chromatography using ethyl acetate and hexane.

Preparation of intermediate compound [213-2]

4.5 g of the target intermediate compound [213-2] as a white solid synthesized in the same manner except for using the intermediate compound [213-1] instead of the intermediate compound [32-1] in the preparation of the intermediate compound [32-2] (87%) was prepared.

Preparation of compound [213]

3.5 g (51%) of the target compound [213] as a white solid was prepared by synthesizing in the same manner except that the intermediate compound [213-2] was used instead of 4-biphenylboronic acid in the preparation of compound [1] .

[Synthesis Example 19] Preparation of compound [224]

Scheme 19

Preparation of compound [224]

5,5-tetramethyl-2-(4-(10-phenylanthracen-9-yl)phenyl)-1,3,2-dioxaboro instead of 4-biphenylboronic acid in the preparation of compound [1] 5.9 g (67%) of the target compound [224] as a white solid was prepared by synthesizing in the same manner except that egg was used.

[Synthesis Example 20] Preparation of compound [229]

Scheme 20

Preparation of intermediate compound [229-1]

In the preparation of the intermediate compound [128-1], (triphenylen-2-yl)boronic acid was replaced with (5,5-dimethyl-5H-dibenzo[b,d]silol-3-yl)boronic acid, 3 ,5-dibromo-1,1'-biphenyl was synthesized in the same manner except that 3,3'-dibromo-1,1'-biphenyl was used instead of the target intermediate compound as a white solid [229] -1] 6.1 g (72%) was prepared.

Preparation of intermediate compound [229-2]

5.7 g of the target intermediate compound [229-2] as a white solid synthesized in the same manner except for using the intermediate compound [229-2] instead of the intermediate compound [32-1] in the preparation of the intermediate compound [32-2] (86%) was prepared.

Preparation of compound [229]

In the preparation of compound [1], 6.1 g (70%) of the target compound [229] as a white solid was prepared by synthesizing in the same manner except that the intermediate compound [229-2] was used instead of 4-biphenylboronic acid. .

[Synthesis Example 21] Preparation of compound [245]

Scheme 21

Preparation of intermediate compound [245-1]

In the preparation of the intermediate compound [128-1], 1-naphthylboronic acid instead of (5,5-dimethyl-5H-dibenzo[b,d]silol-3-yl)boronic acid, 3,5-dibro 6.7 g of the target intermediate compound [245-1] as a white solid synthesized in the same manner except that 1-(2-bromo-5-methoxyphenyl)ethanone was used instead of parent-1,1'-biphenyl (83%) was prepared.

Preparation of intermediate compound [245-2]

In a 250 ml reaction flask under a nitrogen atmosphere, 6.7 g (24.2 mmol) of the intermediate compound [245-1] and 67 ml of tetrahydrofuran were added and stirred. 26.3ml (78.9mmol) of methylmagnesium chloride (3.0M in THF) was slowly added dropwise at 0 ^{o C and stirred at room temperature overnight.} After completion of the reaction, the reactant is slowly added dropwise to 200 ml of distilled water. Extracted with ethyl acetate and distilled water, and the organic layer was treated with anhydrous magnesium sulfate and then concentrated under reduced pressure. The intermediate compound [245-2] as a white solid was prepared by separation and purification by silica gel chromatography using ethyl acetate and hexane (5.5 g (78%)).

Preparation of intermediate compound [245-3]

5.5 g (18.8 mmol) of intermediate compound [245-2] and 55 ml of dichloromethane were added to a 100 ml reaction flask under a nitrogen atmosphere and stirred. At 0 ^o C, 3.1 ml (47 mmol) of methanesulfonic acid was slowly added dropwise and stirred for 2 hours. After completion of the reaction, the mixture was extracted with dichloromethane and aqueous sodium chloride solution, and the organic layer was treated with anhydrous magnesium sulfate and then concentrated under reduced pressure. 4.4 g (85%) of the intermediate compound [245-3] as a white solid was prepared by separation and purification by silica gel chromatography using dichloromethane and hexane.

Preparation of intermediate compound [245-4]

4.4 g (16 mmol) of the intermediate compound [245-3] and 44 ml of dichloromethane were added to a 100 ml reaction flask under a nitrogen atmosphere and stirred. 2.6ml (27.2mmol) of boron tribromide was slowly added dropwise at 0 ^{o C and stirred at room temperature for 2 hours.} After completion of the reaction, the reactant was added dropwise to an aqueous sodium bicarbonate solution, followed by extraction with dichloromethane and distilled water. The organic layer was treated with anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from dichloromethane and hexane to prepare 4.0 g (96%) of the intermediate compound [245-4] as an off-white solid.

Preparation of intermediate compound [245-5]

5.1 g (85%) of the target compound [245-5] as a white solid synthesized in the same manner except that compound [245-4] was used instead of compound [89-1] in the synthesis of compound [89-2] was prepared.

Preparation of intermediate compound [245-6]

4.2 g of the target intermediate compound [245-6] as a white solid synthesized in the same manner except that the intermediate compound [245-5] was used instead of the intermediate compound [32-1] in the preparation of the intermediate compound [32-2] (88%) was prepared.

Preparation of compound [245]

4.3 g (61%) of the target compound [245] as a white solid was prepared by synthesizing in the same manner except that the intermediate compound [245-6] was used instead of 4-biphenylboronic acid in the preparation of compound [1] .

[Synthesis Example 22] Preparation of compound [278]

Scheme 22

Preparation of intermediate compound [278-1]

In the preparation of the intermediate compound [128-1], (2-methoxynaphthalen-1-yl)boronic acid was replaced with (5,5-dimethyl-5H-dibenzo[b,d]silol-3-yl)boronic acid , synthesized in the same manner except that 1-bromo-4-chloro-2-iodobenzene was used instead of 3,5-dibromo-1,1'-biphenyl, and the target intermediate compound as a white solid [278] -1] 5.4 g (63%) was prepared.

Preparation of intermediate compound [278-2]

4.7 g of the target intermediate compound [278-2] as an off-white solid synthesized in the same manner except for using the intermediate compound [278-1] instead of the intermediate compound [245-3] in the preparation of the intermediate compound [245-4] (90%) was prepared.

Preparation of intermediate compound [278-3]

In a 100 ml reaction flask under nitrogen atmosphere, 4.7 g (14 mmol) of intermediate compound [278-2], 47 ml of anhydrous N-methyl-2-pyrrolidone, and 3.9 g (28 mmol) of potassium carbonate were added and ^{stirred at 120 o} C for 4 hours. do. After completion of the reaction, extraction was performed with ethyl acetate and distilled water, and the organic layer was treated with anhydrous magnesium sulfate and then concentrated under reduced pressure. 2.9 g (82%) of the intermediate compound [278-3] as a white solid was prepared by separation and purification by silica gel chromatography using ethyl acetate and hexane.

Preparation of intermediate compound [278-4]

3.7 g of the target intermediate compound [278-4] as a white solid synthesized in the same manner except that the intermediate compound [278-3] was used instead of the intermediate compound [32-1] in the preparation of the intermediate compound [32-2] (95%) was prepared.

Preparation of compound [278]

4.8 g (73%) of the target compound [278] as a white solid was prepared by synthesizing in the same manner except that the intermediate compound [278-4] was used instead of 4-biphenylboronic acid in the preparation of compound [1] .

[Synthesis Example 23] Preparation of compound [310]

Scheme 23

Preparation of intermediate compound [310-1]

9-phenyl-2-(4,4,5; 5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole, 1-bromo-2 instead of 3,5-dibromo-1,1'-biphenyl - 4.4 g (89%) of the target intermediate compound [310-1] as a white solid was prepared by synthesizing in the same manner except that nitrobenzene was used.

Preparation of intermediate compound [310-2]

In a 100 ml reaction flask under a nitrogen atmosphere, 4.4 g (12.1 mmol) of the intermediate compound [310-1], 7.9 g (30.3 mmol) of triphenylphosphine, and 44 ml of 1,2-dichlorobenzene were added, and the mixture was stirred under reflux overnight. After completion of the reaction, the solvent was removed by concentration under reduced pressure, and separation and purification by silica gel chromatography using ethyl acetate and hexane were used to prepare 2.2 g (55%) of the target intermediate compound [310-2] as an off-white solid.

Preparation of compound [310]

2.8 g (59%) of the target compound [310] as a white solid was prepared by synthesizing in the same manner except that the intermediate compound [310-2] was used instead of 4-biphenylboronic acid in the preparation of compound [1] .

[Synthesis Example 24] Preparation of compound [335]

Scheme 24

Preparation of intermediate compound [335-1]

In the preparation of the intermediate compound [128-1], (3,5-dimethylphenyl)boronic acid was replaced with (3,5-dimethylphenyl)boronic acid instead of (5,5-dimethyl-5H-dibenzo[b,d]silol-3-yl)boronic acid, 6.6 g (60%) of the target intermediate compound [335-1] as a white solid synthesized in the same manner except that 2,5-dibromopyrazine was used instead of 5-dibromo-1,1'-biphenyl was prepared.

Preparation of intermediate compound [335-2]

In the preparation of the intermediate compound [1-2], the intermediate compound [335-1] was used instead of 2-bromo-5-phenylpyrazine, and synthesized in the same manner as a white solid target intermediate compound [335-2] 3.3 g (61%) were prepared.

Preparation of intermediate compound [335-3]

2.9 g of the target intermediate compound [335-3] as a white solid synthesized in the same manner except for using the intermediate compound [335-2] instead of the intermediate compound [1-2] in the preparation of the intermediate compound [1-3] (90%) was prepared.

Preparation of intermediate compound [335-4]

3.0 g of the target intermediate compound [335-4] as a white solid synthesized in the same manner except for using the intermediate compound [335-3] instead of the intermediate compound [1-3] in the preparation of the intermediate compound [1-4] (82%) was prepared.

Preparation of compound [335]

In the preparation of compound [1], 2.1 g (70%) of the target compound [335] as a white solid was prepared by synthesizing in the same manner except that the intermediate compound [335-4] was used instead of the intermediate compound [1-4] did

Compounds 1 to 339 were prepared according to the preparation methods of Synthesis Examples 1 to 24, and ¹ H NMR analysis results and mass spectrometry results for each prepared compound are shown in Table 2 below.

[Table 2]

comparative compound

<Comparative compound b>

<Comparative compound e>

[Synthesis Example 25] Preparation of comparative compound b

[Scheme 25]

Preparation of comparative compound b

In the above reaction scheme, in addition to using 4,4,5,5-tetramethyl-2-(10-phenylanthracen-9-yl)-1,3,2-dioxaborolane and 2-bromo-5-phenylpyrazine as starting materials, 224 7.08 g (70%) of the target compound [Comparative Compound b] was prepared in the same manner as in the preparation of the compound.

¹ H NMR (400 MHz, CDCl ₃ ): δ 9.21(s, 2H), 8.72(d, 2H), 8.02(m, 4H), 7.53~7.19(m, 12H)

MS/Q-Tof : 408 (M ⁺ )

[Synthesis Example 26] Preparation of comparative compound e

[Scheme 26]

Preparation of comparative compound e

8.1 g (75%) of the target compound [comparative compound e] was prepared in the same manner as in the synthesis of compound 229 except for using the intermediate compound [229-2] and 2-bromo-5-phenylpyrazine as starting materials in the above reaction scheme .

¹ H NMR (400 MHz, CDCl ₃ ): δ 9.21(s, 2H), 9.15(s, 1H), 9.02(d, 2H), 8.25~8.05(m, 6H), 7.91~7.72(m, 7H) , 7.67~7.38(m, 8H)

MS/Q-Tof : 534 (M ⁺ )

Comparative Example compound

<Formula c>

<Formula d>

<2-TNATA>

<α-NPD>

<BCP>

<Alq3>

Comparative Example 1

Compound c represented by Formula c is used as a fluorescent blue host, Compound d represented by Formula d is used as a fluorescent blue dopant, and 2-TNATA (4,4',4”-tris(N-naphthalen- 2-yl)-N-phenylamino)-triphenylamine) was used as the hole injection layer material, and α-NPD (N,N'-di(naphthalene-1-yl)-N,N'-diphenylbenzidine) was used as the hole transport layer material. It was prepared in an organic electroluminescent device having the following structure: use as: ITO / 2-TNATA (60 nm) / α-NPD (30 nm) / compound c + compound _{d (30 nm) / Alq 3} (25 nm )/Liq (1 nm)/Al (100 nm).

For the anode, a 15Ω/cm ² (1000Å) ITO glass substrate from Corning was cut into 25 mm x 25 mm x 0.7 mm and ultrasonically cleaned in acetone isopropyl alcohol and pure water for 15 minutes each, followed by 30 minutes. It was used after washing with UV ozone. A hole injection layer having a thickness of 60 nm was formed by vacuum deposition of 2-TNATA on the substrate. On the hole injection layer, α-NPD was vacuum deposited to form a hole transport layer with a thickness of 30 nm. A compound represented by Formula c and a compound represented by Formula d (doping rate: 4wt%) were vacuum-deposited on the hole transport layer to form a light emitting layer with a thickness of 30 nm. Then, the Alq ₃ compound was vacuum-deposited to a thickness of 25 nm on the light emitting layer to form an electron transport layer. An organic electroluminescent device was manufactured by sequentially vacuum-depositing 1 nm of Liq (electron injection layer) and 100 nm of Al (cathode) on the electron transport layer.

Comparative Example 2

In Comparative Example 1, by using the comparative compound b instead of the compound Alq3 in the electron transport layer, an organic electroluminescent device having the following structure was prepared: ITO/2-TNATA (60 nm)/α-NPD (30 nm) )/compound c+compound d (30 nm)/comparative compound b (25 nm)/Liq (1 nm)/Al (100 nm).

Comparative Example 3

The organic layer was formed in the same manner as in Comparative Example 1, except that the BCP 5 nm was deposited as a hole blocking layer compound on the light emitting layer to form a hole blocking layer, and Alq3 was vacuum deposited on the hole blocking layer to form an electron transport layer. An electroluminescent device was prepared.

ITO/2-TNATA (60 nm)/α-NPD (30 nm)/ Compound c + Compound d (30 nm)/ BCP (5 nm)/ Alq3 (25 nm)/ Liq (1 nm)/ Al (100 nm)

Comparative Example 4

The same method as in Comparative Example 1, except that 5 nm of Comparative Compound e as a hole blocking layer compound was deposited on the light emitting layer to form a hole blocking layer, and Alq3 was vacuum deposited on the hole blocking layer to form an electron transport layer. to prepare an organic electroluminescent device. ITO/2-TNATA (60 nm)/α-NPD (30 nm)/ Compound c + Compound d (30 nm)/ Comparative compound e (5 nm)/ Alq3 (25 nm)/ Liq (1 nm)/ Al (100 nm)

Examples 1-21

Compounds 1, 18, 22, 32, 36, 48, 54, 67, 89, 117, 128, 162, 177, 193, 199, 213, 224 synthesized as shown in Table 1 instead of Alq3 used as the electron transport layer , 245, 278, 310 or 335 was subjected to a sublimation purification process to prepare an organic electroluminescent device in the same manner as in Comparative Example 1, except that each was used as an electron transport layer. These are referred to as Examples 1 to 21, respectively.

Examples 22 to 24

An organic electroluminescent device was manufactured in the same manner as in Comparative Example 3, except that the compound BCP used as the hole blocking layer was used as the hole blocking layer by sublimation purification of the compounds 103, 147, and 229 disclosed in Table 1, respectively. did These are referred to as Examples 22 to 24, respectively.

Example 25

An organic light emitting diode was manufactured in the same manner as in Comparative Example 3, except that Compound 229 disclosed in Table 1 was used as a hole blocking layer instead of Compound BCP used as a hole blocking layer, and Compound 193 was used instead of Alq3 as an electron transport layer. did This is referred to as Example 25.

Evaluation Example 1: Evaluation of luminescent properties and lifetimes of Comparative Examples 1 to 4 and Examples 1 to 25

For Comparative Examples 1 to 4 and Examples 1 to 25, the luminescence peak and luminous efficiency were evaluated using Keithley sourcemeter “2400” and KONIKA MINOLTA “CS-2000”,

The time (LT98) for the luminance (L) to reach 98% was measured on the basis of the initial luminance (L _{0 ) 1000 nit using the M6000S life measuring device of McScience, and the results are shown in Table 3 and Figures 1 to} 3 is shown.

[Table 3]

As shown in Table 3, Examples 1 to 25 exhibited lower voltage driving and improved light emission characteristics compared to Comparative Examples 1 to 4. In addition, even when the hole blocking layer was included, it exhibited low voltage driving and improved light emitting characteristics and lifespan characteristics.

1 is a life-span characteristic evaluation graph showing the measurement results of the organic electroluminescent devices prepared in Examples 4, 5, 6, 7, and Comparative Examples 1 and 2;

2 is a lifespan characteristic evaluation graph showing the measurement results of the organic electroluminescent devices prepared in Examples 12, 13, 14, 15 and Comparative Examples 1 and 2;

3 is a life-span characteristic evaluation graph showing the measurement results for the organic electroluminescent devices prepared in Examples 22 to 25 and Comparative Examples 3 and 4;

As shown in Table 3, Examples 1 to 25 exhibited improved lifespan characteristics compared to Comparative Examples 1 to 4. In particular, the bisphenyl pyrazine derivatives improved the electron transport ability than the monophenyl pyrazine derivatives, and the organic light-emitting compounds of the bisphenyl pyrazine derivatives showed excellent performance and lifetime.

Although preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention as defined in the following claims are also presented. It belongs to the scope of the right of the invention.

Claims (9)

delete delete delete delete The bisphenyl pyrazine derivative organic light emitting compound of any one of the following 1 to 339.

6. The method of claim 5,
The organic light emitting compound is a bisphenyl pyrazine derivative organic light emitting compound used as a material for a light emitting layer, a hole blocking layer, an electron transport layer or an electron injection layer among materials for an organic light emitting device.
An organic electroluminescent device in which at least one organic thin film layer is sandwiched between a cathode and an anode, wherein the organic thin film layer has a multilayer structure including at least one light emitting layer and an electron transport region, and at least one layer in the organic thin film layer is The bisphenyl pyrazine derivative organic light emitting compound according to claim 5, comprising alone or a mixture of two or more
Organic electroluminescent device.
8. The method of claim 7,
The electron transport region is interposed between the cathode and the light emitting layer, and includes at least one of an electron injection layer, an electron transport layer, a functional layer having an electron injection function and an electron transport function at the same time, a buffer layer, and a hole blocking layer
Organic electroluminescent device.
8. The method of claim 7,
At least one layer selected from the layers formed between the cathode and the anode is formed by a vacuum deposition process or a solution process.
Organic electroluminescent device.

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