CN112062775A - Organic electroluminescent material and preparation method and application thereof - Google Patents

Organic electroluminescent material and preparation method and application thereof Download PDF

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CN112062775A
CN112062775A CN202010986637.8A CN202010986637A CN112062775A CN 112062775 A CN112062775 A CN 112062775A CN 202010986637 A CN202010986637 A CN 202010986637A CN 112062775 A CN112062775 A CN 112062775A
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林存生
高斌
付少邦
慈振华
石宇
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Valiant Co Ltd
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Abstract

The invention relates to an organic electroluminescent material and a preparation method and application thereof, wherein the organic electroluminescent material is shown as the following formula I:
Figure DDA0002689486990000011
wherein, R is1And R2Same or different, said R1And R2Simultaneously or partially present, said R1And R2One selected from hydrogen and a substituted or unsubstituted aromatic heterocyclic group containing at least one of N, S, O and having 4 to 36 carbon atoms. The organic photoelectric material has the characteristics of difficult intermolecular crystallization, difficult aggregation and good film forming property,and the 3D rigid structure in the molecule can improve the thermal stability of the luminescent material, and the luminescent material is applied to an organic electroluminescent device as the luminescent material, so that the maximum current efficiency of the organic electroluminescent device is improved, the turn-on voltage of the organic electroluminescent device is reduced, and the service life of the organic electroluminescent device is greatly prolonged.

Description

Organic electroluminescent material and preparation method and application thereof
Technical Field
The invention relates to an organic electroluminescent material and a preparation method and application thereof, belonging to the technical field of organic luminescent materials.
Background
The origin of Organic Light Emitting Diode (OLED) is traced back to the sixties of the twentieth century, and Pope et al use anthracene single crystal to emit light by applying dc voltage, but the driving voltage is high (100V) and the light emitting brightness and efficiency are low, so that much attention is not paid. With the continuous improvement of the technology, in 1987, 8-hydroxyquinoline aluminum (AIq3) is used as a luminescent material by C.W.Tang et al of Kodak company, and an OLED with a double-layer sandwich structure is manufactured by a vacuum evaporation method, the starting voltage is only a few volts, and the brightness can reach as high as 1000cd/m2Therefore, the marking OLED has taken an important step toward practical application, and thus becomes an important milestone in the field of organic electroluminescence.
Currently, research on the improvement of the performance of OLEDs includes: the driving voltage of the device is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the like. In order to realize the continuous improvement of the performance of the OLED, not only the structure of the OLED and the innovation of the manufacturing process of the OLED are required, but also the photoelectric material used in the OLED needs to be continuously researched and innovated, so that a photoelectric functional material with higher performance and applied to the OLED is created.
The butterfly structure is an aromatic molecule with a unique three-dimensional rigid structure formed by three aromatic rings. There are well-defined angles between each 2 aromatic rings, forming 3 open electron-rich cavities. And it also has large intramolecular cavities also known as internal free volume and rigid spherical steric aromatic structure symmetric to D3 h.
In the current research situation, the butterfly-structure organic materials are modified as organic photoelectric materials to be amorphous materials with high stability, and the preparation method is complicated.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the organic electroluminescent material which has the characteristics of difficult intermolecular crystallization, difficult aggregation and good film forming property, and the rigid group in the molecule can improve the thermal stability of the material.
The technical scheme for solving the technical problems is as follows: an organic electroluminescent material, wherein the organic electroluminescent material is represented by the following formula I:
Figure BDA0002689486970000021
wherein, R is1And R2Same or different, said R1And R2Simultaneously or partially present, said R1And R2One selected from hydrogen and a substituted or unsubstituted aromatic heterocyclic group containing at least one of N, S, O and having 4 to 36 carbon atoms.
Further, the organic electroluminescent material is shown as the following formulas II, III and IV:
Figure BDA0002689486970000022
wherein, R is1And R2Same or different, said R1And R2Simultaneously or partially present, said R1And R2Selected from substituted or unsubstituted polycyclic conjugated aryl containing 4-36 carbon atoms, or R1And R2And one selected from substituted or unsubstituted aromatic heterocyclic groups containing at least one of N, S, O and having 4 to 36 carbon atoms.
Further, said R1And R2Any one selected from the following groups:
Figure BDA0002689486970000023
Figure BDA0002689486970000031
Figure BDA0002689486970000032
denotes the bonding site.
Further, the organic electroluminescent material is any one of the following structural formulas D01-D52:
Figure BDA0002689486970000033
Figure BDA0002689486970000041
Figure BDA0002689486970000051
the invention has the beneficial effects that: the invention provides an organic electroluminescent material containing a butterfly structure, which has the characteristics of difficult crystallization and aggregation among molecules and good film forming property, and rigid groups in the molecules can improve the thermal stability of the material.
The invention also discloses a preparation method of the organic electroluminescent material, which comprises the following steps:
(1) under the protection of inert gas, adding a raw material 1, titanium tetrachloride and an organic solvent into a reaction system, slowly adding ethoxy oxalyl chloride at the temperature of-20-50 ℃, keeping the temperature and stirring for 1-8.0 hrs, pouring into dilute hydrochloric acid to quench after the reaction is finished, thus obtaining the reaction system containing an intermediate 1, wherein the organic solvent is selected from one or more of dichloromethane, chloroform and dichloroethane, the raw material 1 is shown as the following formula 1, and the intermediate 1 is shown as the following formula 2;
Figure BDA0002689486970000052
(2) adding the intermediate 1 obtained in the step (1) and N-bromosuccinimide (NBS) into an organic solvent, reacting for 1-10.0 hrs at 0-80 ℃ under the protection of inert gas, pouring into an aqueous solution of sodium bisulfite, and quenching to obtain a reaction system containing an intermediate 2, wherein the organic solvent is selected from one or more of dichloromethane, chloroform and dichloroethane, and the intermediate 2 is represented by the following formula 3;
Figure BDA0002689486970000061
(3) adding the intermediate 2 obtained in the step (2) and an alkaline substance into an organic solvent, and adding trifluoromethanesulfonyl chloride to react for 1-12.0 hrs at-10-60 ℃ under the protection of inert gas to obtain a reaction system containing an intermediate 3, wherein the alkaline substance is selected from one or more of triethylamine, diisopropylethylamine, pyridine and N, N-dimethylpyridine-4-amine, the organic solvent is selected from one or more of dichloromethane, trichloromethane, dichloroethane or toluene, and the intermediate 3 is shown in the following formula 4;
Figure BDA0002689486970000062
(4) adding the intermediate 3 obtained in the step (3), the raw material 2 and an alkaline substance into an organic solvent, adding a catalyst into the system under the protection of inert gas, and reacting at 60-150 ℃ for 3-12.0 hrs to obtain a reaction system containing an intermediate 4, wherein the alkaline substance is one or more of potassium carbonate, sodium carbonate, potassium phosphate and potassium hydroxide, the catalyst is a palladium-containing catalyst and an organic phosphine ligand, and the palladium-containing catalyst is Pd (OAc)2、Pd(PPh3)4、Pd(PPh3)2Cl2And Pd (dpp)f)Cl2One or more of triphenylphosphine, DPPP (CAS-RN: 6737-42-4), Xantphos (CAS-RN: 161265-03-8), Sphos (CAS-RN: 657408-07-6), P (t-Bu)3·HBF4(CAS-RN: 113978-91-9) by one or more of the following formula 5, wherein X is selected from hydrogen or bromine atom, and formula 6 is shown as intermediate 4;
Figure BDA0002689486970000063
(5) adding the intermediate 4 obtained in the step (4) and an alkaline substance into an organic solvent, and reacting for 1-12.0 hrs at 60-150 ℃ under the protection of inert gas to obtain a reaction system containing an intermediate 5, wherein the alkaline substance is one or more selected from potassium hydroxide, sodium hydroxide and sodium ethoxide, and the intermediate 5 is shown as the following formula 7;
Figure BDA0002689486970000071
(6) adding the intermediate 5 obtained in the step (5) and N, N-carbonyl diimidazole into an organic solvent, and reacting for 1-24.0 hrs at-20-60 ℃ under the protection of inert gas; and then adding titanium tetrachloride at the temperature of-20-60 ℃, reacting for 1-12.0 hrs under heat preservation, pouring into dilute hydrochloric acid, and quenching to obtain a reaction system containing an intermediate 6, wherein the organic solvent is one or more selected from dichloromethane, dichloroethane and chloroform, and the intermediate 6 is shown as the following formula 8.
Figure BDA0002689486970000072
(7) Adding the intermediate 6 obtained in the step (6) into an organic solvent, adding a 1-naphthyl magnesium bromide/4-methyl dihydropyran solution at-20-60 ℃ under the protection of inert gas, and reacting for 1-24.0 hrs at-20-60 ℃; then pouring into diluted hydrochloric acid for quenching to obtain a reaction system containing an intermediate 7, wherein the organic solvent is selected from one or more of THF and 4-methyl dihydropyran, and the intermediate 7 is shown as the following formula 9;
Figure BDA0002689486970000073
(8) adding the intermediate 7 obtained in the step (7) into an organic solvent, adding trifluoromethanesulfonic acid under the protection of inert gas, and reacting at 30-150 ℃ for 1-24.0 hrs to obtain a reaction system containing an intermediate 8, wherein the organic solvent is one or more selected from toluene and xylene, and the intermediate 8 is represented by the following formula 10;
Figure BDA0002689486970000081
(9) under the protection of inert gas, adding the intermediate 8 obtained in the step (8), an aromatic secondary amine compound, an alkaline substance and a reaction solvent into a reaction system, adding a catalyst into the system, and reacting for 1-30.0 hrs at the temperature of 50-150 ℃ to obtain the reaction system containing the organic photoelectric material, wherein the alkaline substance is one or more of sodium tert-butoxide, sodium tert-amylate and potassium tert-butoxide; the catalyst is a palladium-containing catalyst and an organic phosphine ligand, and the palladium-containing catalyst is Pd (OAc)2、Pd(PPh3)4、Pd(PPh3)2Cl2And Pd (dppf) Cl2The organic phosphine ligand is one or more of triphenylphosphine, DPPP (CAS-RN: 6737-42-4), Xantphos (CAS-RN: 161265-03-8), Sphos (CAS-RN: 657408-07-6), P (t-Bu)3 HBF4 (CAS-RN: 113978-91-9) or a mixture of more.
Preferably, in the step (1), the organic solvent is selected from dichloromethane, chloroform or dichloroethane, and the molar ratio of the amount of the raw material 1 to the amount of the titanium tetrachloride is that the raw material 1: titanium tetrachloride is 1: 1.0-1.5, wherein the molar ratio of the dosage of the raw material 1 to the dosage of the ethoxy oxalyl chloride is that the raw material 1: ethoxyoxalyl chloride ═ 1: 1.0 to 1.5;
in the step (2), the organic solvent is selected from dichloromethane, chloroform or dichloroethane, and the molar ratio of the dosage of the intermediate 1 to the dosage of the N-bromosuccinimide (NBS) is that the intermediate 1: n-bromosuccinimide ═ 1: 0.9 to 1.1;
in the step (3), the organic solvent is selected from dichloromethane, chloroform, dichloroethane or toluene, the basic substance is selected from triethylamine, diisopropylethylamine, pyridine or N, N-dimethylpyridine-4-amine, and the molar ratio of the amount of the intermediate 2 to the amount of the basic substance is that the intermediate 2: basic substance 1.0: 1.0-1.5, wherein the molar ratio of the using amount of the intermediate 2 to the using amount of the trifluoromethanesulfonyl chloride is that the intermediate 2: trifluoromethanesulfonyl chloride ═ 1: 1.0 to 1.5;
in the step (4), the organic solvent is selected from tetrahydrofuran, dioxane, toluene, xylene or trimethylbenzene, and the molar ratio of the amount of the intermediate 3 to the amount of the raw material 2 is that the intermediate 3: raw material 2 is 1: 1.0-1.2, wherein the molar ratio of the using amount of the intermediate 3 to the using amount of the alkaline substance is that the intermediate 3: basic substance 1: 1.0-3.0, wherein the molar ratio of the using amount of the intermediate 3 to the using amount of the catalyst is that the intermediate 3: catalyst 1: 0.001-0.1, wherein the molar ratio of the dosage of the palladium-containing catalyst to the dosage of the organic phosphine ligand is as follows: organophosphine ligand ═ 1: 0.5 to 4;
in the step (5), the organic solvent is selected from methanol, ethanol or isopropanol, and the molar ratio of the amount of the intermediate 4 to the amount of the alkaline substance is that the intermediate 4: basic substance 1: 1.0 to 2.0;
in step (6), the organic solvent is selected from dichloromethane, dichloroethane or chloroform, and the molar ratio of the amount of the intermediate 5 to the amount of the N, N-carbonyldiimidazole is intermediate 5: n, N-carbonyldiimidazole ═ 1: 1.5-3.0, wherein the molar ratio of the amount of the intermediate 5 to the amount of the titanium tetrachloride is that the intermediate 5: titanium tetrachloride is 1: 3.0 to 5.0;
in step (7), the organic solvent is selected from THF or 4-methyl dihydropyran, and the molar ratio of the amount of the intermediate 6 to the amount of the 1-naphthyl magnesium bromide is intermediate 6: 1-naphthyl magnesium bromide ═ 1: 2.0 to 2.2;
in step (8), the organic solvent is selected from toluene or xylene, and the molar ratio of the amount of the intermediate 7 to the amount of the trifluoromethanesulfonic acid is intermediate 7: trifluoromethanesulfonic acid ═ 1: 2.0 to 3.0;
in step (9), the organic solvent is selected from toluene, xylene or trimethylbenzene, and the molar ratio of the amount of the intermediate 8 to the amount of the aromatic secondary amine compound is intermediate 8: aromatic secondary amine compound ═ 1: 1.0-1.2, wherein the molar ratio of the use amount of the intermediate 8 to the use amount of the alkaline substance is that the intermediate 8: basic substance 1: 1.0-3.0, wherein the molar ratio of the using amount of the intermediate 3 to the using amount of the catalyst is that the intermediate 8: catalyst 1: 0.001-0.1, wherein the molar ratio of the dosage of the palladium-containing catalyst to the dosage of the organic phosphine ligand is that the palladium catalyst: organophosphine ligand ═ 1: 0.5 to 4.
The preparation method of the organic electroluminescent material has the beneficial effects that: the preparation method of the organic photoelectric material is simple and convenient, easy to operate, low in cost and beneficial to large-scale popularization.
The invention also discloses an application of the organic photoelectric material, wherein the organic photoelectric material is applied to an organic light-emitting device (OLED), and the organic light-emitting device comprises an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode; wherein the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, the electron injection layer and the cathode are sequentially stacked on the anode; application of the organic electroluminescent material as at least one functional layer in organic electroluminescent device
Preferably, the organic photoelectric material is applied to a light emitting layer of the OLED.
The invention has the beneficial effects that: the organic electroluminescent material provided by the invention has high thermal stability and high glass transition temperature, can be used as a luminescent layer doping material of an OLED (organic light emitting diode) to be applied to the OLED, and the OLED comprising the organic electroluminescent material provided by the invention can obtain good device performance, such as the current efficiency, the power efficiency and the quantum efficiency of the OLED are greatly improved; meanwhile, the service life of the OLED can be greatly prolonged. In addition, the spatial structure of the organic electroluminescent material provided by the invention is a rigid 3D structure, and a twisted non-planar structure, so that the tight accumulation of molecules can be effectively avoided. From this it can be seen that: the organic photoelectric material provided by the invention has a good application effect in OLED and a good industrialization prospect.
Drawings
FIG. 1 is a schematic structural diagram of an organic electroluminescent device in a second embodiment;
in the figure, 1 a transparent substrate layer, 2 an anode layer, 3 a hole injection layer, 4 a hole transport layer, 5 an electron blocking layer, 6 a light emitting layer, 7 an electron transport layer, 8 an electron injection layer, 9 a cathode layer, 10 a light extraction layer.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to make the aforementioned objects, features and advantages of the invention more comprehensible. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example one
This example shows the preparation of some of the compounds D01-C52.
EXAMPLE 1 preparation of Compound D01
(1) Preparation of intermediate 1
Figure BDA0002689486970000101
Preparation of intermediate 1: 1-hydroxydibenzofuran (18.4g, 0.1mol), titanium tetrachloride (20.9g, 0.11mol), and 200mL of dry methylene chloride were charged into a 1L three-necked flask under nitrogen, ethoxyoxalyl chloride (15.0g, 0.11mol) was slowly dropped at an internal temperature of-5 to 0 ℃ for about 2.0hrs, the reaction was carried out at an internal temperature of-5 to 0 ℃ for 2.0hrs after completion of dropping, the reaction progress was followed by TLC, and after completion of the reaction, 300mL of methylene chloride was added and slowly poured into 1.0L of 12% dilute hydrochloric acid in ice water. Stirring for 30min, separating, collecting the organic phase, and removing the solvent under reduced pressure to obtain 26.1g of a brown yellow solid intermediate 1 which can be directly used in the next step without purification, wherein the yield is 92.11%.
(2) Preparation of intermediate 2
Figure BDA0002689486970000111
Preparation of intermediate 2: A1L three-necked flask was charged with intermediate 1(25.5g, 0.09mol), NBS (15.1g, 0.085mol), and 400mL of dry dichloroethane under nitrogen protection, the internal temperature was controlled at 25 to 30 ℃, the reaction was maintained for 2.0hrs, the progress of the reaction was followed by TLC, and after confirming the completion of the reaction, 200mL of a saturated aqueous solution of sodium bisulfite was added. Stirring for 30min, separating, collecting organic phase, removing solvent under reduced pressure to obtain brown yellow solid, and further recrystallizing with toluene ethanol to obtain 24.1g of intermediate 2 with yield of 77.99%.
(3) Preparation of intermediate 3
Figure BDA0002689486970000112
Preparation of intermediate 3: adding the intermediate 2(21.8g, 0.06mol) and 400mL of dry dichloroethane in a 1L three-necked bottle under the protection of nitrogen, controlling the internal temperature to be-5-0 ℃, slowly adding triethylamine (7.3g,0.072mol), further controlling the internal temperature to be-5-0 ℃, slowly adding trifluoromethanesulfonyl chloride (12.1g, 0.072mol), and carrying out heat preservation reaction for 2.0 hrs. After the reaction was completed, the reaction system was slowly poured into 200g of ice water, stirred for 30min, separated, washed once with 5% aqueous sodium bicarbonate, the organic phase was collected, dried, and the solvent was removed under reduced pressure to give 27.0g of a brownish black solid intermediate 3, which was used in the next step without purification, with a yield of 90.90%.
(4) Preparation of intermediate 4
Figure BDA0002689486970000113
Preparation of intermediate 4: adding the intermediate 3(24.7g, 0.05mol), dibenzofuran-4-boric acid (12.7g, 0.06mol), potassium carbonate (10.4g, 0.075mol), 60g of water, 120mL of toluene and 60mL of ethanol in a 500L three-necked flask under the protection of nitrogen, adding palladium acetate (450mg, 0.002mol) and tricyclohexylphosphine (1.12g,0.004mol) after nitrogen replacement, heating to reflux, keeping the internal temperature at 75-78 ℃, carrying out reflux heat preservation for 6.0hrs, carrying out TLC tracking reaction, cooling to room temperature, layering, drying organic phase anhydrous sodium sulfate, passing through a silica gel column, and removing a solvent under reduced pressure until no fraction is obtained to obtain 26.7g of pale yellow solid intermediate 4 without purification.
(5) Preparation of intermediate 5
Figure BDA0002689486970000121
Preparation of intermediate 5: crude intermediate 4 (25.7g, 0.05mol), sodium hydroxide (2.4g, 0.06mol) and 150mL of isopropanol were added to a 1L three-necked flask under nitrogen, after nitrogen substitution, heated to reflux, held at reflux for 3.0hrs, and after TLC tracing, cooled to room temperature, poured slowly into 100mL of 6% dilute hydrochloric acid in ice water. Stirring for 30min, suction filtration gave 20.1g of tan solid intermediate 5, which was used in the next step without purification, yield 83.06%.
(6) Preparation of intermediate 6
Figure BDA0002689486970000122
Preparation of intermediate 6: adding the crude intermediate 5 (20.1g, 0.041mol), N, N-carbonyldiimidazole (14.0g, 0.086mol) and 150mL of dichloromethane into a 500mL three-mouth bottle under the protection of nitrogen, after nitrogen replacement, preserving heat at 15-20 ℃ for 12.0hrs, then slowly cooling to-12-5 ℃, dropwise adding TiCl4(31.1g, 0.164mol)/50mL of dichloromethane solution, preserving heat at the temperature for 6.0hrs after dropwise adding, slowly pouring into 300g, 6mol/L of dilute hydrochloric acid, and quenching. Stirring for 30min, suction filtration gave 12.9g of intermediate 6 as a tan solid in 67.36% yield.
(7) Preparation of intermediate 7
Figure BDA0002689486970000131
Preparation of intermediate 7: adding the intermediate 6(11.7g, 0.025mol) and 100mL of 4-methyl dihydropyran into a 500mL three-necked flask under the protection of nitrogen, after nitrogen replacement, slowly cooling to 0-10 ℃, dropwise adding 103mL of 0.5 mol/L1-naphthyl magnesium bromide/4-methyl dihydropyran solution, after dropwise adding, keeping the temperature at the temperature for reacting for 1.0hr, slowly heating to 20-25 ℃, stirring for reacting for 3.0hr, slowly pouring into 200g of 1mol/L dilute hydrochloric acid, and quenching. Stirring for 30min, layering, washing with water, and removing solvent by organic phase under reduced pressure to obtain 12.3g brown viscous solid intermediate 7 without purification, with yield of 100%.
(8) Preparation of intermediate 8
Figure BDA0002689486970000132
Preparation of intermediate 8: adding the intermediate 7(12.3g, 0.025mol) and 120mL of toluene in a 250mL three-neck flask under the protection of nitrogen, slowly dropwise adding trifluoromethanesulfonic acid (8.0g, 0.053mol) under stirring, slowly heating to 120-130 ℃, reacting at the temperature for 5.0hrs while keeping the temperature, slowly heating to 20-25 ℃, and adding 50g of water to quench and react. Stirring for 30min, layering, washing with water, removing solvent by organic phase vacuum pressure until no fraction is produced, and recrystallizing with THF ethanol to obtain 8.3g of off-white solid intermediate 8 without purification, wherein the yield is 48.33%.
(9) Preparation of Compound D01
Figure BDA0002689486970000133
Preparation of compound D01: adding the intermediate 8(6.9g, 0.01mol), 4-tert-butyldiphenylamine (2.5g, 0.011mol), sodium tert-butoxide (1.5g,0.015mol) and 150g of toluene in a 500mL three-necked bottle under the protection of nitrogen, adding catalysts of palladium acetate (18mg, 0.00008mol) and tri-tert-butylphosphine tetrafluoroborate (46mg, 0.00016mol) under the protection of nitrogen, controlling the internal temperature to be 100-105 ℃, carrying out heat preservation reaction for 8.0hrs, then reducing the temperature to 20-25 ℃, adding water for quenching, layering, washing, and removing the solvent by organic phase under reduced pressure until no fraction exists, thus obtaining a D01 crude product. Further recrystallizing with THF/ethanol mixed solvent, vacuum filtering, collecting filter cake to obtain D01 of 6.4g with calculated yield of 77.06%.
The crude product was further purified by sublimation at 360 ℃ in a chemical vapor deposition system to obtain 5.6g of off-white solid powder. HR-MS was used to identify this compound, formula C62H41NO2Detecting value [ M]+831.3139, calculate value 831.3137.
1H NMR(400MHz，CDCl3)(ppm)：9.543～9.564ppm(dd,1H)，7.738～7.757ppm(d,1H)，7.628～7.647ppm(dd,2H)，7.448～7.569ppm(m,4H)，6.962～7.318(m,24H)，1.319ppm(s，9H)。
EXAMPLE 2 preparation of Compound D23
(1) Preparation of intermediate 1
Figure BDA0002689486970000141
Preparation of intermediate 1: 1-hydroxydibenzofuran (18.4g, 0.1mol), titanium tetrachloride (19.9g, 0.105mol) and 200mL of dry methylene chloride were charged into a 1L three-necked flask under nitrogen atmosphere, ethoxyoxalyl chloride (15.0g, 0.11mol) was slowly dropped thereinto at an internal temperature of-10 to-5 ℃ until the dropping was completed for about 2.0hrs, and then the mixture was reacted at an internal temperature of-10 to-5 ℃ for 4.0hrs by TLC to follow the progress of the reaction, and after confirming the completion of the reaction, 300mL of methylene chloride was added and slowly poured into 1.0L of 12% dilute hydrochloric acid in ice water. Stirring for 30min, separating, collecting the organic phase, and removing the solvent under reduced pressure to obtain 25.7g of a brown yellow solid intermediate 1 which can be directly used in the next step without purification, with the yield of 90.49%.
(2) Preparation of intermediate 2
Figure BDA0002689486970000142
Preparation of intermediate 2: A1L three-necked flask was charged with intermediate 1(25.5g, 0.09mol), NBS (16.0g, 0.09mol), and 400mL of dry dichloroethane under nitrogen protection, the internal temperature was controlled at 25 to 30 ℃, the reaction was maintained for 2.0hrs, the progress of the reaction was followed by TLC, and after confirming the completion of the reaction, 200mL of a saturated aqueous solution of sodium bisulfite was added. Stirring for 30min, separating, collecting organic phase, removing solvent under reduced pressure to obtain brown yellow solid, and further recrystallizing with toluene ethanol to obtain 23.8g of intermediate 2 with yield of 72.78%.
(3) Preparation of intermediate 3
Figure BDA0002689486970000151
Preparation of intermediate 3: adding the intermediate 2(21.8g, 0.06mol) and 400mL of dry dichloroethane in a 1L three-necked bottle under the protection of nitrogen, controlling the internal temperature to be-5-0 ℃, slowly adding triethylamine (7.3g,0.072mol), further controlling the internal temperature to be-5-0 ℃, slowly adding trifluoromethanesulfonyl chloride (12.1g, 0.072mol), and carrying out heat preservation reaction for 2.0 hrs. After the reaction was completed, the reaction system was slowly poured into 200g of ice water, stirred for 30min, separated, washed once with 5% aqueous sodium bicarbonate, the organic phase was collected, dried, and the solvent was removed under reduced pressure to give 27.0g of a brownish black solid intermediate 3, which was used in the next step without purification, with a yield of 90.90%.
(4) Preparation of intermediate 4
Figure BDA0002689486970000152
Preparation of intermediate 4: adding the intermediate 3(24.7g, 0.05mol), dibenzofuran-1-boric acid (11.7g, 0.055mol), potassium carbonate (10.4g, 0.075mol), 60g of water, 120mL of toluene and 60mL of ethanol into a 500L three-necked flask under the protection of nitrogen, adding palladium acetate (450mg, 0.002mol) and tricyclohexylphosphine (1.12g,0.004mol) after nitrogen replacement, heating to reflux, keeping the internal temperature at 75-78 ℃, carrying out reflux heat preservation for 6.0hrs, carrying out TLC tracking reaction, cooling to room temperature, layering, drying organic phase anhydrous sodium sulfate, passing through a silica gel column, and removing the solvent under reduced pressure until no fraction exists, thereby obtaining 25.8g of pale yellow solid intermediate 4 without purification.
(5) Preparation of intermediate 5
Figure BDA0002689486970000161
Preparation of intermediate 5: in a 1L three-necked flask, under the protection of nitrogen, the crude intermediate 4 (25.8g, 0.05mol), sodium hydroxide (2.4g, 0.06mol) and 150mL of ethanol were added, after nitrogen substitution, the mixture was heated to reflux, and then the reflux was maintained at the same temperature for 4.0hrs, after TLC tracing, the reaction was cooled to room temperature, and then slowly poured into 100mL of 6% diluted hydrochloric acid in ice water. Stirring for 30min and suction filtration gave 19.3g of tan solid intermediate 5, which was used in the next step without purification, yield 79.55%.
(6) Preparation of intermediate 6
Figure BDA0002689486970000162
Preparation of intermediate 6: adding the crude intermediate 5 (17.0g, 0.035mol), N, N-carbonyldiimidazole (11.4g, 0.07mol) and 150mL of dichloromethane into a 500mL three-neck flask under the protection of nitrogen, after the replacement of nitrogen, keeping the temperature at 15-20 ℃ for 12.0hrs, then slowly cooling to-12-5 ℃, and dropwise adding TiCl4(26.6g, 0.14mol)/50mL of dichloromethane solution, after dropping, the reaction was incubated at this temperature for 6.0hrs and poured slowly into 300g, 6mol/L of dilute hydrochloric acid to quench. Stirring for 30min, suction filtration gave 12.1g of intermediate 6 as a tan solid in 74.00% yield.
(7) Preparation of intermediate 7
Figure BDA0002689486970000163
Preparation of intermediate 7: adding the intermediate 6(11.7g, 0.025mol) and 100mL of 4-methyl dihydropyran into a 500mL three-necked flask under the protection of nitrogen, after nitrogen replacement, slowly cooling to 0-10 ℃, dropwise adding 103mL of 0.5 mol/L1-naphthyl magnesium bromide/4-methyl dihydropyran solution, after dropwise adding, keeping the temperature at the temperature for reacting for 1.0hr, slowly heating to 20-25 ℃, stirring for reacting for 3.0hr, slowly pouring into 200g of 1mol/L dilute hydrochloric acid, and quenching. Stirring for 30min, layering, washing with water, and removing solvent by organic phase under reduced pressure to obtain 18.6g brown viscous solid intermediate 7 without purification, with yield of 100%.
(8) Preparation of intermediate 7
Figure BDA0002689486970000171
Preparation of intermediate 8: adding the crude intermediate 7(18.6g, 0.025mol) and 120mL of toluene into a 250mL three-neck flask under the protection of nitrogen, slowly dropwise adding trifluoromethanesulfonic acid (7.5g, 0.050mol) under stirring, slowly heating to 120-130 ℃, reacting at the temperature for 7.0hrs while keeping the temperature, slowly heating to 20-25 ℃, and adding 50g of water to quench and react. Stirring for 30min, layering, washing with water, removing solvent by organic phase vacuum pressure until no fraction is produced, and recrystallizing with THF ethanol to obtain 7.8g of off-white solid intermediate 8 without purification, wherein the yield is 45.35%.
(9) Preparation of Compound D23
Figure BDA0002689486970000172
Preparation of compound D23: adding the intermediate 8(6.9g, 0.01mol), 4, 4' -di-tert-butyl diphenylamine (3.1g, 0.011mol), sodium tert-butoxide (1.5g,0.015mol) and 150g of toluene in a 500mL three-necked bottle under the protection of nitrogen, adding catalysts of palladium acetate (18mg, 0.00008mol) and tri-tert-butylphosphine tetrafluoroborate (46mg, 0.00016mol) under the protection of nitrogen, controlling the internal temperature to be 100-105 ℃, carrying out heat preservation reaction for 8.0hrs, reducing the temperature to 20-25 ℃, adding water for quenching, layering, washing, and removing the solvent to no fraction by organic phase pressure to obtain a D23 crude product. Further recrystallizing with THF/ethanol mixed solvent, vacuum filtering, collecting filter cake to obtain D23 of 6.7g with calculated yield of 75.45%.
The crude product was further purified by sublimation at 360 ℃ in a chemical vapor deposition system to obtain 5.8g of off-white solid powder. HR-MS was used to identify this compound, formula C66H49NO2Detecting value [ M]And 887.3761, calculate 887.3763.
1H NMR(400MHz，CDCl3)(ppm)：7.982～8.010ppm(m,2H)，7.701～7.719ppm(d,1H)，7.549～7.569ppm(m,2H)，7.219～7.398(m，17H)，7.026～7.118(m，9H)，1.121～1.127ppm(s，18H)。
Embodiment 3 preparation of Compound D40
(1) Preparation of intermediate 1
Figure BDA0002689486970000181
Preparation of intermediate 1: in a 1L three-necked flask, under nitrogen protection, 4-hydroxydibenzofuran (18.4g, 0.1mol), titanium tetrachloride (19.9g, 0.105mol), and 200mL of dry methylene chloride were added, ethoxyoxalyl chloride (15.0g, 0.11mol) was slowly dropped at an internal temperature of-10 to-5 ℃ for about 2.0hrs, and then the mixture was kept at an internal temperature of-10 to-5 ℃ for 4.0hrs, followed by TLC to follow the progress of the reaction, and after confirming the completion of the reaction, 300mL of methylene chloride was added, and the mixture was slowly poured into 1.0L of 12% dilute hydrochloric acid in ice water. Stirring for 30min, separating the liquids, collecting the organic phase, and removing the solvent under reduced pressure to obtain 24.3g of a tan solid intermediate 1, which was used in the next step without purification, with a yield of 85.56%.
(2) Preparation of intermediate 2
Figure BDA0002689486970000182
Preparation of intermediate 2: A1L three-necked flask was charged with intermediate 1(22.7g, 0.08mol), NBS (14.2g, 0.08mol), 400mL of dry dichloroethane under nitrogen protection, the internal temperature was controlled at 25 to 30 ℃, the reaction was maintained for 2.0hrs, the progress of the reaction was followed by TLC, and after confirming the completion of the reaction, 200mL of a saturated aqueous solution of sodium bisulfite was added. Stirring for 30min, separating, collecting the organic phase, removing the solvent under reduced pressure to obtain a tan solid, and further recrystallizing with toluene ethanol to obtain 21.0g of intermediate 2 with a yield of 72.41%.
(3) Preparation of intermediate 3
Figure BDA0002689486970000183
Preparation of intermediate 3: adding the intermediate 2(18.2g, 0.05mol) and 400mL of dry dichloroethane in a 1L three-necked flask under the protection of nitrogen, controlling the internal temperature to be-5-0 ℃, slowly adding triethylamine (6.1g,0.06mol), further controlling the internal temperature to be-5-0 ℃, slowly adding trifluoromethanesulfonyl chloride (10.1g, 0.06mol), and carrying out heat preservation reaction for 2.0 hrs. After the reaction was completed, the reaction system was slowly poured into 200g of ice water, stirred for 30min, separated, washed once with 5% aqueous sodium bicarbonate, the organic phase was collected, dried, and the solvent was removed under reduced pressure to obtain 25.0g of a brownish black solid intermediate 3, which was used in the next step without purification, with a yield of 100%.
(4) Preparation of intermediate 4
Figure BDA0002689486970000191
Preparation of intermediate 4: adding crude intermediate 3(25.0g, 0.05mol), dibenzofuran-1-boric acid (11.7g, 0.055mol), potassium carbonate (10.4g, 0.075mol), 60g of water, 120mL of toluene and 60mL of ethanol in a 500L three-necked flask under the protection of nitrogen, adding palladium acetate (450mg, 0.002mol) and tricyclohexylphosphine (1.12g,0.004mol) after nitrogen replacement, heating to reflux, keeping the temperature at 75-78 ℃ under reflux for 6.0hrs, tracking the reaction by TLC, cooling to room temperature, layering, drying organic phase anhydrous sodium sulfate, passing through a silica gel column, and removing the solvent under reduced pressure until no fraction is obtained, thus obtaining 25.8g of light yellow solid intermediate 4 without purification, wherein the yield is 100%.
(5) Preparation of intermediate 5
Figure BDA0002689486970000192
Preparation of intermediate 5: in a 1L three-necked flask, under the protection of nitrogen, the crude intermediate 4 (25.8g, 0.05mol), sodium hydroxide (2.4g, 0.06mol) and 150mL of ethanol were added, after nitrogen substitution, the mixture was heated to reflux, and then the reflux was maintained at the same temperature for 4.0hrs, after TLC tracing, the reaction was cooled to room temperature, and then slowly poured into 100mL of 6% diluted hydrochloric acid in ice water. Stirring for 30min, suction filtration gave 18.5g of tan solid intermediate 5, which was used in the next step without purification, yield 76.26%.
(6) Preparation of intermediate 6
Figure BDA0002689486970000201
Preparation of intermediate 6: adding the crude intermediate 5 (17.0g, 0.035mol), N, N-carbonyldiimidazole (11.4g, 0.07mol) and 150mL of dichloromethane into a 500mL three-neck flask under the protection of nitrogen, after the replacement of nitrogen, keeping the temperature at 15-20 ℃ for 12.0hrs, then slowly cooling to-12-5 ℃, and dropwise adding TiCl4(26.6g, 0.14mol)/50mL of dichloromethane solution, after dropping, the reaction was incubated at this temperature for 6.0hrs and poured slowly into 300g, 6mol/L of dilute hydrochloric acid to quench. Stirring for 30min, and suction filtering to obtain 10.9 brown yellow solid intermediate 6 with yield 66.67%.
(7) Preparation of intermediate 7
Figure BDA0002689486970000202
Preparation of intermediate 7: adding the intermediate 6(9.3g, 0.020mol) and 100mL of 4-methyl dihydropyran into a 500mL three-necked bottle under the protection of nitrogen, after nitrogen replacement is finished, slowly cooling to 0-10 ℃, dropwise adding 80mL of 0.5 mol/L1-naphthyl magnesium bromide/4-methyl dihydropyran solution, after dropwise adding, keeping the temperature at the temperature for reacting for 1.0hr, slowly heating to 20-25 ℃, stirring for reacting for 4.0hr, slowly pouring into 200g of 1mol/L dilute hydrochloric acid, and quenching. Stirring for 30min, layering, washing with water, and organic phase vacuum desolventizing to no distillate to give 14.5g brown viscous solid intermediate 7 without purification, with 100% yield.
(8) Preparation of intermediate 8
Figure BDA0002689486970000203
Preparation of intermediate 8: adding the crude intermediate 7(14.5g, 0.020mol) and 120mL of toluene into a 250mL three-neck flask under the protection of nitrogen, slowly dropwise adding trifluoromethanesulfonic acid (6.0g, 0.040mol) under stirring, slowly heating to 120-130 ℃, keeping the temperature at the temperature for reaction for 7.0hrs, slowly heating to 20-25 ℃, and adding 50g of water to quench and react. Stirring for 30min, layering, washing with water, removing solvent by organic phase vacuum pressure until no fraction is produced, and recrystallizing with THF ethanol to obtain 5.9g of off-white solid intermediate 8 without purification, wherein the yield is 42.91%.
(9) Preparation of Compound D40
Figure BDA0002689486970000211
Preparation of compound D40: adding the intermediate 8(5.5g, 0.008mol), N- (4-isopropylphenyl) dibenzo [ b, D ] furan-4-amine (2.5g, 0.0084mol), sodium tert-butoxide (1.2g,0.012mol) and 150g of toluene in a 500mL three-necked flask under the protection of nitrogen, adding catalysts of palladium acetate (9mg, 0.00004mol) and tri-tert-butylphosphine tetrafluoroborate (23mg, 0.0008mol) under the protection of nitrogen, controlling the internal temperature to be 100-105 ℃, reducing the temperature to 20-25 ℃ after carrying out heat preservation reaction for 8.0hrs, adding water for quenching, demixing, washing, and decompressing and desolventizing the organic phase until no fraction is obtained, thus obtaining a D40 crude product. Further recrystallizing with THF/ethanol mixed solvent, vacuum filtering, collecting filter cake to obtain D40 of 5.4g with calculated yield of 74.38%.
The crude product was further purified by sublimation at 360 ℃ in a chemical vapor deposition system to obtain 4.7g of off-white solid powder. HR-MS was used to identify this compound, formula C67H41NO3Detecting value [ M]And 907.3088, calculate 907.3086.
1H NMR(400MHz，CDCl3)(ppm)：8.020～8.130ppm(m，4H)，7.641～7.658ppm(dd,2H)，7.443～7.556ppm(m,3H)，7.169～7.338(m，21H)，6.883～7.026(m，4H)，2.880～3.083ppm(m，1H)，1.112～1.127ppm(d，6H)。
EXAMPLE 4 preparation of Compound D50
(1) Preparation of intermediate 1
Figure BDA0002689486970000212
Preparation of intermediate 1: 1-hydroxydibenzofuran (18.4g, 0.1mol), titanium tetrachloride (20.9g, 0.11mol), and 200mL of dry methylene chloride were charged into a 1L three-necked flask under nitrogen, ethoxyoxalyl chloride (15.0g, 0.11mol) was slowly dropped at an internal temperature of-5 to 0 ℃ for about 2.0hrs, the reaction was carried out at an internal temperature of-5 to 0 ℃ for 2.0hrs after completion of dropping, the reaction progress was followed by TLC, and after completion of the reaction, 300mL of methylene chloride was added and slowly poured into 1.0L of 12% dilute hydrochloric acid in ice water. Stirring for 30min, separating, collecting the organic phase, and removing the solvent under reduced pressure to obtain 26.1g of a brown yellow solid intermediate 1 which can be directly used in the next step without purification, wherein the yield is 92.11%.
(2) Preparation of intermediate 2
Figure BDA0002689486970000221
Preparation of intermediate 2: A1L three-necked flask was charged with intermediate 1(25.5g, 0.09mol), NBS (15.1g, 0.085mol), and 400mL of dry dichloroethane under nitrogen protection, the internal temperature was controlled at 25 to 30 ℃, the reaction was maintained for 2.0hrs, the progress of the reaction was followed by TLC, and after confirming the completion of the reaction, 200mL of a saturated aqueous solution of sodium bisulfite was added. Stirring for 30min, separating, collecting organic phase, removing solvent under reduced pressure to obtain brown yellow solid, and further recrystallizing with toluene ethanol to obtain 24.1g of intermediate 2 with yield of 77.99%.
(3) Preparation of intermediate 3
Figure BDA0002689486970000222
Preparation of intermediate 3: adding the intermediate 2(21.8g, 0.06mol) and 400mL of dry dichloroethane in a 1L three-necked bottle under the protection of nitrogen, controlling the internal temperature to be-5-0 ℃, slowly adding triethylamine (7.3g,0.072mol), further controlling the internal temperature to be-5-0 ℃, slowly adding trifluoromethanesulfonyl chloride (12.1g, 0.072mol), and carrying out heat preservation reaction for 2.0 hrs. After the reaction was completed, the reaction system was slowly poured into 200g of ice water, stirred for 30min, separated, washed once with 5% aqueous sodium bicarbonate, the organic phase was collected, dried, and the solvent was removed under reduced pressure to obtain 27.0g of a brownish black solid intermediate 3, which was used in the next step without purification, with a yield of 90.90%.
(4) Preparation of intermediate 4
Figure BDA0002689486970000231
Preparation of intermediate 4: adding the intermediate 3(24.7g, 0.05mol), (1-bromodibenzo [ b, d ] furan-4-yl) boric acid (17.5g, 0.06mol), potassium carbonate (10.4g, 0.075mol), 60g of water, 120mL of toluene and 60mL of ethanol into a 500L three-necked flask under the protection of nitrogen, after nitrogen replacement, adding palladium acetate (450mg, 0.002mol) and tricyclohexylphosphine (1.12g,0.004mol), heating to reflux, keeping the temperature at 75-78 ℃ for 6.0hrs, after TLC tracing reaction, cooling to room temperature, layering, drying organic phase anhydrous sodium sulfate, passing through a silica gel column, removing a solvent under reduced pressure until no fraction exists, and performing column chromatography by using a dichloromethane/petroleum ether mixed solvent to obtain 18.1g of light yellow solid intermediate 4 with the yield of 61.15%.
(5) Preparation of intermediate 5
Figure BDA0002689486970000232
Preparation of intermediate 5: the intermediate 4(14.8g, 0.025mol), sodium hydroxide (1.2g, 0.03mol) and 100mL of ethanol were added to a 1L three-necked flask under nitrogen, after nitrogen substitution, the flask was heated to reflux, the reflux was maintained at a temperature for 3.0hrs, the TLC-traced reaction was completed, the temperature was reduced to room temperature, and the flask was slowly poured into 100mL of 6% diluted hydrochloric acid in ice water. Stirring for 30min and suction filtration gave 10.1g of tan solid intermediate 5, which was used in the next step without purification, yield 71.63%.
(6) Preparation of intermediate 6
Figure BDA0002689486970000233
Preparation of intermediate 6: adding the intermediate 5(10.1g, 0.018mol), N, N-carbonyl diimidazole (5.8g, 0.036mol) and 100mL of dichloromethane into a 500mL three-neck flask under the protection of nitrogen, after the nitrogen replacement is finished, keeping the temperature at 15-20 ℃ for 12.0hrs, then slowly cooling to-5-0 ℃, and dropwise adding TiCl4(13.7g, 0.72mol)/50mL of dichloromethane solution, after dropping, the reaction was incubated at this temperature for 6.0hrs and poured slowly into 300g, 6mol/L of dilute hydrochloric acid to quench. Stirring for 30min, suction filtration gave 6.9g of intermediate 6 as a tan solid in 68.32% yield.
(7) Preparation of intermediate 7
Figure BDA0002689486970000241
Preparation of intermediate 7: adding the intermediate 6(5.6g, 0.010mol) and 100mL of 4-methyl dihydropyran into a 500mL three-necked bottle under the protection of nitrogen, after nitrogen replacement, slowly cooling to 0-10 ℃, dropwise adding 40mL of 0.5 mol/L1-naphthyl magnesium bromide/4-methyl dihydropyran solution, after dropwise adding, keeping the temperature at the temperature for reacting for 1.0hr, slowly heating to 20-25 ℃, stirring for reacting for 3.0hr, slowly pouring into 200g of 1mol/L dilute hydrochloric acid, and quenching. Stirring for 30min, layering, washing with water, and removing solvent by organic phase under reduced pressure to obtain 8.2 brown viscous solid intermediate 7 without purification, with yield of 100%.
(8) Preparation of intermediate 8
Figure BDA0002689486970000242
Preparation of intermediate 8: adding the intermediate 7(8.2g, 0.010mol) and 120mL of toluene into a 250mL three-neck flask under the protection of nitrogen, slowly dropwise adding trifluoromethanesulfonic acid (3.0g, 0.020mol) under stirring, slowly heating to 105-110 ℃, keeping the temperature at the temperature for reaction for 5.0hrs, slowly heating to 20-25 ℃, and adding 50g of water to quench and react. Stirring for 30min, layering, washing with water, removing solvent by organic phase vacuum pressure until no fraction is produced, and recrystallizing with THF ethanol to obtain 3.4g of off-white solid intermediate 8 without purification, wherein the yield is 44.39%.
(9) Preparation of Compound D50
Figure BDA0002689486970000251
Preparation of compound D50: adding the intermediate 8(3.0g, 0.004mol), 4, 4' -di-tert-butyl diphenylamine (1.2g, 0.0042mol), sodium tert-butoxide (0.8g,0.008mol) and 100g of toluene in a 500mL three-necked bottle under the protection of nitrogen, adding catalysts of palladium acetate (18mg, 0.00008mol) and tri-tert-butylphosphine tetrafluoroborate (46mg, 0.00016mol) under the protection of nitrogen, controlling the internal temperature to be 100-105 ℃, carrying out heat preservation reaction for 8.0hrs, reducing the temperature to 20-25 ℃, adding water for quenching, layering, washing, and removing the solvent by organic phase under pressure until no fraction is obtained, thus obtaining a D50 crude product. Further adopting a THF/ethanol mixed solvent for recrystallization, carrying out suction filtration, and collecting a filter cake to obtain 3.2g of D50, wherein the calculated yield is 68.52%.
The crude product was further purified by sublimation at 360 ℃ in a chemical vapor deposition system to obtain 2.4g of off-white solid powder. HR-MS was used to identify this compound, formula C86H74N2O2Detecting value [ M]+＝1166.5752, calculated 1166.5750.
1H NMR(400MHz，CDCl3)(ppm)：9.555～9.576ppm(dd,1H)，7.720～7.740ppm(d,1H)，7.649～7.667ppm(dd,2H)，7.441～7.569ppm(m,4H)，7.241～7.282ppm(m,3H)，7.079～7.118(m,15H)，6.813～6.926(m，10H)，6.662ppm(s,1H)，6.383ppm(s，1H)，1.196～1.290ppm(d，36H)。
Organic photoelectric materials (compounds D01 to D52) prepared by the methods described in embodiments 1 to 4 of compound sample preparation.
The compound of the present invention is used as a material of a light emitting layer in a light emitting device. The compound D01, the compound D23, the compound D40, the compound D50 and the conventional material BD-1 of the present invention were subjected to thermal property tests, and the test results are shown in Table 1.
TABLE 1 thermal stability test
Figure BDA0002689486970000252
Figure BDA0002689486970000261
Note: the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 DSC, Germany Chi corporation), the heating rate is 10 ℃/min; the thermogravimetric temperature Td was a temperature at which the weight loss was 5% in a nitrogen atmosphere, and was measured by a TGA-50H thermogravimetric analyzer of Shimadzu corporation, Japan, and the nitrogen flow rate was 20 mL/min.
As can be seen from the data in the above table, the compound provided by the invention in the above table has higher thermal stability, so that the lifetime of the OLED device containing the compound provided by the invention is improved.
EXAMPLE two preparation of organic electroluminescent device (hereinafter referred to as device)
Device example 1
The preparation process comprises the following steps:
as shown in fig. 1, the transparent substrate layer 1 is a transparent PI film, and the ITO (15nm)/Ag (150nm)/ITO (15nm) anode layer 2 is washed, i.e., sequentially washed with alkali, washed with pure water, dried, and then washed with ultraviolet-ozone to remove organic residues on the surface of the anode layer. HT-1 and P-1 having a film thickness of 10nm were deposited on the anode layer 2 after the above washing as the hole injection layer 3 by a vacuum deposition apparatus, and the mass ratio of HT-1 to P-1 was 97: 3. HT-1 was then evaporated to a thickness of 55nm as the hole transport layer 4. EB-1 was then evaporated to a thickness of 10nm as an electron blocking layer 5. After the evaporation of the electron blocking material is finished, the light-emitting layer 6 of the OLED light-emitting device is manufactured, and the structure of the light-emitting layer 6 comprises that the OLED light-emitting layer 6 uses BH-1 as a main material, the compound D01 of the invention is used as a doping material, the doping proportion of the doping material is 3% by weight, and the thickness of the light-emitting layer is 20 nm. After the light-emitting layer 6, ET-1 and Liq were continuously vacuum-evaporated, the mass ratio of ET-1 to Liq was 1:1, the film thickness was 35nm, and this layer was a hole-blocking/electron-transporting layer 7. On the hole-blocking/electron-transporting layer 7, a Yb layer having a film thickness of 1nm, which is an electron-injecting layer 8, was formed by a vacuum evaporation apparatus. On the electron injection layer 8, a vacuum deposition apparatus was used to produce a 15 nm-thick Mg: an Ag electrode layer, wherein the mass ratio of Mg to Ag is 1:9, and the Ag electrode layer is a cathode layer 9; then, CPL-1 of 80nm was deposited as a light extraction layer 10.
After the electroluminescent device was fabricated according to the above procedure, I-V-L data of the device was measured using FS-1000GA4 test equipment, Foster science instruments, Suzhou, and the lifetime of the device was measured using EAS-62C test equipment, Japan SYSTEM research corporation, and the results are shown in Table 2. The molecular structural formula of the related material is shown as follows:
Figure BDA0002689486970000271
device example 2
This embodiment differs from device embodiment 1 in that: the compound D23 provided by the invention is used for doping the light-emitting layer for preparing an organic electroluminescent device.
Device example 3
This embodiment differs from device embodiment 1 in that: the compound D40 provided by the invention is used as the luminescent layer doping material of the prepared organic electroluminescent device.
Device example 4
This embodiment differs from device embodiment 1 in that: the compound D50 provided by the invention is used as the luminescent layer doping material of the prepared organic electroluminescent device.
Device comparative example 1
Device comparative example 1 differs from the organic electroluminescent device 1 in that: the doping material of the light emitting layer of the organic electroluminescent device 1 is BD-1.
The results of testing device examples 1-4 and device comparative example 1 are shown in table 2 below:
TABLE 2
Figure BDA0002689486970000272
Figure BDA0002689486970000281
From the analysis of the above table 2, it can be seen that the device prepared by applying the organic photoelectric material provided by the present invention has a driving voltage, a current efficiency and a lifetime which are greatly improved compared with those of the known OLED material, and particularly, the driving lifetime of the device is greatly prolonged.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (7)

1. An organic electroluminescent material, characterized in that the organic electroluminescent material is represented by the following formula I:
Figure FDA0002689486960000011
wherein, R is1And R2Same or different, said R1And R2Simultaneously or partially present, said R1And R2One selected from hydrogen and a substituted or unsubstituted aromatic heterocyclic group containing at least one of N, S, O and having 4 to 36 carbon atoms.
2. The organic electroluminescent material according to claim 1, wherein the organic electroluminescent material is represented by the following formulas II, III and IV:
Figure FDA0002689486960000012
wherein, R is1And R2Same or different, said R1And R2Simultaneously or partially present, said R1And R2Selected from substituted or unsubstituted polycyclic conjugated aryl containing 4-36 carbon atoms, or R1And R2And one selected from substituted or unsubstituted aromatic heterocyclic groups containing at least one of N, S, O and having 4 to 36 carbon atoms.
3. The organic electroluminescent material of claim 1, wherein R is1And R2Any one selected from the following groups:
Figure FDA0002689486960000013
Figure FDA0002689486960000021
Figure FDA0002689486960000022
denotes the bonding site.
4. The organic electroluminescent material of claim 1, wherein the organic electroluminescent material has any one of the following structural formulas D01-D52:
Figure FDA0002689486960000023
Figure FDA0002689486960000031
Figure FDA0002689486960000041
5. a method for preparing an organic electroluminescent material according to claim 1, wherein the method comprises the steps of:
(1) under the protection of inert gas, adding a raw material 1, titanium tetrachloride and an organic solvent into a reaction system, slowly adding ethoxy oxalyl chloride at the temperature of-20-50 ℃, keeping the temperature and stirring for 1-8.0 hrs, pouring into dilute hydrochloric acid to quench after the reaction is finished, thus obtaining the reaction system containing an intermediate 1, wherein the organic solvent is selected from one or more of dichloromethane, chloroform and dichloroethane, the raw material 1 is shown as the following formula 1, and the intermediate 1 is shown as the following formula 2;
Figure FDA0002689486960000042
(2) adding the intermediate 1 obtained in the step (1) and N-bromosuccinimide into an organic solvent, reacting for 1-10.0 hrs at 0-80 ℃ under the protection of inert gas, pouring into an aqueous solution of sodium bisulfite, and quenching to obtain a reaction system containing an intermediate 2, wherein the organic solvent is one or more selected from dichloromethane, chloroform and dichloroethane, and the intermediate 2 is represented by the following formula 3;
Figure FDA0002689486960000051
(3) adding the intermediate 2 obtained in the step (2) and an alkaline substance into an organic solvent, and adding trifluoromethanesulfonyl chloride to react for 1-12.0 hrs at-10-60 ℃ under the protection of inert gas to obtain a reaction system containing an intermediate 3, wherein the alkaline substance is selected from one or more of triethylamine, diisopropylethylamine, pyridine and N, N-dimethylpyridine-4-amine, the organic solvent is selected from one or more of dichloromethane, trichloromethane, dichloroethane or toluene, and the intermediate 3 is shown in the following formula 4;
Figure FDA0002689486960000052
(4) adding the intermediate 3 obtained in the step (3), the raw material 2 and an alkaline substance into an organic solvent, adding a catalyst into the system under the protection of inert gas, and reacting at 60-150 ℃ for 3-12.0 hrs to obtain a reaction system containing the intermediate 3, wherein the alkaline substance is one or more of potassium carbonate, sodium carbonate, potassium phosphate and potassium hydroxide, the catalyst is a palladium-containing catalyst and an organic phosphine ligand, and the palladium-containing catalyst is Pd (OAc)2、Pd(PPh3)4、Pd(PPh3)2Cl2And Pd (dppf) Cl2One ofOne or more of the organic phosphine ligands are triphenylphosphine, DPPP, Xantphos, Sphos, P (t-Bu)3·HBF4Wherein, X is selected from hydrogen or bromine atom, and the intermediate 4 is shown as the following formula 6;
Figure FDA0002689486960000053
(5) adding the intermediate 4 obtained in the step (4) and an alkaline substance into an organic solvent, and reacting for 1-12.0 hrs at 60-150 ℃ under the protection of inert gas to obtain a reaction system containing an intermediate 5, wherein the alkaline substance is one or more selected from potassium hydroxide, sodium hydroxide and sodium ethoxide, and the intermediate 5 is shown as the following formula 7;
Figure FDA0002689486960000061
(6) adding the intermediate 5 obtained in the step (5) and N, N-carbonyl diimidazole into an organic solvent, and reacting for 1-24.0 hrs at-20-60 ℃ under the protection of inert gas; and then adding titanium tetrachloride at the temperature of-20-60 ℃, reacting for 1-12.0 hrs under heat preservation, pouring into dilute hydrochloric acid, and quenching to obtain a reaction system containing an intermediate 6, wherein the organic solvent is one or more selected from dichloromethane, dichloroethane and chloroform, and the intermediate 6 is shown as the following formula 8.
Figure FDA0002689486960000062
(7) Adding the intermediate 6 obtained in the step (6) into an organic solvent, adding a 1-naphthyl magnesium bromide/4-methyl dihydropyran solution at-20-60 ℃ under the protection of inert gas, and reacting for 1-24.0 hrs at-20-60 ℃; then pouring into diluted hydrochloric acid for quenching to obtain a reaction system containing an intermediate 7, wherein the organic solvent is selected from one or more of THF and 4-methyl dihydropyran, and the intermediate 7 is shown as the following formula 9;
Figure FDA0002689486960000063
(8) adding the intermediate 7 obtained in the step (7) into an organic solvent, adding trifluoromethanesulfonic acid under the protection of inert gas, and reacting at 30-150 ℃ for 1-24.0 hrs to obtain a reaction system containing an intermediate 8, wherein the organic solvent is one or more selected from toluene and xylene, and the intermediate 8 is represented by the following formula 10;
Figure FDA0002689486960000071
(9) under the protection of inert gas, adding the intermediate 8 obtained in the step (8), an aromatic secondary amine compound, an alkaline substance and a reaction solvent into a reaction system, adding a catalyst into the system, and reacting for 1-30.0 hrs at the temperature of 50-150 ℃ to obtain the reaction system containing the organic photoelectric material, wherein the alkaline substance is one or more of sodium tert-butoxide, sodium tert-amylate and potassium tert-butoxide; the catalyst is a palladium-containing catalyst and an organic phosphine ligand, and the palladium-containing catalyst is Pd (OAc)2、Pd(PPh3)4、Pd(PPh3)2Cl2And Pd (dppf) Cl2One or more of triphenylphosphine, DPPP, Xantphos, Sphos, P (t-Bu)3·HBF4One or more of them are mixed.
6. The method for preparing an organic photoelectric material according to claim 5, wherein:
in the step (1), the organic solvent is selected from dichloromethane, chloroform or dichloroethane, and the molar ratio of the amount of the raw material 1 to the amount of the titanium tetrachloride is that the raw material 1: titanium tetrachloride is 1: 1.0-1.5, wherein the molar ratio of the dosage of the raw material 1 to the dosage of the ethoxy oxalyl chloride is that the raw material 1: ethoxyoxalyl chloride ═ 1: 1.0 to 1.5;
in the step (2), the organic solvent is selected from dichloromethane, chloroform or dichloroethane, and the molar ratio of the dosage of the intermediate 1 to the dosage of the N-bromosuccinimide is that the intermediate 1: n-bromosuccinimide ═ 1: 0.9 to 1.1;
in the step (3), the organic solvent is selected from dichloromethane, chloroform, dichloroethane or toluene, the basic substance is selected from triethylamine, diisopropylethylamine, pyridine or N, N-dimethylpyridine-4-amine, and the molar ratio of the amount of the intermediate 2 to the amount of the basic substance is that the intermediate 2: basic substance 1.0: 1.0-1.5, wherein the molar ratio of the using amount of the intermediate 2 to the using amount of the trifluoromethanesulfonyl chloride is that the intermediate 2: trifluoromethanesulfonyl chloride ═ 1: 1.0 to 1.5;
in the step (4), the organic solvent is selected from tetrahydrofuran, dioxane, toluene, xylene or trimethylbenzene, and the molar ratio of the amount of the intermediate 3 to the amount of the raw material 2 is that the intermediate 3: raw material 2 is 1: 1.0-1.2, wherein the molar ratio of the using amount of the intermediate 3 to the using amount of the alkaline substance is that the intermediate 3: basic substance 1: 1.0-3.0, wherein the molar ratio of the using amount of the intermediate 3 to the using amount of the catalyst is that the intermediate 3: catalyst 1: 0.001-0.1, wherein the molar ratio of the dosage of the palladium-containing catalyst to the dosage of the organic phosphine ligand is as follows: organophosphine ligand ═ 1: 0.5 to 4;
in the step (5), the organic solvent is selected from methanol, ethanol or isopropanol, and the molar ratio of the amount of the intermediate 4 to the amount of the alkaline substance is that the intermediate 4: basic substance 1: 1.0 to 2.0;
in step (6), the organic solvent is selected from dichloromethane, dichloroethane or chloroform, and the molar ratio of the amount of the intermediate 5 to the amount of the N, N-carbonyldiimidazole is intermediate 5: n, N-carbonyldiimidazole ═ 1: 1.5-3.0, wherein the molar ratio of the amount of the intermediate 5 to the amount of the titanium tetrachloride is that the intermediate 5: titanium tetrachloride is 1: 3.0 to 5.0;
in step (7), the organic solvent is selected from THF or 4-methyl dihydropyran, and the molar ratio of the amount of the intermediate 6 to the amount of the 1-naphthyl magnesium bromide is intermediate 6: 1-naphthyl magnesium bromide ═ 1: 2.0 to 2.2;
in step (8), the organic solvent is selected from toluene or xylene, and the molar ratio of the amount of the intermediate 7 to the amount of the trifluoromethanesulfonic acid is intermediate 7: trifluoromethanesulfonic acid ═ 1: 2.0 to 3.0;
in step (9), the organic solvent is selected from toluene, xylene or trimethylbenzene, and the molar ratio of the amount of the intermediate 8 to the amount of the aromatic secondary amine compound is intermediate 8: aromatic secondary amine compound ═ 1: 1.0-1.2, wherein the molar ratio of the use amount of the intermediate 8 to the use amount of the alkaline substance is that the intermediate 8: basic substance 1: 1.0-3.0, wherein the molar ratio of the using amount of the intermediate 3 to the using amount of the catalyst is that the intermediate 8: catalyst 1: 0.001-0.1, wherein the molar ratio of the dosage of the palladium-containing catalyst to the dosage of the organic phosphine ligand is that the palladium catalyst: organophosphine ligand ═ 1: 0.5 to 4.
7. Use of the organic photoelectric material according to any one of claims 1 to 4, wherein the organic photoelectric material is used in an OLED, and the organic photoelectric material according to any one of claims 1 to 4 is used in a light emitting layer of the OLED.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009302469A (en) * 2008-06-17 2009-12-24 Mitsui Chemicals Inc Organic transistor
KR20140021969A (en) * 2012-08-09 2014-02-21 희성소재 (주) Novel compounds, organic light emitting device display and organic solar battery using the same
CN110291064A (en) * 2017-02-02 2019-09-27 默克专利有限公司 Material for electronic device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009302469A (en) * 2008-06-17 2009-12-24 Mitsui Chemicals Inc Organic transistor
KR20140021969A (en) * 2012-08-09 2014-02-21 희성소재 (주) Novel compounds, organic light emitting device display and organic solar battery using the same
CN110291064A (en) * 2017-02-02 2019-09-27 默克专利有限公司 Material for electronic device

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