An isoquinoline phosphine compound and an organic electroluminescent device using the same

Abstract

The present invention relates to the technical field of organic electroluminescence, and in particular to an isoquinoline phosphine compound and an organic electroluminescent device using the same, wherein the general structure of the isoquinoline phosphine compound is: Ar is phenyl, deuterated phenyl, biphenyl, partially deuterated biphenyl, terphenyl, partially deuterated terphenyl, naphthyl, 9-phenylanthracenyl, pyrenyl, chrysene, benzanthracenyl, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9-phenyldibenzocarbazolyl, partially deuterated 9-phenyldibenzocarbazolyl, and 3,5-diphenyltriazine. The isoquinoline phosphine compound is suitable as an electron transport layer material of an organic electroluminescent device, and the organic electroluminescent device using the isoquinoline phosphine compound of the present invention as an electron transport material has higher luminous efficiency and longer service life.

Description

Technical Field

[0001] The invention relates to an isoquinoline phosphine compound and an organic electroluminescent device using the same, belonging to the technical field of organic electroluminescence. Background Art

[0002] Organic Light-Emitting Diode (UIV OLED) is also known as organic electroluminescence display and organic light-emitting semiconductor (Organic Electroluminesence Display, UIV OLED). It has a different type of light-emitting principle from Liquid Crystal Display (LCD). OLED display technology has the advantages of self-luminescence, wide viewing angle, almost infinitely high contrast, low power consumption, and extremely high response speed. The light-emitting principle of organic light-emitting diodes is similar to that of inorganic light-emitting diodes. When the component is subjected to a forward bias derived from direct current (DC), the applied voltage energy will drive electrons (Electron) and holes (Hole) to be injected into the component from the cathode and anode respectively. When the two meet and combine during conduction, the so-called electron-hole recombination (Electron-Hole Capture) is formed. When a chemical molecule is excited by external energy, if the electron spin (Electron Spin) and the ground state electron are paired, it is called a singlet state (Singlet), and the light it releases is the so-called fluorescence (Fluorescence); conversely, if the excited state electron and the ground state electron spin are not paired and are parallel, it is called a triplet state (Triplet), and the light it releases is the so-called phosphorescence (Phosphorescence).

[0003] OLED devices generally have the problem of unbalanced carrier transport. For example, the mobility of electrons in the electron transport layer is several orders of magnitude lower than the mobility of holes in the hole transport layer. The unbalanced electron / hole transport leads to an increase in the turn-on voltage and a decrease in the life of phosphorescent OLED devices. Therefore, the active development of electron transport materials with high mobility remains a hot topic in research.

[0004] Nitrogen aromatic compounds are usually used as electron transport materials due to their chemical stability and efficient electron transport performance, such as pyridines, quinolines, etc. TmPyPB, B3PYMPM, TPBi, Alq3, BCP and Bphen are all widely used electron transport materials. Among them, compound molecules containing quinoline structures have been used in OLED electron transport layers, but further structural modification is needed to obtain better electron transport effects. The properties of electron transport materials are usually the limiting factors of the lifespan and efficiency of organic electroluminescent devices, and new materials are needed to further improve the luminous efficiency of organic light-emitting elements. Summary of the invention

[0005] The present invention aims at the deficiencies of the prior art and provides an isoquinoline phosphine compound and an organic electroluminescent device using the same. The organic electroluminescent device using the compound of the present invention as an electron transport material has higher luminous efficiency and longer life.

[0006] The technical solution of the present invention to solve the above technical problem is as follows: an isoquinoline phosphine compound, the general structure of the isoquinoline phosphine compound is:

[0007] ;

[0008] Ar is any one of phenyl, deuterated phenyl, biphenyl, partially deuterated biphenyl, terphenyl, partially deuterated terphenyl, naphthyl, 9-phenylanthracenyl, pyrene, chrysene, benzanthracenyl, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9-phenyldibenzocarbazolyl, partially deuterated 9-phenyldibenzocarbazolyl, and 3,5-diphenyltriazine.

[0009] Further, Ar is selected from any one of the following structures:

[0010] .

[0011] Preferably, the isoquinoline phosphine compound is selected from any one of the following structures:

[0012] ;

[0013] ;

[0014] ;

[0015] .

[0016] Preferred compounds of the invention are characterized in that they are sublimable. These compounds generally have a molar mass of less than about 1000 g / mol.

[0017] The invention also discloses an organic electroluminescent device, wherein the organic electroluminescent device contains the isoquinoline phosphine compound of the invention.

[0018] Furthermore, the organic electroluminescent device comprises a cathode, an anode and an organic thin film layer sandwiched between the cathode and the anode, and the organic thin film layer contains the isoquinoline phosphine compound.

[0019] Furthermore, the organic thin film layer at least contains an electron transport layer.

[0020] Furthermore, the electron transport layer contains the isoquinoline phosphine compound.

[0021] The beneficial effects of the present invention are:

[0022] 1. The isoquinoline phosphine compound structure of the present invention has strong rigidity, high atomic bond energy, and high thermal stability. It is beneficial to the injection and migration of excitons. When used as an electron transport material, it can effectively reduce the driving voltage of the organic electroluminescent element, so that it has higher luminous efficiency and longer life.

[0023] 2. The isoquinoline phosphine compound of the present invention has a strong degree of structural conjugation, which makes the biquinoline molecules compactly and orderly stacked, thus having good charge transport and stability. And the symmetrical molecules can effectively promote the orderly arrangement of molecules, thereby improving the charge transport capacity. The phenylphosphine oxygen group in the isoquinoline phosphine compound of the present invention has excellent chemical modifiability, which is connected to the isoquinoline structure as a modifying group to construct a compound with excellent carrier transport properties. Thereby, the organic electroluminescent element using the compound has good electron mobility, relatively balanced carrier transport, and improved efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 is a schematic structural diagram of the organic electroluminescent device described in the embodiment;

[0025] In the figure, 1, substrate; 2, ITO; 3, hole injection layer; 4, hole transport layer; 5, light-emitting layer; 6, electron transport layer; 7, electron injection layer; 8, cathode reflective electrode layer. DETAILED DESCRIPTION

[0026] The specific implementation of the present invention is described in detail below. The present invention can be implemented in many other ways than those described herein, and those skilled in the art can make similar improvements without violating the connotation of the present invention, so the present invention is not limited by the specific embodiments disclosed.

[0027] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which the present invention belongs. The terms used are only for describing specific embodiments and are not intended to limit the present invention.

[0028] The preparation route of the isoquinoline phosphine compound of the present invention is as follows:

[0029] ;

[0030] The main raw materials are diethyl phosphite, 4-amino-7-bromoquinoline and 4-bromo-7-chloroquinoline, all of which are purchased. The synthetic compounds are represented by A, B, C, D, and E, and the final product is represented by F; wherein X is Cl, Br, and I.

[0031] The above synthesis method takes X=Br as an example, and the specific preparation process is as follows:

[0032] 1. Preparation of compound A: 4-amino-7-bromoquinoline (CAS: 65340-74-1) was used as the main raw material. 4-amino-7-bromoquinoline 10.0 g (44.8 mmol), potassium iodide (CAS: 7681-11-0) 14.8 g (89.6 mmol), and dichloromethane 120 ml were added to a 500 ml three-necked flask. The mixture was stirred and cooled to 10-20 ° C. The temperature was controlled at 10-20 ° C. 7.2 g (156.8 mmol) of isoamyl nitrite (CAS: 110-46-3) was added dropwise. After the addition was completed, the mixture was heated to 30-35 ° C and kept warm for 10 h. The mixture was hydrolyzed and washed with water. Activated carbon was used for decolorization. The mixture was passed through a silica gel chromatography column and concentrated. The crude product was beaten and dried with 3 times ethyl acetate to obtain 10.0 g of the target product A. The yield was 66.8%. GC: 99.8%. 1 HNMR:7.40-7.62 (2H, 7.47 (dd, J = 8.5, 2.0 Hz), 7.57 (dd, J = 5.1, 0.4 Hz)), 7.89-8.06 (2H, 7.94 (dt, J = 2.0, 0.5 Hz), 8.00 (dt, J= 8.5, 0.4 Hz)), 8.78(1H, dd, J = 5.1, 0.5 Hz).

[0033] Elemental analysis structure: molecular formula is C9H5BrIN; LC-MS product molecular weight: 333.9.

[0034] 2. Preparation of compound B: 4-bromo-7-chloroquinoline (CAS: 98519-65-4) was used as the main raw material. 4-bromo-7-chloroquinoline 10g (41.2mmol), triisopropyl borate 10g (53.6mmol) and tetrahydrofuran 100g were added to a 250ml three-necked flask. After the addition of the materials, the temperature was cooled to -80~-90°C with stirring. 16.2mL (40.4mmol) (2.5M / L) of n-butyl lithium was added dropwise. After the addition was completed and the temperature was kept warm for 2h, a sample was taken to track TLC and no 4-bromo-7-chloroquinoline remained. After the reaction was qualified, hydrolysis was performed with hydrochloric acid, extraction was performed with chloroform, the organic phase was separated and discarded, the aqueous phase was adjusted to neutral with potassium hydroxide water, the aqueous phase was extracted with ethyl acetate and then washed with water, and the crude product was pulped and dried with 2 times petroleum ether to obtain 6.7g of the target product B, HPLC: 97.5%, and the yield was 80%. 1 H NMR:7.47 (1H, dd, J = 8.6, 2.0 Hz), 7.72 (1H, dd, J = 5.2, 0.5 Hz), 7.99 (1H,ddd, J = 2.0, 0.6, 0.4 Hz), 8.28 (1H, dt,J = 8.6, 0.5 Hz), 8.90 (1H, dd, J = 5.2, 0.6 Hz).

[0035] Elemental analysis structure: molecular formula is C9H7BClNO2; LC-MS detection product molecular weight: 207.2.

[0036] 3. Preparation of compound C: With compound A and compound B as main raw materials, add compound A 10g (29.9mmol), potassium hydroxide 3.3g (59.8mmol), dioxane 100g, and water 18.7g into a 250ml three-necked flask filled with nitrogen. After the addition of the materials, add tetrakis(triphenylphosphine)palladium (CAS:14221-01-3) 0.34g (0.29mmol) under stirring. Raise the temperature to 60-65°C and begin to dropwise add compound B 5.9g (28.4mmol) in 15g tetrahydrofuran. Keep warm at 60-65°C for 5h. Take a sample and track TLC to find no compound B remaining. After the reaction is qualified, extract with toluene, wash with water, remove the solvent, and recrystallize with 1x toluene to obtain 8.1g of the target product C, HPLC: 99.26%, yield 77%. 1H NMR:7.85 (1H, dd, J = 8.7, 2.0 Hz), 7.97-8.28 (6H, 8.03(dt, J = 2.0, 0.5 Hz),8.06 (dd, J = 8.7, 2.0 Hz), 8.08 (dt, J = 2.0, 0.4 Hz), 8.17 (dt, J = 8.7, 0.4 Hz), 8.20 (dd, J = 5.5, 0.4 Hz), 8.22 (dt, J = 8.7, 0.4 Hz)), 8.38 (1H, dd, J =5.5, 0.4 Hz), 9.06-9.18 (2H, 9.12 (dd, J = 5.5,0.5 Hz), 9.13 (dd, J = 5.5, 0.4 Hz)).

[0037] Elemental analysis structure: molecular formula is C 18 H 10 BrClN2; LC-MS detected the molecular weight of the product: 368.8.

[0038] 4. Preparation of compound D: Compound C and dimethylphosphine oxide (CAS: 7211-39-4) were used as the main raw materials. Compound C was added into a 250 ml three-necked flask filled with nitrogen. 15.0g (40.6mmol), dimethylphosphine oxide 3.17g (40.6mmol), triethylamine 5.7g (56.8mmol), tri(dibenzylideneacetone) dipalladium (CAS: 52409-22-0) 0.37g (0.4mmol), 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (CAS: 564483-18-7) 0.46g (0.8mmol), dioxane 100.0g, stirring and heating to 80-90℃ for reaction, keeping warm for 5h, sampling and tracking TLC, no dimethylphosphine oxide remains, after the reaction is qualified, extraction with toluene, washing with water, desolventizing, dissolving with toluene through a silica gel column, desolventizing, recrystallizing with tetrahydrofuran / n-hexane, and drying to obtain 11.5g of compound D, HPLC: 99.42%, yield 77.6%. 1H NMR:2.01-2.11 (6H, 2.06 (s), 2.06 (s)), 7.80(1H, dd, J = 8.6, 1.9 Hz), 8.06-8.20 (3H, 8.12 (dt, J = 8.7, 0.4 Hz), 8.12(dt, J = 2.0,0.4 Hz), 8.13 (dd, J = 8.7, 2.0 Hz)), 8.21-8.39 (3H, 8.27 (dd, J= 5.4, 0.4 Hz), 8.28 (dd, J = 5.5, 0.4 Hz), 8.34 (dt, J = 1.9, 0.5 Hz)), 8.53(1H, ddd, J= 8.6, 0.5, 0.4 Hz), 9.08-9.26 (2H, 9.13 (dd, J = 5.5, 0.4 Hz), 9.20 (dd, J = 5.4, 0.5 Hz)).

[0039] Elemental analysis structure: molecular formula is C 20 H 16 ClN2OP; LC-MS detected the product molecular weight: 366.7.

[0040] 5. Preparation of compound E: Compound D was used as the raw material. Compound D 8g (21.8mmol), 6.6g (26.2mmol) of biboric acid pinacol ester (CAS: 73183-34-3), 4.3g (43.6mmol) of potassium acetate, 0.125g (0.22mmol) of Pd(dba)2 (CAS: 32005-36-0), 0.123g (0.44mmol) of tricyclohexylphosphine (CAS: 2622-14-2), and 80g of dioxane were added to a 250ml three-necked flask filled with nitrogen. The mixture was stirred and heated to 100-110°C, and the temperature was kept at 90-100°C for 5h. TLC determined that no compound E remained. After the reaction was qualified, the mixture was extracted, washed with water, passed through a column, desolvated, recrystallized, and dried to obtain 8g of compound E with a yield of 77.5%. HPLC: 99.2%. 1H NMR:1.35 (12H, s), 2.05-2.15 (6H, 2.10 (s), 2.10 (s)), 7.79-7.98 (2H, 7.85 (dd, J = 7.9, 2.0 Hz), 7.91 (dd, J = 8.6, 1.9 Hz)), 8.08(1H, dt, J = 2.0, 0.4 Hz), 8.18-8.36 (3H, 8.23 ​​(dt, J = 1.9, 0.5 Hz), 8.28(dd, J = 5.4, 0.4 Hz), 8.30 (dd, J = 5.5, 0.5 Hz)), 8.47-8.59 (2H, 8.53 (dt,J =7.9, 0.5 Hz), 8.53 (ddd, J = 8.6, 0.6, 0.4 Hz)), 9.20 (1H, dd, J = 5.4,0.5 Hz), 9.35 (1H, dd, J = 5.5, 0.4 Hz).

[0041] Elemental analysis structure: molecular formula is C 26 H 28 BN2O3P; LC-MS detected the product molecular weight: 477.3.

[0042] 6. The target product F (isoquinoline phosphine compound) uses compound D and aryl boronic acid as main raw materials, and adds compound D and aryl boronic acid, potassium carbonate, water, palladium catalyst in sequence, stirs and mixes with toluene, and potassium carbonate aqueous solution provides alkaline environment, controls the temperature to 70-80°C for reaction, keeps warm for 12-24 hours, takes samples for TLC detection, and shows that compound D has no residue, and is washed with water, desolventized, passed through a column, and refined with toluene to obtain the final product; or uses compound structure E and halogenated aromatic hydrocarbon as main raw materials, and similarly adds compound E and halogenated aromatic hydrocarbon, potassium carbonate, water, tetrakis(triphenylphosphine)palladium in sequence, stirs and mixes with toluene, and potassium carbonate aqueous solution provides alkaline environment, controls the temperature to 70-80°C for reaction, keeps warm for 12-24 hours, takes samples for TLC detection, and shows that compound E has no residue, and is washed with water, desolventized, passed through a column, and refined with toluene to obtain the final product

[0043] The aromatic boronic acid is selected from phenylboronic acid, 2-biphenylboronic acid, 2-terphenylboronic acid, 2-naphthaleneboric acid, 1-pyreneboric acid, 3-dibenzofuranboric acid, 9,9-dimethyl-1-fluoreneboric acid, N-phenyl-2-carbazoleboric acid, 9,9-diphenyl-2-fluoreneboric acid, etc.; the halogenated aromatic hydrocarbon is selected from chlorobenzene, iodobenzene, bromobenzene, 1-bromonaphthalene, 2-iodonaphthalene, 3-bromodibenzofuran, 9-bromophenanthrene, 2-bromo-9,9-dimethylfluorene, 3-bromo-N-phenylcarbazole, 4-chlorobiphenyl, etc.

[0044] 1. Compound Preparation Examples

[0045] Example 1: Preparation of Compound 2

[0046] The synthetic route is:

[0047] ;

[0048] The specific preparation steps are as follows:

[0049] Preparation of compound 2: Compound D and deuterated phenylboronic acid (CAS: 215527-70-1) were used as the main raw materials. Under nitrogen protection, 30 g (81.8 mmol) of compound D, 10.4 g (81.8 mmol) of deuterated phenylboronic acid, 28.2 g (204.5 mmol) of potassium carbonate, 65.8 ml of water, and 0.94 g (0.82 mmol) of tetrakis(triphenylphosphine)palladium were added in sequence into a 500 ml three-necked flask. 300 ml of toluene was used for stirring and mixing. The temperature was raised to 75-85°C for insulation reaction. The reaction was tracked by TLC. After about 10 hours of reaction, no compound D remained. The reaction was then allowed to stand for stratification. The organic phase was washed with water, desolvated, chromatographed on a silica gel column, recrystallized from toluene, and dried to obtain 25.3 g of off-white solid of compound 2, HPLC: 99.9%, yield 75%.

[0050] Elemental analysis structure: molecular formula is C 26 H 16 D5N2OP; LC-MS detected product molecular weight: 413.2; 1H NMR:2.08-2.18 (6H, 2.13 (s), 2.13 (s), 2.13 (s), 2.13 (s)), 7.49-7.81 (6H, 7.55(tdd, J = 7.6, 2.0, 1.4 Hz), 7.57 (dddd, J= 8.2, 7.6, 1.5, 0.4 Hz), 7.57(dddd, J = 7.8, 7.6, 1.5, 0.5 Hz), 7.70 (dd, J = 8.7, 2.0 Hz), 7.70 (dt, J =2.0, 0.5 Hz), 7.75 (dtd, J = 8.2, 1.5, 0.5 Hz)),7.89-8.07 (2H, 7.95 (dddd, J= 7.8, 2.0, 1.5, 0.4 Hz), 8.00 (dd, J = 8.7, 2.0 Hz)), 8.17 (1H, dd, J = 5.5,0.4 Hz), 8.35 (1H, dd, J = 5.5, 0.4 Hz), 8.45-8.65 (3H, 8.51 (dt, J = 2.0,0.5 Hz), 8.52 (ddd, J = 8.7, 0.5, 0.4 Hz), 8.59 (dd, J= 5.5, 0.5 Hz)), 8.80-9.05 (4H, 8.86 (dt, J = 8.7, 0.5 Hz), 8.96 (dd, J = 5.5, 0.5 Hz), 9.00 (d, J= 3.2 Hz)).

[0051] Example 2: Preparation of Compound 4

[0052] The synthetic route is:

[0053] ;

[0054] The specific preparation steps are as follows:

[0055] Preparation of compound 4: Compound D and 3-biphenylboronic acid (CAS: 5122-95-2) were used as the main raw materials. Under nitrogen protection, compound D was added into a 500 ml three-necked flask in sequence. 30g (81.8mmol), 16.2g (81.8mmol) of 3-biphenylboronic acid, 28.2g (204.5mmol) of potassium carbonate, 65.8ml of water, 0.18g (0.82mmol) of palladium acetate (CAS: 3375-31-3), 0.78g (1.64mmol) of 2-dicyclohexylphospho-2',4',6'-triisopropylbiphenyl, 300ml of toluene was used for stirring and mixing, and the temperature was raised to 65-75℃ for reaction. The reaction was tracked by TLC. After about 3h of reaction, no compound D remained. After the reaction was completed, the system was separated and the organic phase was washed with water, desolvated, chromatographed on a silica gel column, recrystallized from toluene, and dried to obtain 30.9g of compound 4 as an off-white solid, HPLC: 99.89%, yield 78%.

[0056] Elemental analysis structure: molecular formula is C 32 H 25 N2OP; LC-MS detected product molecular weight: 484.2; 1H NMR: 2.10-2.20 (6H, 2.15 (s), 2.15 (s), 2.15 (s), 2.15 (s)), 7.51-7.82 (7H, 7.57 (dtd,J = 7.5, 3.7, 3.1 Hz), 7.65 (dddd, J= 7.8, 1.9, 1.1, 0.5 Hz), 7.65 (dd, J =8.7, 2.0 Hz), 7.72 (dt, J = 2.0, 0.5 Hz), 7.76 (td, J = 7.9, 0.5 Hz)), 7.84-8.29 (6H, 7.91 (dddd, J = 8.1, 2.4, 1.9,0.5 Hz), 7.92 (ddd, J = 7.9, 2.6, 2.4Hz), 8.01 (dd, J = 8.7, 2.0 Hz), 8.12 (dt, J = 2.0, 0.5 Hz), 8.19 (dd, J =5.5, 0.4 Hz), 8.22 (ddd, J = 7.9, 2.6, 2.4Hz)), 8.30-8.46 (2H, 8.35 (dd, J =5.6, 0.4 Hz), 8.41 (td, J = 2.4, 0.5 Hz)), 8.59 (1H, ddd, J = 8.7, 0.5, 0.4Hz), 8.75-9.05 (5H, 8.80 (dd, J = 5.6, 0.5Hz), 8.87 (ddd, J = 8.7, 0.5, 0.4Hz), 8.91 (dd, J = 5.5, 0.5 Hz), 9.00 (d, J = 3.2 Hz), 9.00 (d, J = 3.2 Hz)).

[0057] Example 3: Preparation of Compound 6

[0058] The synthetic route is:

[0059] ;

[0060] The specific preparation steps are as follows:

[0061] Preparation of compound H-6: Deuterated benzene boronic acid and p-chlorobromobenzene (CAS: 106-39-8) were used as the main raw materials. Under nitrogen protection, p-chlorobromobenzene 30g (156.7mmol), potassium carbonate 54g (391.7mmol), and water 126.2ml were added to a 500ml three-necked flask in sequence. After the addition of the materials, 0.9g (0.78mmol) of tetrakis(triphenylphosphine)palladium was added under stirring. 300ml of toluene was used to stir and mix. The temperature was raised to 65-75°C. A solution of 19.9g (156.7mmol) of deuterated benzene boronic acid in 40g of tetrahydrofuran was added dropwise to the reaction. After the addition was completed, the reaction was kept warm and the reaction was tracked by TLC. The reaction was completed in about 2h, and no p-chlorobromobenzene remained. After the reaction, the system was separated, and the organic phase was washed with water, desolventized, recrystallized from toluene, and dried to obtain 25.5g of compound H-6 as a light yellow solid, GC: 99.25%, and the yield was 84%.

[0062] Elemental analysis structure: molecular formula is C 12 H4D5Cl; GC-MS detected the product molecular weight: 193.5.

[0063] Preparation of compound 6: Compound H-6 and compound E were used as main raw materials. Under nitrogen protection, 20 g (103.3 mmol) of compound H-6, 49.3 g (103.3 mmol) of compound E, 35.6 g (258.3 mmol) of potassium carbonate and 83.2 ml of water were added to a 500 ml three-necked flask in sequence. After the addition of the materials, 0.23 g (1.033 mmol) of palladium acetate and 0.58 g (2.066 mmol) of tricyclohexylphosphine were added under stirring. 300 ml of tetrahydrofuran was used to stir and mix. The temperature was raised to 50-60 ° C and the reaction was kept warm. The reaction was tracked by TLC. The reaction was completed in about 10 hours, and no compound H-6 remained. After the reaction, the system was separated, and the organic phase was washed with water, silica gel column chromatography, desolvated, recrystallized from toluene, and dried to obtain 41.9 g of compound 6 as an off-white solid, HPLC: 99.90%, yield 82.9%.

[0064] Elemental analysis structure: molecular formula is C 32 H 20 D5N2OP; LC-MS detected product molecular weight: 489.2; 1H NMR:2.20-2.30 (6H, 2.25 (s), 2.25 (s)), 7.47 (1H, tdd, J = 7.7, 2.0, 1.2 Hz), 7.61-7.82 (4H, 7.68 (dddd, J = 8.2, 7.7,1.5, 0.5 Hz), 7.76 (dtd, J = 8.2,1.5, 0.5 Hz)), 7.87-8.07 (4H, 7.93 (dd, J = 8.7, 2.0 Hz), 7.96 (dd, J = 7.3,1.8 Hz), 8.01 (ddd, J = 8.4, 1.5, 0.5 Hz)),8.19-8.40 (5H, 8.26 (ddd, J = 8.4,2.2, 0.5 Hz), 8.26 (dd, J = 5.4, 0.4 Hz), 8.29 (dt, J = 1.8, 0.5 Hz), 8.35(dd, J = 5.4, 0.5 Hz)), 8.51-8.77 (3H, 8.56(dt, J = 2.0, 0.5 Hz), 8.59 (dt, J= 7.3, 0.5 Hz), 8.70 (dt, J = 8.7, 0.5 Hz)), 9.40 (1H, dd, J = 5.4, 0.5 Hz), 9.61 (1H, dd, J = 5.4, 0.5 Hz).

[0065] Example 4: Preparation of Compound 11

[0066] The synthetic route is:

[0067] ;

[0068] The specific preparation steps are as follows:

[0069] Preparation of compound 11: Compound D and 2-naphthaleneboric acid (CAS: 32316-92-0) were used as the main raw materials. Under nitrogen protection, 30 g (81.8 mmol) of compound D, 14.1 g (81.8 mmol) of 2-naphthaleneboric acid, 28.2 g (204.5 mmol) of potassium carbonate, 65.8 mL of water, and 0.94 g (0.82 mmol) of tetrakis(triphenylphosphine)palladium were added in sequence into a 500 ml three-necked flask. 300 g of toluene was used for stirring and mixing. The temperature was raised to 70-75°C for insulation reaction. The reaction was tracked by TLC. After about 3 hours of reaction, no compound D remained. After the reaction was completed, the system was separated and the organic phase was washed with water, desolvated, recrystallized from toluene, and dried to obtain 31.5 g of brown-gray solid of compound 11, HPLC: 99.75%, yield 84%.

[0070] Elemental analysis structure: molecular formula is C 30 H 23 N2OP; LC-MS detected product molecular weight: 458.2; 1 H NMR: 2.19-2.29 (6H, 2.24 (s), 2.24 (s)), 7.61 (1H, dddd, J = 7.9, 7.7, 1.8, 0.5 Hz), 7.81 (1H, dddd, J = 8.0, 7.7, 2.6, 0.5 Hz), 7.89-8.10 (3H, 7.95 (dd, J = 7.3,1.8 Hz), 8.03 (dd, J = 8.7, 2.0 Hz), 8.05 (dd, J = 5.4, 0.5 Hz)), 8.17-8.68(9H, 8.23 ​​(ddd, J = 8.4, 2.0, 0.5 Hz),8.27 (dddt, J = 7.9, 2.6, 1.9, 0.5 Hz), 8.26 (dd, J = 5.4, 0.4 Hz), 8.28 (dt, J = 1.8, 0.5 Hz), 8.37 (ddq, J = 2.0,1.9, 0.5 Hz), 8.40 (dddq, J = 8.0, 2.0,1.8, 0.4 Hz), 8.45 (ddq, J = 8.4, 2.0,0.5 Hz), 8.56 (dt, J = 2.0, 0.5 Hz), 8.62 (dt, J = 7.3, 0.5 Hz)), 8.78 (1H,dt, J = 8.7, 0.5 Hz), 9.41 (1H, dd, J =5.4, 0.5 Hz), 9.65 (1H, dd, J = 5.4,0.5 Hz).

[0071] Example 5: Preparation of Compound 15

[0072] The synthetic route is:

[0073] ;

[0074] The specific preparation steps are as follows:

[0075] Preparation of compound 15: Compound D and 2-chryseneboric acid (CAS: 1922905-61-0) were used as the main raw materials. Under nitrogen protection, 30 g (81.8 mmol) of compound D, 22.2 g (81.8 mmol) of 2-chryseneboric acid, 28.2 g (204.5 mmol) of potassium carbonate, 65.8 ml of water, 0.18 g (0.82 mmol) of palladium acetate, and 0.78 g (1.64 mmol) of 2-dicyclohexylphospho-2',4',6'-triisopropylbiphenyl were added to a 500 ml three-necked flask in sequence. 300 ml of toluene was used to stir and mix. The temperature was raised to 75-80°C for reaction. The reaction was tracked by TLC. After 6 hours of reaction, no compound D remained. After the reaction was completed, the organic phase was washed with water, desolventized, recrystallized from toluene, and dried to obtain 39.6 g of compound 15 as a light yellow solid. HPLC: 99.94%, yield 86.7%.

[0076] Elemental analysis structure: molecular formula is C 38 H 27 N2OP; LC-MS detected product molecular weight: 558.2; 1H NMR: 2.29-2.39 (6H, 2.34 (s), 2.34 (s)), 7.72-7.89 (2H, 7.79 (dddd, J = 7.7, 6.0, 2.2,0.4 Hz), 7.82 (ddd, J = 7.7, 5.8,1.8 Hz)), 8.04-8.17 (2H, 8.10 (dd, J = 5.8,1.5 Hz), 8.12 (dt, J = 1.5, 0.5 Hz)), 8.20-8.43 (3H, 8.26 (dd, J = 5.4, 0.4Hz), 8.34 (dd, J = 5.2, 0.5 Hz),8.36 (dd, J = 7.9, 2.0 Hz)), 8.44-8.90 (12H,8.50 (dd, J = 5.1, 2.0 Hz), 8.56 (dt, J = 2.0,0.5 Hz), 8.60 (dtt, J = 6.0,1.8, 0.5 Hz), 8.62 (ddq, J = 5.8, 2.2, 0.5 Hz), 8.63 (dddd, J = 5.4, 1.8,0.5, 0.4 Hz), 8.70 (dt, J = 5.8, 0.5Hz), 8.70 (dddd, J = 5.1, 2.0, 0.5 Hz), 8.74 (dq, J = 5.1, 0.5 Hz), 8.78 (tt, J = 2.0, 0.5 Hz), 8.79 (dq, J = 5.1,0.5 Hz), 8.81 (dq, J = 5.4, 0.5 Hz), 8.84(dt, J = 7.9, 0.5 Hz)), 9.29 (1H,dd, J = 5.4, 0.5 Hz), 9.64 (1H, dd, J = 5.2, 0.5 Hz).

[0077] Example 6: Preparation of Compound 20

[0078] The synthetic route is:

[0079] ;

[0080] The specific preparation steps are as follows:

[0081] Preparation of compound 20: Compound D and 2-phenanthrene boronic acid (CAS: 1188094-10-1) were used as the main raw materials. Under nitrogen protection, 30 g (81.8 mmol) of compound D, 18.1 g (81.8 mmol) of 2-phenanthrene boronic acid, 28.2 g (204.5 mmol) of potassium carbonate, 65.8 ml of water, 0.18 g (0.82 mmol) of palladium acetate, and 0.94 g (1.64 mmol) of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (CAS: 161265-03-8) were added into a 500 ml three-necked flask in sequence. 300 ml of toluene was used to stir and mix. The temperature was raised to 75-80 ° C and the reaction was kept warm. The reaction was tracked by TLC. After 5 h of reaction, no compound D remained. After the reaction was completed, the organic phase was washed with water, desolventized, recrystallized from toluene, and dried to obtain 32.6 g of brown-yellow solid compound 20, HPLC: 99.74%, yield 78.5%.

[0082] Elemental analysis structure: molecular formula is C 34 H 25 N2OP; LC-MS detected product molecular weight: 508.1; 1H NMR: 2.24-2.34 (6H, 2.29 (s), 2.29 (s)), 7.66-7.83 (2H, 7.73 (dddd, J = 7.7, 6.5, 2.3,0.4 Hz), 7.76 (ddd, J = 7.7, 7.3,1.8 Hz)), 8.05 (1H, dd, J = 5.9, 1.8 Hz), 8.20-8.83 (14H, 8.26 (dd, J = 5.4, 0.4 Hz), 8.29 (dd, J = 5.4, 0.5 Hz), 8.36 (dt, J = 1.8, 0.5 Hz), 8.41 (dd, J =8.5, 1.9 Hz), 8.43 (ddt, J = 5.5, 2.0,0.5 Hz), 8.46 (dd, J = 8.7, 2.0 Hz), 8.51 (dddt, J = 6.5, 2.0, 1.8, 0.5 Hz), 8.52 (ddq, J = 7.3, 2.3, 0.5 Hz), 8.52(tt, J = 2.0, 0.4 Hz), 8.56 (dt, J =2.0, 0.5 Hz), 8.65 (dt, J = 5.9, 0.5 Hz), 8.65 (dq, J = 8.5, 0.4 Hz), 8.66(ddq, J = 5.5, 2.0, 0.4 Hz), 8.77 (dt, J =8.7, 0.5 Hz)), 9.42 (1H, dd, J =5.4, 0.5 Hz), 9.63 (1H, dd, J = 5.4, 0.5 Hz).

[0083] Example 7: Preparation of Compound 31

[0084] The synthetic route is:

[0085] ;

[0086] The specific preparation steps are as follows:

[0087] Preparation of compound 31: Compound D and 4-dibenzofuranboronic acid (CAS: 100124-06-9) were used as the main raw materials. Under nitrogen protection, 30 g (81.8 mmol) of compound D, 17.3 g (81.8 mmol) of 4-dibenzofuranboronic acid, 28.2 g (204.5 mmol) of potassium carbonate, 65.8 ml of water, 0.75 g (0.82 mmol) of tris(dibenzylideneacetone)dipalladium, and 0.43 g (1.64 mmol) of triphenylphosphine (CAS: 603-35-0) were added into a 500 ml three-necked flask in sequence. 300 g of toluene was used for stirring and mixing. The temperature was raised to 85-90°C for reaction. The reaction was monitored by TLC. After about 10 hours of reaction, no compound D remained. After the reaction was completed, the system was separated and the organic phase was washed with water, desolvated, recrystallized from toluene, and dried to obtain 36.7 g of off-white solid compound 31. HPLC: 99.88%, yield 90%.

[0088] Elemental analysis structure: molecular formula is C 32 H 23 N2O2P; LC-MS detected product molecular weight: 498.2; 1H NMR:2.30-2.40 (6H, 2.35 (s), 2.35 (s)), 7.87-8.33 (6H, 7.94 (dd, J = 7.9, 2.0Hz), 7.99 (ddd, J = 5.5, 5.0, 1.5 Hz), 8.06 (dd, J = 5.0, 1.5 Hz), 8.10 (ddd,J = 5.5, 1.9, 0.5 Hz), 8.16 (dt, J = 1.8, 0.5 Hz), 8.27 (td, J = 5.0, 1.9Hz)), 8.33-8.47 (2H, 8.39 (dd, J = 5.4,0.5 Hz), 8.42 (dt, J = 1.5, 0.5 Hz)), 8.55-8.94 (7H, 8.61 (dd, J = 6.2, 1.8 Hz), 8.68 (dd, J = 5.1, 0.5 Hz), 8.70 (dt, J = 5.0, 0.5 Hz), 8.72 (ddt, J =5.0, 1.5, 0.5 Hz), 8.74 (dd, J = 7.9,5.9 Hz), 8.77 (ddd, J = 5.9, 2.0, 0.5 Hz), 8.88 (dt, J = 6.2, 0.5 Hz)), 9.19-9.36 (2H, 9.25 (dd, J = 5.4, 0.5 Hz),9.30 (dd, J = 5.1, 0.5 Hz)).

[0089] Example 8: Preparation of Compound 41

[0090] The synthetic route is:

[0091] ;

[0092] The specific preparation steps are as follows:

[0093] Preparation of compound 41: Compound D and 9,9-dimethyl-2-fluoreneboronic acid (CAS: 569343-09-5) were used as the main raw materials. Under nitrogen protection, 30 g (81.8 mmol) of compound D, 19.5 g (81.8 mmol) of 9,9-dimethyl-2-fluoreneboronic acid, 28.2 g (204.5 mmol) of potassium carbonate, 65.8 ml of water, 0.18 g (0.82 mmol) of palladium acetate, and 0.46 g (1.64 mmol) of tricyclohexylphosphine were added into a 500 ml three-necked flask in sequence. 300 ml of toluene was used to stir and mix. The temperature was raised to 75-85°C for reaction. The reaction was tracked by TLC. After 5 hours of reaction, no compound D remained. After the reaction was completed, the organic phase was washed with water, desolventized, recrystallized from toluene, and dried to obtain 35.8 g of compound 41 as a light yellow solid. HPLC: 99.68%, yield 83.4%.

[0094] Elemental analysis structure: molecular formula is C 35 H 29 N2OP; LC-MS detected product molecular weight: 524.2; 1H NMR: 2.20-2.33 (12H, 2.25 (s), 2.28 (s), 2.28 (s)), 7.31-7.69 (4H, 7.38 (ddd, J = 8.3,8.0, 1.6 Hz), 7.53 (ddd, J = 8.3,8.0, 1.8 Hz), 7.60 (ddd, J = 8.3, 1.8, 0.4Hz), 7.62 (ddd, J = 8.3, 1.6, 0.4 Hz)), 7.70-8.00 (4H, 7.76 (dd, J = 8.2, 1.6Hz), 7.86 (dd, J = 1.6, 0.4 Hz),7.89 (dd, J = 7.3, 1.8 Hz), 7.94 (dd, J =8.7, 2.0 Hz)), 8.07-8.37 (4H, 8.13 (dt, J = 1.8, 0.5 Hz), 8.22 (dd, J = 8.2,0.4 Hz), 8.26 (dd, J = 5.4, 0.4 Hz), 8.32 (dd, J = 5.4, ​​0.5 Hz)), 8.49-8.61(2H, 8.55 (dt, J = 7.3, 0.5 Hz), 8.56 (dt, J = 2.0, 0.5 Hz)), 8.68 (1H, dt, J= 8.7, 0.5 Hz), 8.90 (1H, dd, J = 5.4,0.5 Hz), 9.39 (1H, dd, J = 5.4, 0.5Hz).

[0095] Example 9: Preparation of Compound 47

[0096] The synthetic route is:

[0097] ;

[0098] The specific preparation steps are as follows:

[0099] Preparation of compound H-47: Using o-chlorobromobenzene (CAS: 694-80-4) and carbazole (CAS: 86-74-8) as the main raw materials, under nitrogen protection, o-chlorobromobenzene 30g (156.7mmol), carbazole 26.2g (156.7mmol), sodium tert-butoxide 22.5g (235.1mmol), palladium acetate 0.35g (1.567mmol), 2-dicyclohexylphosphine-2', 1.49 g (3.13 mmol) of 4',6'-triisopropylbiphenyl was stirred and mixed with 300 ml of toluene, and the temperature was raised to 95-100°C for reaction. The reaction was tracked by TLC. After about 12 hours of reaction, no compound o-chlorobromobenzene remained. After the reaction was completed, 100 g of water was added to the system for hydrolysis. The organic phase was washed with water, subjected to silica gel column chromatography, desolvated, recrystallized from toluene, and dried to obtain 36 g of compound H-47 as a light yellow solid, GC: 99.84%, yield 82.6%.

[0100] Elemental analysis structure: molecular formula is C 18 H 12 ClN; GC-MS detected the molecular weight of the product: 277.1;

[0101] Preparation of compound 47: With compound H-47 and compound E as main raw materials, in a 500 ml three-necked flask under nitrogen protection, 30 g (65.4 mmol) of compound E, 18.1 g (65.4 mmol) of compound H-47, 22.6 g (163.5 mmol) of potassium carbonate, 52.7 ml of water, 0.6 g (0.654 mmol) of tris(dibenzylideneacetone)dipalladium, and 0.34 g (1.3 mmol) of triphenylphosphine were added in sequence, and 300 ml of toluene was used to stir and mix, and the temperature was raised to 70-80 ° C for reaction. The reaction was tracked by TLC. The reaction was carried out for about 24 hours until no compound E remained. After the reaction, the system was separated and the organic phase was washed with water, silica gel column chromatography, desolvated, recrystallized from toluene, and dried to obtain 30.7 g of compound 47 as an off-white solid, HPLC: 99.88%, yield 81.8%.

[0102] Elemental analysis structure: molecular formula is C 38 H 28 N3OP; LC-MS detected product molecular weight: 573.4; 1H NMR:2.44-2.53 (6H, 2.48 (s), 2.48 (s)), 7.71-7.96 (6H, 7.78 (ddd, J = 8.5, 5.7,1.8 Hz), 7.86 (ddd, J = 8.5, 1.5, 0.4Hz), 7.87 (td, J = 8.23 (dd, J = 5.8, 1.7 Hz), 8.26 (dt, J =2.0, 0.5 Hz), 8.36 (ddd, J = 5.0, 1.7, 0.5 Hz), 8.43 (dt, J = 1.7, 0.5 Hz), 8.46 (dd, J = 6.4, 2.0 Hz)), 8.52-8.73 (5H, 8.58 (ddt, J = 5.0, 1.8, 0.5 Hz), 8.62 (dd, J = 5.1, 0.5 Hz), 8.64 (dt, J = 5.8, 0.5Hz), 8.67 (dd, J = 6.4, 0.5Hz)), 8.89 (1H, dt, J = 6.4, 0.5 Hz), 9.17-9.30 (2H, 9.23 (dd, J = 5.1, 0.5Hz), 9.24 (dd, J = 6.4, 0.5 Hz)).

[0103] Example 10: Preparation of Compound 50

[0104] The synthetic route is:

[0105] ;

[0106] The specific preparation steps are as follows:

[0107] Preparation of compound H-50: Deuterated bromobenzene (CAS: 4165-57-5) and 2-chloro-9H-carbazole (CAS: 10537-08-3) are the main raw materials. Under nitrogen protection, 24.9 g (123.4 mmol) of 2-chloro-9H-carbazole, 22 g (135.7 mmol) of deuterated bromobenzene, 14.2 g (148.1 mmol) of sodium tert-butoxide, 1.12 g (1.23 mmol) of tris(dibenzylideneacetone)dipalladium, and 1.17 g (2.26 mmol) of 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl were added to a 500 ml three-necked flask in sequence, and the mixture was stirred and mixed with 250 ml of toluene, and the mixture was heated to 100-105°C for reaction. The reaction was followed by TLC. After about 5 hours of reaction, no 2-chloro-9H-carbazole remained. After the reaction was completed, 100 g of water was added to the system for hydrolysis, and the organic phase was washed with water, desolventized, recrystallized from toluene, and dried to obtain compound H-50, 32 g of yellow solid, GC: 98.98%, yield 91.5%. Elemental analysis structure: Molecular formula is C 18 H7D5ClN; GC-MS detected the molecular weight of the product: 282.1;

[0108] Preparation of compound 50: With compound H-50 and compound E as main raw materials, in a 500 ml three-necked flask under nitrogen protection, 30 g (65.4 mmol) of compound E, 18.5 g (65.4 mmol) of compound H-50, 22.6 g (163.5 mmol) of potassium carbonate, 52.7 ml of water, 0.6 g (0.654 mmol) of tris(dibenzylideneacetone)dipalladium, and 0.34 g (1.3 mmol) of triphenylphosphine were added in sequence, and 300 ml of toluene was used to stir and mix, and the temperature was raised to 70-80 ° C for reaction. The reaction was tracked by TLC. The reaction lasted for about 15 h until no compound E remained. After the reaction, the system was separated and the organic phase was washed with water, desolventized, recrystallized from toluene, and dried to obtain 33.1 g of yellow solid compound 50, HPLC: 99.55%, yield 87.5%.

[0109] Elemental analysis structure: molecular formula is C 38 H 23 D5N3OP; LC-MS detected product molecular weight: 578.2; 1H NMR:2.33-2.43 (6H, 2.38 (s), 2.38 (s)), 7.42-7.64 (3H, 7.48 (tdd, J = 7.6, 1.6,1.2 Hz), 7.57 (dddd, J = 8.2, 7.6, 1.5,0.4 Hz)), 7.82-7.99 (3H, 7.88 (dd, J =5.1, 2.0 Hz), 7.92 (dtd, J = 8.2, 1.5, 0.4 Hz)), 8.01-8.13 (2H, 8.07 (dd, J =5.0, 1.7 Hz), 8.07 (td, J = 5.0, 1.7Hz)), 8.18-8.47 (5H, 8.25 (ddd, J = 5.5,5.0, 1.8 Hz), 8.26 (dt, J = 2.0, 0.5 Hz), 8.33 (dd, J = 2.0, 0.5 Hz), 8.38 (dd, J = 5.4, 0.6 Hz), 8.41 (dt, J = 1.7,0.5 Hz)), 8.60-8.79 (3H, 8.66 (dd, J= 5.1, 0.5 Hz), 8.72 (dt, J = 5.0, 0.5 Hz), 8.73 (dd, J = 6.1, 2.0 Hz)), 8.79-8.95 (2H, 8.85 (ddd, J = 5.5, 1.7, 0.6Hz), 8.89 (dt, J = 6.1, 0.5 Hz)),8.96-9.13 (2H, 9.02 (ddt, J = 5.0, 1.8, 0.5 Hz), 9.07 (dt, J = 5.1, 0.5 Hz)),9.17-9.35 (2H, 9.23 (dd, J = 5.4, 0.5 Hz),9.29 (dd, J = 5.1, 0.5 Hz)).

[0110] Example 11: Preparation of Compound 55

[0111] The synthetic route is:

[0112] ;

[0113] The specific preparation steps are as follows:

[0114] Preparation of compound 55: Compound D and 9,9-diphenyl-2-fluoreneboronic acid (CAS: 400607-31-0) were used as the main raw materials. Under nitrogen protection, compound D was added into a 500 ml three-necked flask in sequence. 30g (81.8mmol), 40.9g (81.8mmol) of 9,9-diphenyl-2-fluoreneboronic acid, 28.2g (204.5mmol) of potassium carbonate, 65.8ml of water, 0.18g (0.82mmol) of palladium acetate, 0.78g (1.64mmol) of 2-dicyclohexylphospho-2',4',6'-triisopropylbiphenyl, 300ml of toluene were used for stirring and mixing, and the temperature was raised to 85-95℃ for reaction. The reaction was tracked by TLC. The reaction lasted for about 18h until no compound D remained. After the reaction, the system was separated and the organic phase was washed with water, desolvated, recrystallized from toluene, and dried to obtain 42.9g of compound 55 as a gray-brown solid, HPLC: 99.87%, yield 80.8%.

[0115] Elemental analysis structure: molecular formula is C 45 H 33 N2OP; LC-MS detected product molecular weight: 648.3; 1H NMR:2.23-2.32 (6H, 2.27 (s), 2.27 (s)), 7.16-7.34 (10H, 7.22 (dddd, J = 7.9, 1.4, 1.2,0.5 Hz), 7.23 (tt, J = 7.7, 1.2Hz), 7.27 (dddd, J = 7.9, 7.7, 1.8, 0.5 Hz)),7.48-8.01 (7H, 7.55 (ddd, J = 8.4, 7.7, 1.8 Hz), 7.58 (ddd, J = 8.3, 7.7, 1.8Hz), 7.66 (ddd, J = 8.4, 1.8,0.4 Hz), 7.70 (ddd, J = 8.3, 1.8, 0.4 Hz), 7.77(dd, J = 8.2, 1.8 Hz), 7.89 (dd, J = 7.3, 1.8 Hz), 7.95 (dd, J = 8.7, 2.0Hz)), 8.07-8.38 (5H, 8.12 (dd, J= 1.8, 0.4 Hz), 8.13 (dt, J = 1.8, 0.5 Hz), 8.24 (dd, J = 8.2, 0.4 Hz), 8.26 (dd, J = 5.4, 0.4 Hz), 8.32 (dd, J = 5.4,0.5 Hz)), 8.49-8.62 (2H, 8.55 (dt, J= 7.3, 0.5 Hz), 8.56 (dt, J = 2.0, 0.5Hz)), 8.68 (1H, dt, J = 8.7, 0.5 Hz), 8.91 (1H, dd, J = 5.4, 0.5 Hz), 9.40 (1H, dd, J = 5.4, 0.5 Hz).

[0116] Example 12: Preparation of Compound 58

[0117] The synthetic route is:

[0118] ;

[0119] The specific preparation steps are as follows:

[0120] Preparation of compound H-58: Deuterated bromobenzene and cyanuric chloride (CAS: 108-77-0) were used as the main raw materials. Under nitrogen protection, 6 g (250 mmol) of magnesium flakes were added to a 500 ml three-necked flask to prepare a solution of 40.5 g (250 mmol) of deuterated bromobenzene and 120 g of tetrahydrofuran. A small amount of the solution was added to the magnesium flakes to raise the temperature for initiation. After successful initiation, the temperature was controlled at 60-65 °C and the remaining solution was added dropwise. After the addition was completed, the reaction was completed by keeping the temperature for 2 hours. After the reaction, the reaction liquid was added dropwise to a solution of 15.4 g (83.3 mmol) of cyanuric chloride in 50 g of tetrahydrofuran at a temperature of -5 to 0 °C. After the addition, the temperature was kept at -5 to 0 °C for reaction. The reaction was followed by GC. The reaction was completed in about 16 hours with a purity of 72%. After the reaction, the reaction liquid was hydrolyzed into a hydrochloric acid aqueous solution for quenching, and then toluene was added for extraction. The organic phase was washed with water, desolventized, decolorized with activated carbon, chromatographed on a silica gel column, recrystallized with ethyl acetate, and dried to obtain compound H-58, 13.4 g of white solid, GC: 99.65%, yield 58%. Elemental analysis structure: Molecular formula is C 15 D 10 ClN3; GC-MS detected the molecular weight of the product: 277.1;

[0121] Preparation of compound 58: With compound H-58 and compound E as main raw materials, in a 500ml three-necked flask under nitrogen protection, 30g (65.4mmol) of compound E, 18.1g (65.4mmol) of compound H-58, 22.5g (163.5mmol) of potassium carbonate, 52.7ml of water, 300ml of toluene, 0.60g (0.65mmol) of tris(dibenzylideneacetone)dipalladium, and 0.62g (1.3mmol) of 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl were added in sequence, and the mixture was stirred and heated to 65-75℃ for reaction. The reaction was tracked by TLC. The reaction was carried out for 13h until no compound E remained. The layers were separated, and the organic phase was washed with water, desolventized, recrystallized from toluene, and dried to obtain 31.5g of yellow solid compound 58, HPLC: 99.91%, yield 84%.

[0122] Elemental analysis structure: molecular formula is C 35 H 16 D 10 N5OP; LC-MS detected product molecular weight: 573.2; 1H NMR:2.20-2.30 (6H, 2.25 (s), 2.25 (s)), 7.75-8.04 (7H, 7.83 (dddd, J = 8.2, 7.5,2.2, 0.5 Hz), 7.96 (tdd, J = 7.5, 1.7,1.5 Hz), 7.98 (dd, J = 5.9, 1.8 Hz)),8.13-8.35 (7H, 8.19 (dtd, J = 8.2, 1.6, 0.5 Hz), 8.26 (dt, J = 1.4, 0.5 Hz),8.29 (dd, J = 5.4, 0.5 Hz), 8.30 (dt, J =1.8, 0.5 Hz)), 8.52 (1H, dd, J =6.4, 0.5 Hz), 8.60-8.80 (3H, 8.66 (dt, J = 8.7, 0.5 Hz), 8.72 (dt, J = 5.9,0.5 Hz), 8.74 (dd, J = 8.7, 1.4 Hz)),9.18-9.31 (2H, 9.24 (dd, J = 6.4, 0.5Hz), 9.25 (dd, J = 5.4, 0.5 Hz)).

[0123] 2. Application Examples

[0124] This application example provides an organic electroluminescent device, the structural schematic diagram of which is shown in FIG. Figure 1 As shown, 1 is the substrate, 2 is ITO (anode), 3 is the hole injection layer (HIM), 4 is the hole transport layer (HTL), 5 is the light emitting layer (EML), 6 is the electron transport layer (ETL), 7 is the electron injection layer, and 8 is the cathode reflective electrode layer.

[0125] The substrate 1 used is a glass plate coated with structured ITO 2 (indium tin oxide) with a thickness of 40 nm. The ITO 2 (indium tin oxide) glass plate is ultrasonically cleaned and degreased using acetone and ethanol in sequence, and then stored in isopropanol after being completely dried and anhydrous. The ITO 2 substrate is then mounted on a substrate holder of a vacuum vapor deposition device. Compound HIM-1 is introduced into a unit of the vacuum vapor deposition device, and the pressure in the chamber of the device is then controlled to 10E -6 Entrust.

[0126] Thereafter, a current was applied to the cell to evaporate the above-introduced material, thereby forming a hole injection layer 3 having a thickness of 80 nm by evaporation on the ITO 2 substrate. Next, the compound HTL-1 was introduced into another cell of the vacuum vapor deposition apparatus, and evaporated by applying a current to the cell, thereby forming a hole transport layer 4 having a thickness of 30 nm on the hole injection layer 3. Thereafter, a light-emitting layer 5 (EML) was evaporated on the hole transport layer 4, and the light-emitting layer 5 (EML) included a main light-emitting material EML-1 and a dopant PG-1, and the dopant was deposited in a doping amount of 20% by weight based on the total amount of the main body and the dopant, and a light-emitting layer 5 having a thickness of 50 nm was formed on the hole transport layer 4.

[0127] The compound of the present invention was introduced as the electron transport layer 6 material into a unit of a vacuum vapor deposition device and evaporated by applying an electric current to the unit, so that it formed an electron transport layer 6 with a thickness of 30 nm on the light emitting layer 5. The materials used are listed in Table 1 below.

[0128] ETM-2 is deposited on the electron transport layer 6 to form an electron injection layer 7 with a thickness of 20 nm. The cathode reflective electrode layer 8 is formed by evaporation of an aluminum layer with a thickness of 100 nm. An organic electroluminescent device is formed. The compound structure involved in the preparation process of the organic electroluminescent device is:

[0129] .

[0130] Table 1 Electron transport layer materials in Application Examples 1 to 12 and Comparative Examples 1 to 2

[0131]

[0132] The organic electroluminescent devices prepared in the above Application Examples 1 to 12 and Comparative Examples 1 to 2 were subjected to performance tests. The specific test results are shown in Table 2 below.

[0133] Table 2 Organic electroluminescent device performance test results

[0134]

[0135] The compounds of the present invention are used as electron transport layer materials. As shown in Table 2, the organic electroluminescent element using the compounds of the present invention has improved operation voltage stability, efficiency and operation voltage compared with the prior art. It can be driven by low voltage and shows high luminous efficiency and high operation voltage stability at high temperature.

[0136] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are exhaustively listed. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0137] For those skilled in the art, several modifications and improvements may be made without departing from the concept of the present invention, all of which belong to the protection scope of the present invention. The protection scope of the present invention shall be based on the attached claims.

Claims

1. An isoquinoline phosphine compound, characterized in that: The general structure of the isoquinoline phosphine compound is: ； Ar is deuterated phenyl, biphenyl, partially deuterated biphenyl, naphthyl, chrysyl, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, , , , Any one of .

2. An isoquinoline phosphine compound according to claim 1, characterized in that: The Ar is selected from any one of the following structures: 。 3. An isoquinoline phosphine compound, characterized in that: The isoquinoline phosphine compound is selected from any one of the following structures: ； 。 4. An organic electroluminescent device, characterized in that: The electron transport layer of the organic electroluminescent device contains the isoquinoline phosphine compound according to any one of claims 1 to 3.

5. An organic electroluminescent device according to claim 4, characterized in that: The organic electroluminescent device comprises a cathode, an anode and an organic thin film layer sandwiched between the cathode and the anode, wherein the organic thin film layer at least contains an electron transport layer.

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