Compound and organic electroluminescent device containing the compound

Abstract

The present invention discloses a compound and its application as well as an organic electroluminescent device containing the compound. The compound is represented by the general formula (1): #imgabs0# wherein R1 to R 14 Each is independently selected from a hydrogen atom or a substituent, and at least one of them has a structure represented by the following general formula (2): #imgabs1# Such compounds provided by the present invention are used as hole transport layers and / or electron blocking layers of organic electroluminescent devices. By introducing compounds with flexible alkyl structures into the fluorene structure, the energy level and hole mobility of the material can be adjusted at the same time, so that the device can improve the luminous efficiency while maintaining a slightly lower driving voltage and a slightly longer life of the OLED.

Description

Technical Field

[0001] The invention relates to the technical field of organic electroluminescence, and in particular to a novel organic compound and application thereof, and an organic electroluminescence device containing the compound. Background Art

[0002] Organic light emitting devices (OLEDs) are current-driven thin-film devices with a sandwich-like structure, with a single or multiple layers of organic functional materials sandwiched between the anode and the cathode. Under the action of an electric field, the holes generated by the anode and the electrons generated by the cathode will move, and are injected into the hole transport layer and the electron transport layer respectively, and migrate to the light-emitting layer. When the two meet and recombine in the light-emitting layer, energy excitons are generated, thereby exciting the light-emitting molecules to finally produce visible light. OLEDs have the characteristics of self-luminescence, wide viewing angle, wide color gamut, short response time, high luminous efficiency, low operating voltage, low cost, and simple production process. They can be made into large-size and / or flexible ultra-thin panels. It is a new display technology that is developing rapidly and has a high degree of process integration. It has been widely used in display products such as televisions, smart phones, tablets, car displays, and lighting, and will be further used in creative display products such as large-size displays and flexible screens.

[0003] Organic optoelectronic materials used in OLED devices can be divided into light-emitting layer materials and auxiliary functional layer materials based on their uses. Among them, the light-emitting layer materials include guest materials (also known as light-emitting materials, doping materials) and host materials (also known as matrix materials). Light-emitting materials are divided into fluorescent materials, phosphorescent materials and thermally activated delayed fluorescent materials according to different energy transfer methods. Auxiliary functional layer materials are divided into electron injection materials, electron transport materials, hole blocking materials, electron blocking materials, hole transport materials and hole injection materials according to the different properties of electron or hole transmission speeds.

[0004] OLED devices used in display products are mainly composed of red, green and blue primary color devices constructed with different functional layers, which are controlled by circuits to achieve colorful products. Among the three primary color devices, blue light devices are the most difficult to develop, especially as the market has increasingly higher requirements for the performance of blue light. Usually, devices have three indicators: low voltage, high efficiency and long life. Through material and device optimization, two of the three indicators can be achieved, but the other indicator will be reduced. Therefore, how to achieve low voltage, high efficiency, long life and other indicators at the same time is the goal pursued by the industry.

[0005] Therefore, the art urgently needs to develop a class of OLED functional materials to obtain low-voltage, high-efficiency, and long-life devices. Based on this consideration, the present invention provides a compound that introduces a flexible alkyl structure into a fluorene structure, and can adjust the energy level and hole mobility of the material at the same time, so that the device can improve the efficiency while maintaining a slightly lower driving voltage and a slightly longer life of the OLED. This provides a feasible solution for obtaining high-performance blue light. Summary of the invention

[0006] In order to solve the above technical problems, the present invention provides: 1) a compound for an organic electroluminescent device, wherein the compound has a structure represented by the following general formula (1):

[0007]

[0008] Among them, R1~R 14 Each is independently selected from a hydrogen atom or a substituent, and at least one of them has a structure represented by the following general formula (2):

[0009]

[0010] X is selected from CR 15 R 16 、O、S、Se、NR 17 ,SiR 18 R 19 ; Y is selected from the group consisting of absence, single bond, CR 20 R 21 、O、S、Se、NR 22 、SiR 23 R 24 ; R 15 ~R 24 are each independently selected from a hydrogen atom or a substituent;

[0011] L is selected from a single bond, a substituted or unsubstituted arylene group, and a substituted or unsubstituted heteroarylene group;

[0012] Ar1 and Ar2 each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.

[0013] 2) The compound for an organic electroluminescent device according to 1), wherein L is selected from a single bond, and a substituted or unsubstituted arylene group.

[0014] 3) The compound for an organic electroluminescent device according to 1), wherein L is a single bond.

[0015] 4) The compound for an organic electroluminescent device according to 1), wherein R1 to R 24Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 ring carbon atoms.

[0016] 5) The compound for an organic electroluminescent device according to 1), wherein the "substituted" in the "substituted or unsubstituted" in the compound means that the substituent is independently selected from a deuterium atom, a tritium atom, a hydroxyl group, a monovalent alkyl group or a cycloalkyl group having 1 to 10 carbon atoms, a monovalent monocyclic aromatic group or a condensed aromatic group having 6 to 30 carbon atoms, and a monovalent heterocyclic group or a condensed heteroaryl group having 2 to 50 carbon atoms.

[0017] 6) The compound for an organic electroluminescent device according to 1), characterized in that the compound is selected from the following structures:

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026] 7) An organic electroluminescent device, comprising an anode, a cathode and at least one organic thin film between the anode and the cathode, wherein the organic thin film contains the compound for an organic electroluminescent device described in any one of 1) to 6).

[0027] 8) According to the organic electroluminescent device described in 7), the organic thin film includes any one of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, an exciton blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer, or a combination of at least two of them, and at least one of the hole transport layer, the electron blocking layer, and the light-emitting layer contains the compound for an organic electroluminescent device described in any one of 1) to 6).

[0028] 9) The organic electroluminescent device according to 8), wherein the compound for an organic electroluminescent device is used as a hole transport layer and / or an electron blocking layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The drawings described herein are used to provide a further understanding of the present application and constitute a part of the present application. The illustrative embodiments of the present application and their descriptions are used to explain the present application and do not constitute an improper limitation on the present application. In the drawings:

[0030] Figure 1 This is a schematic diagram of the structure of an organic electroluminescent device to which the compound of the present invention is applied, wherein the meanings of the various layers of the device structure are as follows:

[0031] 1. Transparent substrate layer, 2. ITO anode layer, 3. Hole injection layer, 4. Hole transport layer A, 5. Hole transport layer B (or electron blocking layer), 6. Light-emitting layer, 7. Electron transport layer B (or hole blocking layer), 8. Electron transport layer A, 9. Electron injection layer, 10. Cathode reflective electrode layer. DETAILED DESCRIPTION

[0032] The principles and features of the present invention are further illustrated below by taking a number of synthetic examples as examples. The examples given are only used to explain the present invention but are not used to limit the scope of the present invention.

[0033] The synthetic methods of the specific compounds of formula (1) listed below are all carried out in anhydrous solvents under a protective gas atmosphere unless otherwise stated.

[0034] Synthesis Example 1: Synthesis of Chemical 4

[0035]

[0036] A mixture of a4 (5.76 g, 20 mmol) and 20 mL of tetrahydrofuran was added dropwise to a 100 mL three-necked flask containing dry magnesium chips, a catalytic amount of iodine and 30 mL of tetrahydrofuran. After the addition was complete, the reaction was refluxed for 2 h. A mixture of 4-chloro-benzophenone b4 (4.32 g, 20 mmol) and 20 mL of tetrahydrofuran was slowly added dropwise to the prepared Grignard reagent. After the addition was complete, the reaction was refluxed overnight. The reaction solution was poured into a saturated ammonium chloride solution to quench the reaction, extracted with ethyl acetate three times, and the solvent was removed by rotary evaporation. After drying, it was directly used in the next step of the reaction.

[0037] The crude product from the previous step, 20 mL of hydrochloric acid and 40 mL of acetic acid were added to the reaction flask and reacted at 80°C for 2 h. After the reaction was completed, the mixture was poured into ice water and extracted with ethyl acetate three times. The solvent was removed by rotary evaporation, separated by silica gel column, eluted with ethyl acetate / petroleum ether (1:10), the solvent was dried by rotary evaporation, and vacuum dried to obtain 6.20 g of the target product M4 with a yield of 76%. The product was a white solid with a molecular weight of m / z=408.2 (M+H) as measured by mass spectrometry. + .

[0038] The intermediate M4 (4.08g, 10.0mmol), diphenylamine c4 (3.79g, 10.5mmol), tri(dibenzylideneacetone)dipalladium (0.18g, 0.2mmol), (1.92g, 20mmol) sodium tert-butoxide. The reaction system was ventilated three times and protected by nitrogen. Then, a syringe was used to add (0.8mL, 0.8mmol) of a toluene solution of tri-tert-butylphosphine (1mol / L) and 30ml of toluene. Under nitrogen protection, heated and stirred, refluxed at 120°C for 12h. Stop the reaction, cool to room temperature, add 100ml of deionized water, and extract three times with ethyl acetate. The solvent was removed by rotary evaporation, separated by a silica gel column, washed with dichloromethane / petroleum ether (1:10), the solvent was dried by spin drying, and vacuum dried to obtain 6.37g of the target product with a yield of 87%. White solid, mass spectrometry measured molecular weight of 733.2.

[0039] Synthesis Example 2: Synthesis of Chemical 6

[0040]

[0041] A mixture of a6 (6.44 g, 20 mmol) and 20 mL of tetrahydrofuran was added dropwise to a 100 mL three-necked flask containing dry magnesium chips, a catalytic amount of iodine and 30 mL of tetrahydrofuran. After the addition was complete, the reaction was refluxed for 2 h. A mixture of benzophenone b6 (3.62 g, 20 mmol) and 20 mL of tetrahydrofuran was slowly added dropwise to the prepared Grignard reagent. After the addition was complete, the reaction was refluxed overnight. The reaction solution was poured into a saturated ammonium chloride solution to quench the reaction, extracted three times with ethyl acetate, and the solvent was removed by rotary evaporation. After drying, it was directly used in the next step of the reaction.

[0042] The crude product from the previous step, 20 mL of hydrochloric acid and 40 mL of acetic acid were added to the reaction flask and reacted at 80°C for 2 h. After the reaction was completed, the mixture was poured into ice water and extracted with ethyl acetate three times. The solvent was removed by rotary evaporation, separated by silica gel column, eluted with ethyl acetate / petroleum ether (1:10), the solvent was dried by rotary evaporation, and vacuum dried to obtain 6.04 g of the target product M6 with a yield of 74%. The product was a white solid with a molecular weight of m / z=408.2 (M+H) as measured by mass spectrometry. + .

[0043] The intermediate M6 (4.08g, 10.0mmol), c6 (3.52g, 10.5mmol), tri(dibenzylideneacetone)dipalladium (0.18g, 0.2mmol), (1.92g, 20mmol) of sodium tert-butoxide. The reaction system was ventilated three times and protected by nitrogen. Then, a syringe was used to add (0.8mL, 0.8mmol) of a toluene solution of tri-tert-butylphosphine (1mol / L) and 30ml of toluene. Under nitrogen protection, heated and stirred, refluxed at 120°C for 12h. Stop the reaction, cool to room temperature, add 100ml of deionized water, and extract three times with ethyl acetate. The solvent was removed by rotary evaporation, separated by a silica gel column, rinsed with dichloromethane / petroleum ether (1:10), the solvent was dried by spin drying, and vacuum dried to obtain 5.80g of the target product with a yield of 82%. White solid, mass spectrometry measured molecular weight of 707.2.

[0044] Synthesis Example 3: Synthesis of Chemical 11

[0045]

[0046] A mixture of a11 (6.28 g, 20 mmol) and 20 mL of tetrahydrofuran was added dropwise to a 100 mL three-necked flask containing dry magnesium chips, a catalytic amount of iodine and 30 mL of tetrahydrofuran. After the addition was complete, the reaction was refluxed for 2 h. A mixture of 3-chloro-benzophenone b11 (4.32 g, 20 mmol) and 20 mL of tetrahydrofuran was slowly added dropwise to the prepared Grignard reagent. After the addition was complete, the reaction was refluxed overnight. The reaction solution was poured into a saturated ammonium chloride solution to quench the reaction, extracted with ethyl acetate three times, and the solvent was removed by rotary evaporation. After drying, it was directly used in the next step of the reaction.

[0047] The crude product from the previous step, 20 mL of hydrochloric acid and 40 mL of acetic acid were added to the reaction flask and reacted at 80°C for 2 h. After the reaction was completed, the mixture was poured into ice water and extracted with ethyl acetate three times. The solvent was removed by rotary evaporation, separated by silica gel column, eluted with ethyl acetate / petroleum ether (1:10), the solvent was dried by rotary evaporation, and vacuum dried to obtain 6.60 g of the target product M11 with a yield of 76%. The product was a white solid with a molecular weight of m / z=434.2 (M+H) as measured by mass spectrometry. + .

[0048] The intermediate M11 (4.34g, 10.0mmol), c11 (4.17g, 10.5mmol), tri(dibenzylideneacetone)dipalladium (0.18g, 0.2mmol), (1.92g, 20mmol) sodium tert-butoxide. The reaction system was ventilated three times and protected by nitrogen. Then, a syringe was used to add (0.8mL, 0.8mmol) of a toluene solution of tri-tert-butylphosphine (1mol / L) and 30ml of toluene. Under nitrogen protection, heated and stirred, refluxed at 120°C for 12h. Stop the reaction, cool to room temperature, add 100ml of deionized water, and extract three times with ethyl acetate. The solvent was removed by rotary evaporation, separated by a silica gel column, washed with dichloromethane / petroleum ether (1:10), the solvent was dried by spin drying, and vacuum dried to obtain 6.76g of the target product with a yield of 85%. White solid, mass spectrometry measured molecular weight of 795.4.

[0049] Synthesis Example 4: Synthesis of Chemical 17

[0050]

[0051] A mixture of a17 (7.64 g, 20 mmol) and 20 mL of tetrahydrofuran was added dropwise to a 100 mL three-necked flask containing dry magnesium chips, a catalytic amount of iodine and 30 mL of tetrahydrofuran. After the addition was complete, the reaction was refluxed for 2 h. A mixture of benzophenone b6 (3.62 g, 20 mmol) and 20 mL of tetrahydrofuran was slowly added dropwise to the prepared Grignard reagent. After the addition was complete, the reaction was refluxed overnight. The reaction solution was poured into a saturated ammonium chloride solution to quench the reaction, extracted three times with ethyl acetate, and the solvent was removed by rotary evaporation. After drying, it was directly used in the next step of the reaction.

[0052] The crude product from the previous step, 20 mL of hydrochloric acid and 40 mL of acetic acid were added to the reaction flask and reacted at 80°C for 2 h. After the reaction was completed, the mixture was poured into ice water and extracted with ethyl acetate three times. The solvent was removed by rotary evaporation, separated by silica gel column, eluted with ethyl acetate / petroleum ether (1:10), the solvent was dried by rotary evaporation, and vacuum dried to obtain 6.75 g of the target product M17 with a yield of 72%. The product was a white solid with a molecular weight of m / z=469.2 (M+H) as measured by mass spectrometry. + .

[0053] The intermediate M17 (4.34g, 10.0mmol), c17 (3.55g, 21.0mmol), tri(dibenzylideneacetone)dipalladium (0.18g, 0.2mmol), (1.92g, 20mmol) sodium tert-butoxide. The reaction system was ventilated three times and protected by nitrogen. Then, a syringe was used to add (0.8mL, 0.8mmol) of a toluene solution of tri-tert-butylphosphine (1mol / L) and 30ml of toluene. Under nitrogen protection, heated and stirred, refluxed at 120°C for 12h. Stop the reaction, cool to room temperature, add 100ml of deionized water, and extract three times with ethyl acetate. The solvent was removed by rotary evaporation, separated by a silica gel column, washed with dichloromethane / petroleum ether (1:10), the solvent was dried by rotary evaporation, and 5.95g of the target product was obtained with a yield of 81%. White solid, the molecular weight was 734.4 by mass spectrometry.

[0054] Synthesis Example 5: Synthesis of Chemical 22

[0055]

[0056] A mixture of a22 (6.96 g, 20 mmol) and 20 mL of tetrahydrofuran was added dropwise to a 100 mL three-necked flask containing dry magnesium chips, a catalytic amount of iodine and 30 mL of tetrahydrofuran. After completion of the addition, the reaction was refluxed for 2 h. A mixture of benzophenone b6 (3.62 g, 20 mmol) and 20 mL of tetrahydrofuran was slowly added dropwise to the prepared Grignard reagent. After completion of the addition, the reaction was refluxed overnight. The reaction solution was poured into a saturated ammonium chloride solution to quench the reaction, extracted three times with ethyl acetate, and the solvent was removed by rotary evaporation. After drying, it was directly used in the next step of the reaction.

[0057] The crude product from the previous step, 20 mL of hydrochloric acid and 40 mL of acetic acid were added to the reaction flask and reacted at 80°C for 2 h. After the reaction was completed, the mixture was poured into ice water and extracted with ethyl acetate three times. The solvent was removed by rotary evaporation, separated by silica gel column, eluted with ethyl acetate / petroleum ether (1:10), the solvent was dried by rotary evaporation, and vacuum dried to obtain 6.51 g of the target product M22 with a yield of 75%. The product was a white solid with a molecular weight of m / z=434.2 (M+H) as measured by mass spectrometry. + .

[0058] The intermediate M22 (4.34g, 10.0mmol), c22 (3.79g, 10.5mmol), tri(dibenzylideneacetone)dipalladium (0.18g, 0.2mmol), (1.92g, 20mmol) of sodium tert-butoxide. The reaction system was ventilated three times and protected by nitrogen. Then, a syringe was used to add (0.8mL, 0.8mmol) of a toluene solution of tri-tert-butylphosphine (1mol / L) and 30ml of toluene. Under nitrogen protection, heated and stirred, refluxed at 120°C for 12h. Stop the reaction, cool to room temperature, add 100ml of deionized water, and extract three times with ethyl acetate. The solvent was removed by rotary evaporation, separated by a silica gel column, washed with dichloromethane / petroleum ether (1:10), the solvent was dried by spin drying, and vacuum dried to obtain 6.31g of the target product with a yield of 83%. White solid, mass spectrometry measured molecular weight of 760.1.

[0059] Synthesis Example 6: Synthesis of Chemical 32

[0060]

[0061] A mixture of a11 (6.28 g, 20 mmol) and 20 mL of tetrahydrofuran was added dropwise to a 100 mL three-necked flask containing dry magnesium chips, a catalytic amount of iodine and 30 mL of tetrahydrofuran. After the addition was complete, the mixture was refluxed for 2 h. A mixture of 2-bromofluorenone b32 (5.18 g, 20 mmol) and 20 mL of tetrahydrofuran was slowly added dropwise to the prepared Grignard reagent. After the addition was complete, the mixture was refluxed for overnight. The reaction solution was poured into a saturated ammonium chloride solution to quench the reaction, extracted with ethyl acetate three times, and the solvent was removed by rotary evaporation. After drying, it was directly used in the next step of the reaction.

[0062] The crude product from the previous step, 20 mL of hydrochloric acid and 40 mL of acetic acid were added to the reaction flask and reacted at 80°C for 2 h. After the reaction was completed, the mixture was poured into ice water and extracted with ethyl acetate three times. The solvent was removed by rotary evaporation, separated by silica gel column, eluted with ethyl acetate / petroleum ether (1:10), the solvent was dried by rotary evaporation, and vacuum dried to obtain 7.24 g of the target product M32 with a yield of 76%. The product was a white solid with a molecular weight of m / z = 476.2 (M+H) as measured by mass spectrometry. + .

[0063] The intermediate M32 (4.76g, 10.0mmol), c22 (3.79g, 10.5mmol), tri(dibenzylideneacetone)dipalladium (0.18g, 0.2mmol), (1.92g, 20mmol) of sodium tert-butoxide. The reaction system was ventilated three times and protected by nitrogen. Then, a syringe was used to add (0.8mL, 0.8mmol) of a toluene solution of tri-tert-butylphosphine (1mol / L) and 30ml of toluene. Under nitrogen protection, heated and stirred, refluxed at 120°C for 12h. Stop the reaction, cool to room temperature, add 100ml of deionized water, and extract three times with ethyl acetate. The solvent was removed by rotary evaporation, separated by a silica gel column, washed with dichloromethane / petroleum ether (1:10), the solvent was dried by spin drying, and vacuum dried to obtain 6.37g of the target product with a yield of 84%. White solid, mass spectrometry measured molecular weight of 758.1.

[0064] Synthesis Example 7: Synthesis of Chemical 54

[0065]

[0066] A mixture of a11 (6.28 g, 20 mmol) and 20 mL of tetrahydrofuran was added dropwise to a 100 mL three-necked flask containing dry magnesium chips, a catalytic amount of iodine and 30 mL of tetrahydrofuran. After the addition was complete, the mixture was refluxed for 2 h. A mixture of 4-bromofluorenone b54 (5.18 g, 20 mmol) and 20 mL of tetrahydrofuran was slowly added dropwise to the prepared Grignard reagent. After the addition was complete, the mixture was refluxed overnight. The reaction solution was poured into a saturated ammonium chloride solution to quench the reaction, extracted with ethyl acetate three times, and the solvent was removed by rotary evaporation. After drying, it was directly used in the next step of the reaction.

[0067] The crude product from the previous step, 20 mL of hydrochloric acid and 40 mL of acetic acid were added to the reaction flask and reacted at 80°C for 2 h. After the reaction was completed, the mixture was poured into ice water and extracted with ethyl acetate three times. The solvent was removed by rotary evaporation, separated by silica gel column, eluted with ethyl acetate / petroleum ether (1:10), the solvent was dried by rotary evaporation, and vacuum dried to obtain 7.24 g of the target product M32 with a yield of 76%. The product was a white solid with a molecular weight of m / z = 476.2 (M+H) as measured by mass spectrometry. + .

[0068] The intermediate M54 (4.76g, 10.0mmol), c54 (4.21g, 10.5mmol), tri(dibenzylideneacetone)dipalladium (0.18g, 0.2mmol), (1.92g, 20mmol) of sodium tert-butoxide. The reaction system was ventilated three times and protected by nitrogen. Then, a syringe was used to add (0.8mL, 0.8mmol) of a toluene solution of tri-tert-butylphosphine (1mol / L) and 30ml of toluene. Under nitrogen protection, heated and stirred, refluxed at 120°C for 12h. Stop the reaction, cool to room temperature, add 100ml of deionized water, and extract three times with ethyl acetate. The solvent was removed by rotary evaporation, separated by a silica gel column, washed with dichloromethane / petroleum ether (1:10), the solvent was dried by spin drying, and vacuum dried to obtain 6.78g of the target product with a yield of 85%. White solid, mass spectrometry measured molecular weight of 798.1.

[0069] Synthesis Example 8: Synthesis of Chemical 117

[0070]

[0071] A mixture of a11 (6.28 g, 20 mmol) and 20 mL of tetrahydrofuran was added dropwise to a 100 mL three-necked flask containing dry magnesium chips, a catalytic amount of iodine and 30 mL of tetrahydrofuran. After the addition was complete, the mixture was refluxed for 2 h. A mixture of 2-bromofluorenone b32 (5.18 g, 20 mmol) and 20 mL of tetrahydrofuran was slowly added dropwise to the prepared Grignard reagent. After the addition was complete, the mixture was refluxed for overnight. The reaction solution was poured into a saturated ammonium chloride solution to quench the reaction, extracted with ethyl acetate three times, and the solvent was removed by rotary evaporation. After drying, it was directly used in the next step of the reaction.

[0072] The crude product from the previous step, 20 mL of hydrochloric acid and 40 mL of acetic acid were added to the reaction flask and reacted at 80°C for 2 h. After the reaction was completed, the mixture was poured into ice water and extracted with ethyl acetate three times. The solvent was removed by rotary evaporation, separated by silica gel column, eluted with ethyl acetate / petroleum ether (1:10), the solvent was dried by rotary evaporation, and vacuum dried to obtain 7.24 g of the target product M32 with a yield of 76%. The product was a white solid with a molecular weight of m / z = 476.2 (M+H) as measured by mass spectrometry. + .

[0073] The intermediate M32 (4.76g, 10.0mmol), c117 (4.63g, 10.5mmol), tri(dibenzylideneacetone)dipalladium (0.18g, 0.2mmol), (2.76g, 20mmol) potassium carbonate, 30ml toluene and 10mL water were used to evacuate the reaction system three times and nitrogen was protected. Then (0.8mL, 0.8mmol) tri-tert-butylphosphine toluene solution (1mol / L) was added with a syringe. Under nitrogen protection, heated and stirred, refluxed at 120℃ for 12h. Stop the reaction, cool to room temperature, add 100ml deionized water, and extract three times with ethyl acetate. The solvent was removed by rotary evaporation, separated by silica gel column, washed with dichloromethane / petroleum ether (1:10), the solvent was dried by rotary evaporation, and vacuum dried to obtain 6.98g of the target product with a yield of 88%. White solid, mass spectrometry measured molecular weight of 794.1.

[0074] Synthesis Example 9: Synthesis of Chemical 128

[0075]

[0076] A mixture of a128 (6.44 g, 20 mmol) and 20 mL of tetrahydrofuran was added dropwise to a 100 mL three-necked flask containing dry magnesium chips, a catalytic amount of iodine and 30 mL of tetrahydrofuran. After the addition was complete, the mixture was refluxed for 2 h. A mixture of fluorenone b128 (3.60 g, 20 mmol) and 20 mL of tetrahydrofuran was slowly added dropwise to the prepared Grignard reagent. After the addition was complete, the mixture was refluxed for overnight. The reaction solution was poured into a saturated ammonium chloride solution to quench the reaction, extracted with ethyl acetate three times, and the solvent was removed by rotary evaporation. After drying, it was directly used in the next step of the reaction.

[0077] The crude product from the previous step, 20 mL of hydrochloric acid and 40 mL of acetic acid were added to the reaction flask and reacted at 80°C for 2 h. After the reaction was completed, the mixture was poured into ice water and extracted with ethyl acetate three times. The solvent was removed by rotary evaporation, separated by silica gel column, eluted with ethyl acetate / petroleum ether (1:10), the solvent was dried by rotary evaporation, and vacuum dried to obtain 6.25 g of the target product M128 with a yield of 77%. The product was a white solid with a molecular weight of m / z=407.1 (M+H) as measured by mass spectrometry. + .

[0078] The intermediate M128 (4.07g, 10.0mmol), c128 (5.05g, 10.5mmol), tri(dibenzylideneacetone)dipalladium (0.18g, 0.2mmol), (2.76g, 20mmol) potassium carbonate, 30ml toluene and 10mL water were used to evacuate the reaction system three times and nitrogen was protected. Then (0.8mL, 0.8mmol) tri-tert-butylphosphine toluene solution (1mol / L) was added with a syringe. Under nitrogen protection, heated and stirred, refluxed at 120℃ for 12h. Stop the reaction, cool to room temperature, add 100ml deionized water, and extract three times with ethyl acetate. The solvent was removed by rotary evaporation, separated by silica gel column, washed with dichloromethane / petroleum ether (1:10), the solvent was dried by spin drying, and vacuum dried to obtain 7.19g of the target product with a yield of 89%. White solid, mass spectrometry measured molecular weight of 808.0.

[0079] Synthesis Example 10: Synthesis of Chemical 149

[0080]

[0081] A mixture of a22 (7.00 g, 20 mmol) and 20 mL of tetrahydrofuran was added dropwise to a 100 mL three-necked flask containing dry magnesium chips, a catalytic amount of iodine and 30 mL of tetrahydrofuran. After the addition was complete, the mixture was refluxed for 2 h. A mixture of b149 (3.92 g, 20 mmol) and 20 mL of tetrahydrofuran was slowly added dropwise to the prepared Grignard reagent. After the addition was complete, the reaction was refluxed overnight. The reaction solution was poured into a saturated ammonium chloride solution to quench the reaction, extracted with ethyl acetate three times, and the solvent was removed by rotary evaporation. After drying, it was directly used in the next step.

[0082] The crude product from the previous step, 20 mL of hydrochloric acid and 40 mL of acetic acid were added to the reaction flask and reacted at 80°C for 2 h. After the reaction was completed, the mixture was poured into ice water and extracted with ethyl acetate three times. The solvent was removed by rotary evaporation, separated by silica gel column, eluted with ethyl acetate / petroleum ether (1:10), the solvent was dried by rotary evaporation, and vacuum dried to obtain 6.56 g of the target product M149 with a yield of 73%. The product was a white solid with a molecular weight of m / z=448.2 (M+H) as measured by mass spectrometry. + .

[0083] The intermediate M149 (4.48g, 10.0mmol), c149 (3.37g, 10.5mmol), tri(dibenzylideneacetone)dipalladium (0.18g, 0.2mmol), (1.92g, 20mmol) sodium tert-butoxide. The reaction system was ventilated three times and protected by nitrogen. Then, a syringe was used to add (0.8mL, 0.8mmol) of a toluene solution of tri-tert-butylphosphine (1mol / L) and 30ml of toluene. Under nitrogen protection, heated and stirred, refluxed at 120°C for 12h. Stop the reaction, cool to room temperature, add 100ml of deionized water, and extract three times with ethyl acetate. The solvent was removed by rotary evaporation, separated by a silica gel column, washed with dichloromethane / petroleum ether (1:10), the solvent was dried by spin drying, and vacuum dried to obtain 6.17g of the target product with a yield of 84%. White solid, mass spectrometry measured molecular weight of 733.4.

[0084] Similar reactions can be used to prepare the following compounds:

[0085] Table 1

[0086]

[0087]

[0088]

[0089]

[0090]

[0091] Table 2 Materials used for OLED

[0092]

[0093] Device Example 1:

[0094] ITO(130) / HATCN(15) / Chemical 4(60) / EBL(5) / BH:BD(20, 2 wt%) / HBL(5) / ETL:Liq(30, 50 wt%) / Liq(1) / Al(80).

[0095] The difference between device examples 2-20 and device example 1 is that the compound 4 of the present invention used in the hole transport layer is replaced by other compounds of the present invention, as shown in Table 3 for details.

[0096] Comparative Examples 1 to 3:

[0097] Compared with device embodiment 1, this comparative example is different in that the HTL in the organic electroluminescent device is changed to one that is well known in the industry and has been commercially applied. The obtained device performance test data is shown in Table 3.

[0098] The OLEDs were characterized by standard methods. For this purpose, the electroluminescence spectrum, the current efficiency (measured in cd / A), the power efficiency (measured in lm / W) and the external quantum efficiency (EQE, measured in %) were determined, which were calculated as a function of the luminous density from a current / voltage / luminous density characteristic line (IUL characteristic line) exhibiting Lambertian emission characteristics. 2 The required voltage V1000 is determined at the brightness of 1000cd / m 2 Finally, EQE1000 means the current efficiency achieved at 1000cd / m 2 External quantum efficiency at working brightness, T90 means the device is at 1000cd / m 2 The device performances of Examples 1 to 20 of the present invention and Comparative Examples 1 to 3 are summarized in Table 3.

[0099] Table 3

[0100]

[0101]

[0102] As can be seen from Table 3, compared with the prior art, using one of the materials of the present invention, the device can improve efficiency while maintaining a slightly lower driving voltage and slightly longer life of the OLED. For example, compared with Comparative Example 2, the CE1000 of the device Example 7 where Chemical 48 is located is increased by 11.8%, and the life is increased by 12%.

[0103] It can be seen from Table 3 that the introduction of a flexible alkyl structure into the fluorene structure can adjust the energy level and hole mobility of the material, and can be better matched with the electron blocking layer, which can ensure efficient hole injection and transmission, and avoid device deterioration caused by hole aggregation at the interface between the electron blocking layer and the light-emitting layer; thus, the efficiency and life of the device can be effectively improved. This provides a feasible solution for obtaining high-performance blue light.

Claims

1. A compound for an organic electroluminescent device, characterized in that: The compound has a structure represented by the following general formula (1): Among them, R1~R 14 Each is independently selected from a hydrogen atom or a substituent, and at least one of them has a structure represented by the following general formula (2): X is selected from CR 15 R 16 , O; Y is selected from the group consisting of not existing, single bond; R 15 , R 16 Each is independently selected from an unsubstituted alkyl group having 1 to 50 carbon atoms; L is selected from a single bond; Ar1 and Ar2 each independently represent an unsubstituted aryl group or an unsubstituted heteroaryl group; R1~R 14 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 ring carbon atoms; The "substituted" in "substituted or unsubstituted" in the above compound means that the substituent is independently selected from a deuterium atom, a tritium atom, a hydroxyl group, a monovalent alkyl group or cycloalkyl group having 1 to 10 carbon atoms, a monovalent monocyclic aromatic group or condensed aromatic group having 6 to 30 carbon atoms, and a monovalent heterocyclic group or condensed heteroaryl group having 2 to 50 carbon atoms.

2. The compound for an organic electroluminescent device according to claim 1, characterized in that The compound is selected from the following structures:

3. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises an anode, a cathode and at least one organic thin film between the anode and the cathode, wherein the organic thin film contains the compound for an organic electroluminescent device according to any one of claims 1 to 2.

4. The organic electroluminescent device according to claim 3, characterized in that: The organic film comprises any one of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, an exciton blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer, or a combination of at least two of them, and at least one of the hole transport layer, the electron blocking layer, and the light-emitting layer contains the compound for an organic electroluminescent device described in any one of claims 1 to 2.

5. The organic electroluminescent device according to claim 4, characterized in that: The compound for an organic electroluminescent device is used as a hole transport layer and / or an electron blocking layer.

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