An organic electroluminescence compound and a preparation method and application thereof

Abstract

The application provides a blue organic electroluminescent compound containing a boron heterocyclic structure, which has a structure shown in formula I. The blue organic electroluminescent material with a novel structure provided by the application is combined by selecting a specific heterocyclic ligand, so that the compound has a narrow half-peak width, a high fluorescence quantum yield, a high glass transition temperature and molecular thermal stability, and suitable HOMO and LUMO energy levels, and the obtained organic compound is used in an organic electroluminescent device, so that the luminous brightness and luminous efficiency of the device are improved, and the service life is long.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic photoelectric materials, in particular to an organic electroluminescent compound and a preparation method and application thereof. BACKGROUND

[0002] As the latest generation of display technology, the organic electroluminescent technology is gradually recognized by the public due to its low power consumption, fast response speed, wide viewing angle, high resolution, wide temperature characteristics, light weight and curling characteristics. The organic electroluminescent display technology is different from the traditional LCD display method, and does not need a backlight, adopts a very thin organic material coating and a glass substrate, and when a current passes through, the organic material will emit light. And the organic electroluminescent display screen can be made lighter and thinner, and has a larger viewing angle, which can significantly save power. Since the organic electroluminescent diode (OLED) has many advantages, the OLED technology is more widely used than the LCD technology, and can be extended to the fields of electronic products, business, transportation, industrial control and medical treatment. In addition, in recent years, international enterprises have been continuously strengthening the research on OLED technology, and OLED technology has been further improved.

[0003] At present, the material of the organic light-emitting device mainly has the technical problem of short service life, and the luminous efficiency and power efficiency are low and the driving voltage is high, which increases the use cost of the material, and the later use exists great obstacle to the development of the market.

[0004] However, the currently disclosed light-emitting material has relatively high synthesis process requirements, and the driving voltage or luminous efficiency and service life of the prepared device are not ideal. Therefore, developing a material with high luminous brightness and long service life is a technical problem to be solved at present. SUMMARY

[0005] Therefore, the technical problem to be solved by the present application is to provide an organic electroluminescent compound and a preparation method and application thereof, which can improve the luminous brightness, luminous efficiency and service life of the organic light-emitting device.

[0006] To achieve the above-mentioned purpose, the present application provides an organic electroluminescent compound having the structure shown in formula I:

[0007]

[0008] wherein Q1, Q2, Q3, Q4 are each independently selected from any one of substituted or unsubstituted C5-C30 alkyl, substituted or unsubstituted C5-C30 cycloalkyl, substituted or unsubstituted 5- to 30-membered heterocycloalkyl, substituted or unsubstituted C5-C30 alkoxy, C5-C30 alkylamino, C6-C30 arylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 4- to 30-membered heteroaryl;

[0009] and Q1 and Q2 cannot be a six-membered aryl at the same time;

[0010] R1, R2, R3, R4, R5 are each independently selected from any one of hydrogen, deuterium, tritium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted 3- to 30-membered heterocycloalkyl, substituted or unsubstituted C1-C30 alkoxy, C1-C30 alkylamino, C6-C30 arylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 4- to 30-membered heteroaryl; 30 alkyl, substituted or unsubstituted C3-C 30 cycloalkyl, substituted or unsubstituted 3- to 30-membered heterocycloalkyl, substituted or unsubstituted C1-C 30 alkyl, substituted or unsubstituted C1-C 30 alkoxy, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted 4- to 30-membered heteroaryl; 30 aryl, substituted or unsubstituted 4- to 30-membered heteroaryl;

[0011] a, b, c, d, e are each independently selected from 0, 1, 2, 3, or 4;

[0012] one of X, Y is N-R6, and the other is a bond;

[0013] the dotted line represents a single bond, -O-, -S-, -NR7-, -CR8R9-, or nothing;

[0014] R6, R7, R8, R9 are each independently selected from any one of hydrogen, deuterium, tritium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted 3- to 30-membered heterocycloalkyl, substituted or unsubstituted C1-C30 alkoxy, C6-C30 aryl, substituted or unsubstituted 4- to 30-membered heteroaryl; 30 alkyl, substituted or unsubstituted C3-C 30 cycloalkyl, substituted or unsubstituted 3- to 30-membered heterocycloalkyl, substituted or unsubstituted C1-C 30 alkyl, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted 4- to 30-membered heteroaryl.

[0015] In the present invention, the alkylamino group is composed of an alkyl group and an amino group.

[0016] In the present invention, the arylamino group is composed of an aryl group and an amino group.

[0017] In the present application, the cycloalkyl and heterocycloalkyl are any one of monocyclic group, polycyclic group, spirocyclic group and fused ring group, and the carbon atoms in the heterocycloalkyl can be substituted by at least one heteroatom, which is at least one of N, O, S, Si, Se and Ge.

[0018] Optionally, the cycloalkyl is one or more of cyclopropyl, cyclopentyl, cyclohexyl and adamantyl.

[0019] Optionally, the aryl and heteroaryl are monocyclic group or polycyclic group; the polycyclic group has multiple rings with two carbon atoms shared by two adjacent rings, wherein at least one ring is aromatic ring, and the other rings are at least one of cycloalkyl, cycloalkenyl, aryl and heteroaryl; and the heteroatom is at least one of N, O, S, Si, Se and Ge.

[0020] Optionally, the aryl is any one or more of benzene, biphenyl, terphenyl, naphthalene, anthracene, phenanthrene and pyrene.

[0021] Optionally, the heteroaryl is any one or more of furan, thiophene and pyridine.

[0022] In the present application, "substituted" means substituted by one, two or more substituents selected from C1-C 20 alkyl, C1-C 20 alkoxy, C6-C 30 aryl and C6-C 30 heteroaryl, wherein the heteroatom is selected from oxygen, nitrogen and sulfur.

[0023] In the structure of formula I of the present application, the ring containing X and Y can be fused to any two carbon atom positions marked in the following structural formula:

[0024]

[0025] Optionally, the structure of formula I has the structure shown in formula I-1 or formula I-2:

[0026]

[0027] The above Q1, Q2, Q3 and Q4 are the same or different from each other, and each is independent.

[0028] Optionally, the Q1, Q2, Q3 and Q4 are each independently selected from any one of substituted or unsubstituted monocyclic aryl, substituted or unsubstituted monocyclic heteroaryl, substituted or unsubstituted polycyclic aryl and substituted or unsubstituted polycyclic heteroaryl;

[0029] The polycyclic aryl is formed by 2-5 monocyclic aryls being fused;

[0030] The polycyclic heteroaryl group has multiple fused rings, wherein at least one ring is a heteroaryl group, and the other rings are at least one of cycloalkyl, cycloalkenyl, aryl, and heteroaryl groups; wherein the heteroatom is at least one of N, O, S, Si, Se, and Ge.

[0031] Optionally, the monocyclic aryl group is phenyl.

[0032] Optionally, the heteroaryl group is a five- or six-membered heteroaryl group containing N, O, and S, including but not limited to pyrrole, thiophene, furanyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, pyranyl, imidazolyl, thiazolyl, oxazolyl, etc.

[0033] Optionally, the cycloalkyl group is cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.

[0034] Optionally, the cycloalkenyl group is a five-membered or six-membered cycloalkenyl group.

[0035] Optionally, the aryl group is phenyl.

[0036] Optionally, Q1, Q2, Q3, and Q4 are each independently selected from substituted or unsubstituted phenyl, biphenyl, terphenyl, pyridyl, benzothiophene, benzofuranyl, naphthothiophene, naphthofuranyl, carbazothiophene, carbazofuranyl, fluorenzothiophene, fluorenzofuranyl, naphthyl, anthracene, phenanthrene, pyrene, perylene, dihydroanthrazothiophene, dihydroanthrazofuranyl, dihydronaphthothiophene, dihydronaphthofuranyl, tetrahydronaphthyl, dihydronaphthyl, carbazoyl, fluorenyl, dibenzothiophene, dibenzofuranyl, or the following structures:

[0037]

[0038] R1, R2, R3, R4, and R5 can be monosubstituted, disubstituted, trisubstituted, or tetrasubstituted, and each substituent can be the same or different.

[0039] Optionally, R1, R2, R3, R4, and R5 are each independently selected from hydrogen, deuterium, tritium, halogen, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C6 alkyl. 10 Cycloalkyl, substituted or unsubstituted 3- to 6-membered heterocyclic alkyl, substituted or unsubstituted C1- to C6 alkoxy, substituted or unsubstituted C1- to C6 alkylamino, substituted or unsubstituted C6- to C6 alkylamino 12 arylamino, substituted or unsubstituted C6-C 30 Any of the following: aryl, substituted or unsubstituted 4- to 30-membered heteroaryl groups.

[0040] Optionally, each of R1, R2, R3, R4, R5is independently selected from hydrogen, deuterium, tritium, halogen, cyano, substituted or unsubstituted phenyl, biphenyl, terphenyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, triazinyl, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, diphenylamino, carbazolyl, fluorenyl, dibenzothiophenyl, dibenzofuranyl, trimethylsilyl, or adamantyl.

[0041] Optionally, the substituents of each of R1, R2, R3, R4, R5are independently selected from deuterium, tritium, halogen, cyano, C1-C6alkyl, adamantyl, trimethylsilyl.

[0042] Optionally, any one or more hydrogen atoms in the C1-C6alkyl, adamantyl, trimethylsilyl can be further substituted by deuterium, tritium, halogen.

[0043] Optionally, the C1-C6alkyl is selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neopentyl, n-hexyl.

[0044] Optionally, each of R6, R7, R8, R9is independently selected from hydrogen, deuterium, tritium, substituted or unsubstituted C1-C6alkyl, phenyl, biphenyl, terphenyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, triazinyl, adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.

[0045] Optionally, the substituents of each of R6, R7, R8, R9are independently selected from deuterium, tritium, halogen, cyano, C1-C6alkyl, adamantyl, trimethylsilyl.

[0046] Optionally, any one or more hydrogen atoms in the C1-C6alkyl, adamantyl, trimethylsilyl can be further substituted by deuterium, tritium, halogen.

[0047] Optionally, the C1-C6alkyl is selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neopentyl, n-hexyl.

[0048] Optionally, the organic electroluminescence compound has a structure represented by Formula I-a or Formula I-b:

[0049]

[0050] wherein Q5, Q6, Q7, Q8are each independently selected from any one of substituted or unsubstituted C6-C30aryl, substituted or unsubstituted 5- to 30-membered heteroaryl;

[0051] R1, R2, R3, R4, and R5 are each independently selected from hydrogen, deuterium, tritium, halogen, cyano, and substituted or unsubstituted C1-C6 groups. 30 Alkyl, substituted or unsubstituted C3-C 30 Cycloalkyl, substituted or unsubstituted 3- to 30-membered heterocycloalkyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C1-C 30 Alkylamino, substituted or unsubstituted C6-C 30 arylamino, substituted or unsubstituted C6-C 30 Any one of aryl, substituted or unsubstituted 4- to 30-membered heteroaryl groups;

[0052] a, b, c, d, and e are each independently selected from 0, 1, 2, 3, or 4;

[0053] Z is either O or S;

[0054] Dashed lines indicate single bonds, -O-, -S-, -NR7-, -CR8R9-, or non-existent bonds;

[0055] R6, R7, R8, and R9 are each independently selected from hydrogen, deuterium, tritium, and substituted or unsubstituted C1 to C2 atoms. 30 Alkyl, substituted or unsubstituted C3-C 30 Cycloalkyl, substituted or unsubstituted 3- to 30-membered heterocycloalkyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C6-C 30 Any of the following: aryl, substituted or unsubstituted 4- to 30-membered heteroaryl groups.

[0056] The ranges of Q6, Q7, and Q8 are the same as those of Q2, Q3, and Q4.

[0057] The ranges of R1 to R9 are the same as above.

[0058] Optionally, Q5, Q6, Q7, and Q8 are each independently selected from substituted or unsubstituted phenyl, biphenyl, terphenyl, pyridyl, naphthyl, carbazolyl, fluorenyl, dibenzothiophene, dibenzofuranyl, anthracene, phenanthrene, pyrene, perylene, dihydroanthrene, dihydronaphthyl, tetrahydronaphthyl, 9,9,10,10-tetramethyl-9,10-dihydroanthrene, 1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthyl, or the following structures:

[0059]

[0060] R1, R2, R3, R4, R5are each independently selected from hydrogen, deuterium, tritium, halogen, cyano, substituted or unsubstituted phenyl, biphenyl, terphenyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, triazinyl, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, diphenylamino, carbazolyl, fluorenyl, dibenzothiophenyl, dibenzofuranyl, trimethylsilyl, or adamantyl.

[0061] The substituents of R1, R2, R3, R4, R5are independently selected from deuterium, tritium, halogen, cyano, C1-C6 alkyl, adamantyl, trimethylsilyl, or any one or more of them.

[0062] a, b, c, d, e are each independently selected from 0, 1, 2, 3, or 4.

[0063] R6, R7are each independently selected from hydrogen, substituted or unsubstituted phenyl, biphenyl, terphenyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, triazinyl, adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.

[0064] R8, R9are each independently selected from hydrogen, deuterium, tritium, substituted or unsubstituted methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, or tert-butyl.

[0065] Optionally, the organic electroluminescent compound has any one of the following structures:

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112] The above only lists some specific structural forms, but the series of compounds is not limited to the above molecular structures, and other specific molecular structures can be obtained by simple transformation of some simple groups and their substituted groups and substitution positions, which will not be described one by one here.

[0113] The novel blue organic light-emitting material provided by the application has excellent luminous efficiency, thermal stability, high life and the like, and can be applied to electroluminescent devices.

[0114] The application provides a preparation method of the organic electroluminescent compound, and the preparation method comprises the following steps.

[0115] S1) under the protection of nitrogen, reacting raw material D1 and raw material D2 under the action of a catalyst to obtain intermediate D3;

[0116] S2) under the protection of nitrogen, reacting raw material D3 and raw material D4 under the action of a catalyst to obtain intermediate D5;

[0117] S3) under the protection of nitrogen, mixing raw material D5 and tert-butylbenzene, then dropping tert-butyllithium, and then reacting under the action of temperature rising, evaporating low-boiling-point solvents, then dropping boron tribromide under the action of temperature falling, and then reacting under the action of temperature rising, dropping N,N-diisopropylethylamine under the action of temperature falling, and then reacting under the action of temperature rising, dropping saturated potassium acetate solvent after the reaction is completed, and then extracting and separating to obtain the compound shown in formula I.

[0118] In some specific embodiments of the application, the preparation method specifically comprises the following steps.

[0119] (1) under the protection of nitrogen, raw material D1, raw material D2 and potassium carbonate are mixed, then toluene, ethanol and water are added, then a catalyst is added, heated and stirred uniformly, and reacted; after the reaction is completed, cooling, filtration, purification, drying, to obtain intermediate D3;

[0120] (2) under the protection of nitrogen, raw material D3 and D4, and potassium carbonate are mixed, then toluene, ethanol and water are added, then a catalyst is added, heated and stirred uniformly, and reacted; after the reaction is completed, cooling, filtration, purification, drying, to obtain intermediate D5;

[0121] (3) under the protection of nitrogen, raw material D5 and tert-butyl benzene are mixed, then tert-butyllithium is added dropwise, heated and reacted, then low-boiling-point solvent is evaporated, then boron tribromide is added dropwise, heated and reacted, then N, N-diisopropylethylamine is added dropwise, heated and reacted, then saturated potassium acetate solution is added dropwise after the reaction is completed, extraction, purification, drying, to obtain end product D.

[0122] The synthesis route is as follows:

[0123]

[0124] Preferably, in step (1), the molar ratio of the raw material D1 to the raw material D2 is (1.05-1.3):1; the molar ratio of the raw material D1 to potassium carbonate is 1:(1.5-2); the catalyst is tetrakis(triphenylphosphine)palladium, the molar ratio of the raw material D1 to tetrakis(triphenylphosphine)palladium is 1:(0.01-0.1); the raw material D1 is mixed with toluene in a ratio of 4.3 mmol:10-20 mL; the raw material D1 is mixed with ethanol in a ratio of 4.3 mmol:10-20 mL; the raw material D1 is mixed with water in a ratio of 4.3 mmol:5-10 mL; the heating temperature is 80-100 DEG C, the reaction time is 20-30 h; the drying temperature is 70-80 DEG C; the column chromatography is carried out by using a silica gel column, and dichloromethane and petroleum ether are mixed in a volume ratio of 1:(1-15) as the solvent.

[0125] The preparation method of the organic electroluminescent compound provided by the application is simple in process, and the prepared product has high yield and purity.

[0126] The application also provides the use of the above-mentioned organic electroluminescent compound for preparing an organic electroluminescent device.

[0127] The application provides an organic electroluminescent compound, which comprises an anode, a cathode and a plurality of organic layers deposited between the anode and the cathode, wherein at least one of the organic layers comprises the above-mentioned organic electroluminescent compound.

[0128] Optionally, the organic layer comprises a hole injection layer, an electron transport layer, a light-emitting layer, an electron transport layer and an electron injection layer, wherein the light-emitting layer comprises the organic electroluminescent compound described above.

[0129] The device described in the present application can be used in an organic light-emitting device, an organic solar cell, electronic paper, an organic photoreceptor or an organic thin-film transistor.

[0130] Compared with the prior art, the present application provides a blue organic electroluminescent compound containing a boron heterocyclic structure, having a structure shown in Formula I. The blue organic electroluminescent material of the novel structure provided in the present application, by selecting a specific heterocyclic ligand combination, makes the compound of the present application have a narrow half-peak width, a high fluorescence quantum yield, a high glass transition temperature and molecular thermal stability, and suitable HOMO and LUMO energy levels, so that the organic compound obtained after being used in an organic electroluminescent device improves the luminous brightness and luminous efficiency of the device, and has a long service life. DETAILED DESCRIPTION

[0131] The technical solutions in the embodiments of the present application will be described below in a clear and complete manner. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0132] Embodiment 1

[0133] Compound D001 is prepared, and the specific steps are as follows:

[0134]

[0135] The specific preparation method comprises the following steps:

[0136] (1) Under a nitrogen protection system, compound 2-chloro-4-bromo-1-iodobenzene (53.34 g, 168.08 mmol), o-nitrophenyl boronic acid pinacol ester (41.6 g, 168.08 mmol), potassium carbonate (46.4 g, 336.16 mmol) were weighed into the reaction system, followed by adding 800 ml of a toluene solution, 200 ml of ultrapure water, and then adding tetrakis(triphenylphosphine)palladium (3.9 g, 3.36 mmol). The system was heated to 90°C, stirred uniformly and reacted for 18 hours. After the reaction was stopped, the system was cooled to room temperature, pure water was added, and the organic phase was extracted with DCM. After the organic phase was dried with anhydrous sodium sulfate, it was concentrated to dryness to obtain a solid powder. The solid powder was dissolved in a mixed solution of dichloromethane and petroleum ether (V 二氯甲烷 :V 石油醚= 1:10) as the solvent, and column chromatography was performed on silica gel. The filtrate was concentrated, and solid was precipitated to obtain D001-1 (31.52 g, yield: 60%).

[0137] (2) Under a nitrogen protection system, compound D001-1 (28.65 g, 91.66 mmol), triphenylphosphine (52.88 g, 183.32 mmol), and dichlorobenzoyl chloride (DCB) (250 ml) were weighed into a reaction system, and heated to reflux. After 18 hours of reaction, the system was cooled to room temperature. Pure water and DCM were added to extract the reaction solution, which was dried and concentrated to obtain a solid powder. A mixture of dichloromethane and petroleum ether (V 二氯甲烷 :V 石油醚 = 1:6) was used as the solvent, and column chromatography was performed on silica gel. The filtrate was concentrated, and solid was precipitated to obtain D001-2 (18 g, yield: 70%).

[0138] (3) Under a nitrogen protection system, compound D001-2 (18 g, 63.6 mmol), iodobenzene (12.98 g, 63.6 mmol), and sodium tert-butoxide (7.69 g, 80.06 mmol) were weighed into a reaction system, and 300 ml of toluene solution was then added to the reaction system, followed by the addition of tris(dibenzylideneacetone)dipalladium (0.37 g, 0.40 mmol) and 50% tri-tert-butylphosphine (0.32 g, 0.80 mmol). After uniform stirring and 18 hours of reaction, the system was cooled to room temperature. Pure water and DCM were added to extract the reaction solution, which was dried and concentrated to obtain a solid powder. A mixture of dichloromethane and petroleum ether (V 二氯甲烷 :V 石油醚 = 1:15) was used as the solvent, and column chromatography was performed on silica gel. The filtrate was concentrated, and solid was precipitated to obtain D001-3 (14.29 g, yield: 63%).

[0139] (4) Under a nitrogen protection system, compound D001-3 (14.29 g, 40.07 mmol), 5-(tert-butyl)-N-(4-(tert-butyl)phenyl)benzo[b]thiophen-3-amine (13.52 g, 40.07 mmol), and sodium tert-butoxide (6.38 g, 66.44 mmol) were weighed into a reaction system, and 150 ml of toluene solution was then added to the reaction system, followed by the addition of tris(dibenzylideneacetone)dipalladium (0.91 g, 0.99 mmol) and Xant-phos (1.15 g, 1.98 mmol). After 18 hours of reaction at 70°C, the system was cooled to room temperature. Pure water and DCM were added to extract the reaction solution, which was dried and concentrated. A mixture of dichloromethane and petroleum ether (V 二氯甲烷 :V 石油醚= 1 :20) as solvent, and the filtrate was concentrated to obtain solid D001-4 (17.32 g, yield: 70%).

[0140] (5) Under a nitrogen protection system, D001-4 (15 g, 24.46 mmol), D001-5 (4', 5-di-tert-butyl-[1,1'-biphenyl]-2-amine, 6.88 g, 24.46 mmol), and sodium tert-butoxide (4.7 g, 48.92 mmol) were weighed into a reaction system, 150 ml of a toluene solution was then added to the reaction system, followed by the addition of tris(dibenzylideneacetone)dipalladium (0.45 g, 0.49 mmol) and 50% tri-tert-butylphosphine (0.4 g, 0.98 mmol), and the system was heated to 100°C for 18 hours. After the reaction was stopped, the system was cooled to room temperature, pure water and DCM were added to extract the reaction solution, which was dried, concentrated, and subjected to silica gel column chromatography using a mixture of dichloromethane and petroleum ether (V 二氯甲烷 :V 石油醚 = 1 :20) as solvent, and the filtrate was concentrated to obtain solid D001-4 (17.32 g, yield: 70%).

[0141] (6) Under a nitrogen protection system, D001-6 (20 g, 23.30 mmol), 4-tert-butyl iodobenzene (12.12 g, 46.60 mmol), and sodium tert-butoxide (4.48 g, 46.60 mmol) were weighed into a reaction system, 150 ml of a toluene solution was then added to the reaction system, followed by the addition of tris(dibenzylideneacetone)dipalladium (0.42 g, 0.46 mmol) and 50% tri-tert-butylphosphine (0.37 g, 0.92 mmol), and the system was heated to 60°C for 18 hours. After the reaction was stopped, the system was cooled to room temperature, pure water and DCM were added to extract the reaction solution, which was dried, concentrated, and subjected to silica gel column chromatography using a mixture of dichloromethane and petroleum ether (V 二氯甲烷 :V 石油醚 = 1 :20) as solvent, and the filtrate was concentrated to obtain solid D001-4 (17.32 g, yield: 70%).

[0142] (7) Under the nitrogen protection system, D001-7 (16.15 g, 16.31 mmol) and tert-butylbenzene (200 ml) were weighed and dissolved, then the system was cooled to -40 °C, 1.3 mol / L tert-butyllithium (37.64 ml, 48.93 mmol) was added dropwise, after the dropwise addition was completed, the system was warmed to 70 °C, and reacted for 24 hours. Then the system was cooled to -40 °C, boron tribromide (12.26 g, 48.93 mmol) was added dropwise, and the system was warmed to 30 °C while reacting for 24 hours. Then the system was cooled to -40 °C, N,N-diisopropylethylamine (6.32 g, 48.93 mmol) was added dropwise, the system was warmed to 90 °C, and reacted for 24 hours. After the reaction was completed, the system was cooled to -30 °C, potassium acetate saturated solution was added dropwise to neutralize the reaction, and the system was allowed to stand and separate. The organic phase was extracted with DCM, dried over anhydrous sodium sulfate, and then concentrated. The residue was dissolved in a mixture of dichloromethane and petroleum ether (V 二氯甲烷 :V 石油醚 = 1:20) as a solvent, and then subjected to silica gel column chromatography. The filtrate was concentrated to obtain solid, and then D001 (4.1 g, yield: 25%) was obtained.

[0143] The structure of the compound in Example 1 was determined, and the measured data included: 1 H NMR (500 MHz, Chloroform-d) δ 7.90 (dd, J = 7.5, 1.6 Hz, 1H), 7.85 (d, J = 1.7 Hz, 1H), 7.83 (d, J = 7.5 Hz, 1H), 7.72 (dd, J = 7.5, 1.4 Hz, 1H), 7.52-7.48 (m, 2H), 7.48-7.45 (m, 2H), 7.40 (ddt, J = 4.8, 2.9, 1.5 Hz, 3H), 7.37 (dd, J = 7.3, 1.5 Hz, 2H), 7.35-7.33 (m, 3H), 7.33-7.29 (m, 1H), 7.26-7.24 (m, 2H), 7.24-7.22 (m, 3H), 7.19 (d, J = 7.5 Hz, 1H), 7.12 (d, J = 7.5 Hz, 1H), 7.09 (s, 1H), 7.06-7.03 (m, 2H), 1.42 (s, 9H), 1.39 (d, J = 2.3 Hz, 27H), 1.38 (s, 9H).

[0144] HPLC purity: greater than 99.9%;

[0145] Mass spectrum: calculated value 998.24, tested value 998.12;

[0146] Elemental analysis:

[0147] Calculated value C: 84.23%; H: 7.27%; N: 4.21%;

[0148] Test value C: 84.67%; H: 7.20%; N: 4.20%.

[0149] Example 2

[0150] Compound D069 was prepared, and the specific steps were as follows:

[0151]

[0152] D001-4 was synthesized by the method in Example 1.

[0153] (1) Under a nitrogen protection system, D001-4 (15 g, 24.46 mmol), 4-tert-butylaniline (3.65 g, 24.46 mmol), and sodium tert-butoxide (4.7 g, 48.92 mmol) were weighed into a reaction system, then 150 ml of a toluene solution was added to the reaction system, followed by the addition of tris(dibenzylideneacetone)dipalladium (0.45 g, 0.49 mmol) and 50% tri-tert-butylphosphine (0.4 g, 0.98 mmol), and heating to 100°C for 18 hours. After the reaction was stopped, the system was cooled to room temperature, pure water and DCM were added to extract the reaction solution, dried, concentrated, and column chromatography was performed using a mixture of dichloromethane and petroleum ether (V dichloromethane:V petroleum ether = 1:20) as the solvent. The filtrate was concentrated and solid was precipitated to obtain D069-1 (16.34 g, yield: 92%).

[0154] (2) Under a nitrogen protection system, D069-1 (16.34 g, 22.51 mmol), 3-iodo-tert-butylbenzene (11.71 g, 45.02 mmol), and sodium tert-butoxide (4.33 g, 45.02 mmol) were weighed into a reaction system, then 150 ml of a toluene solution was added to the reaction system, followed by the addition of tris(dibenzylideneacetone)dipalladium (0.41 g, 0.45 mmol) and 50% tri-tert-butylphosphine (0.36 g, 0.90 mmol), and heating to 60°C for 18 hours. After the reaction was stopped, the system was cooled to room temperature, pure water and DCM were added to extract the reaction solution, dried, concentrated, and column chromatography was performed using a mixture of dichloromethane and petroleum ether (V dichloromethane:V petroleum ether = 1:20) as the solvent. The filtrate was concentrated and solid was precipitated to obtain D069-2 (13.91 g, yield: 72%).

[0155] (8) Under nitrogen protection system, D069-2 (13.91 g, 16.31 mmol), t-butyl benzene (200 ml) were weighed, after dissolution, the system was cooled to -40 °C, 1.3 mol / L t-butyllithium (37.64 ml, 48.93 mmol) was slowly added dropwise, after the dropwise addition was completed, the system was warmed to 70 °C, and reacted for 16 hours, and then cooled to -40 °C, boron tribromide (12.26 g, 48.93 mmol) was added dropwise, and after the dropwise addition was completed, the system was warmed to 30 °C, and reacted for 16 hours, and then cooled to -40 °C, N,N-diisopropylethylamine (6.32 g, 48.93 mmol) was added dropwise, the system was warmed to 90 °C, and reacted for 18 hours, after the reaction was completed, the system was cooled to -30 °C, potassium acetate saturated solution was added dropwise to neutralize the reaction, and after standing and liquid separation, DCM was used for extraction, the organic phase was dried over anhydrous sodium sulfate, a mixed solution of dichloromethane and petroleum ether (V dichloromethane:V petroleum ether =1:20) was used as a solvent, and the filtrate was concentrated to obtain a solid, and D069 (4.0 g, yield: 28%) was obtained.

[0156] HPLC purity: greater than 99.9%;

[0157] Mass spectrum: the calculated value is 866.03, and the tested value is 866.2;

[0158] Elemental analysis:

[0159] Calculated value C: 83.21%; H: 6.98%; N: 4.85%;

[0160] Test value C: 83.17%; H: 6.92%; N: 4.79%.

[0161] Example 3

[0162] The compound D091 was prepared, and the specific steps were as follows:

[0163]

[0164]

[0165] D001-3 was synthesized by the method in Example 1.

[0166] (1) Under the nitrogen protection system, 6-bromobenzothiophene (1200 g, 938.58 mmol), 2-(methoxycarbonyl) phenylboronic acid (185.8 g, 1032.44 mmol), anhydrous sodium carbonate (298.18 g, 2815.74 mmol) were weighed into the reaction system, then 4800 ml of toluene solution, 1200 ml of anhydrous ethanol, 61200 ml of ultrapure water were added to the reaction system, then tetrakis(triphenylphosphine)palladium (10.84 g, 9.38 mmol) was added, heated to reflux for 18 hours, after the reaction stopped, the system was cooled to room temperature, the organic phase was extracted with ethyl acetate, dried, concentrated to obtain yellow solid D091-5 (151 g, yield: 60%).

[0167] (2) Under the nitrogen protection system, D091-5 (151 g, 563.14 mmol) was weighed and dissolved in 2000 ml of tetrahydrofuran, then methyl magnesium bromide (147.74 g, 1238.9 mmol) was added, -30℃ reaction for 2 hours, room temperature reaction for 12 hours, after the reaction was completed, pure water was added, and white solid was precipitated, suction filtration, oven drying, to obtain white solid D091-6 (60.46 g, yield: 40%).

[0168] (3) Under the nitrogen protection system, D091-6 (60.46 g, 225.26 mmol) was weighed and then 2000 ml of glacial acetic acid was added, heated to 120℃ for 12 hours, after the reaction was completed, the temperature was lowered to room temperature, pure water was added, and white solid was precipitated, washed with water, suction filtration, oven drying, to obtain off-white solid, recrystallized with toluene to obtain white solid D091-7 (134.96 g, yield: 62%).

[0169] (4) Under the nitrogen protection system, D091-7 (34.96 g, 139.6 mmol) was weighed and then 1000 ml of dichloromethane was added, stirred and dissolved, NBS (24.86 g, 139.6 mmol) was added in batches, room temperature reaction for 12 hours, after the reaction was completed, pure water was added, and white solid was precipitated, washed with water, suction filtration, oven drying, to obtain off-white solid, recrystallized with n-heptane to obtain white solid D091-8 (25.22 g, yield: 72%).

[0170] (5) Under the protection of nitrogen system, D091-8 (20 g, 50.30 mmol), 4-tert-butyl aniline (7.51 g, 50.30 mmol), sodium tert-butoxide (9.67 g, 100.6 mmol) were put into the reaction system, then 300 ml of toluene solution was added into the reaction system, followed by adding tris(dibenzylideneacetone)dipalladium (0.92 g, 1 mmol), 50% tri-tert-butyl phosphine (0.81 g, 2 mmol), heated to 60°C for 18 hours, after the reaction stopped, the system was cooled to room temperature, pure water, DCM was added to extract the reaction solution, dried, concentrated, and used silica gel column chromatography with a mixture of dichloromethane and petroleum ether (V 二氯甲烷 :V 石油醚 = 1:20) as solvent, and the filtrate was concentrated to obtain solid D091-1 (15 g, yield: 75%).

[0171] (6) Under the protection of nitrogen system, D091-1 (15 g, 37.73 mmol), D001-3 (13.456 g, 37.73 mmol), sodium tert-butoxide (7.25 g, 75.46 mmol) were put into the reaction system, then 300 ml of toluene solution was added into the reaction system, followed by adding tris(dibenzylideneacetone)dipalladium (0.69 g, 0.75 mmol), Xant-phos (0.87 g, 1.5 mmol), heated to 70°C for 18 hours, after the reaction stopped, the system was cooled to room temperature, pure water, DCM was added to extract the reaction solution, dried, concentrated, and used silica gel column chromatography with a mixture of dichloromethane and petroleum ether (V 二氯甲烷 :V 石油醚 = 1:20) as solvent, and the filtrate was concentrated to obtain solid D091-2 (20.32, yield: 80%).

[0172] (7) Under the protection of nitrogen system, D091-2 (20.32 g, 30.18 mmol), D001-5 (8.49 g, 30.18 mmol), sodium tert-butoxide (4.7 g, 60.36 mmol) were put into the reaction system, then 200 ml of toluene solution was added into the reaction system, followed by adding tris(dibenzylideneacetone)dipalladium (0.55 g, 0.60 mmol), 50% tri-tert-butyl phosphine (0.49 g, 1.2 mmol), heated to 100°C for 18 hours, after the reaction stopped, the system was cooled to room temperature, pure water, DCM was added to extract the reaction solution, dried, concentrated, and used silica gel column chromatography with a mixture of dichloromethane and petroleum ether (V 二氯甲烷 :V 石油醚 = 1:20) as solvent, and the filtrate was concentrated to obtain solid D091-3 (26.33 g, yield: 95%).

[0173] (8) Under nitrogen protection system, D091-3 (26.33 g, 28.67 mmol), 3-iodo-tert-butylbenzene (14.91 g, 57.34 mmol), sodium tert-butoxide (5.51 g, 57.34 mmol) were weighed into the reaction system, then 200 ml of toluene solution was added to the reaction system, followed by the addition of tris(dibenzylideneacetone)dipalladium (0.52 g, 0.57 mmol), 50% tri-tert-butylphosphine (0.46 g, 1.14 mmol), heated to 60°C for 18 hours, after the reaction stopped, the system was cooled to room temperature, pure water, DCM was added to extract the reaction solution, dried, concentrated, and column chromatography was performed using a mixture of dichloromethane and petroleum ether (V 二氯甲烷 :V 石油醚 = 1:20) as the solvent, the filtrate was concentrated and solid was precipitated to obtain D091-4 (19.57 g, yield: 65%).

[0174] (9) Under nitrogen protection system, D091-4 (19.57 g, 18.64 mmol), tert-butylbenzene (200 ml) was weighed into the reaction system, after dissolution, the system was cooled to -40°C, 1.3 mol / L tert-butyllithium (43.02 ml, 55.92 mmol) was slowly added dropwise, after the addition was completed, the system was warmed to 70°C, and reacted for 16 hours, then cooled to -40°C, and boron tribromide (14.01 g, 55.92 mmol) was added dropwise, after the dropwise addition was completed, the system was warmed to 30°C, and reacted for 16 hours, then cooled to -40°C, and N,N-diisopropylethylamine (7.2 g, 55.92 mmol) was added dropwise, after the dropwise addition was completed, the system was warmed to 90°C, and reacted for 18 hours, after the reaction was completed, the system was cooled to -30°C, and potassium acetate saturated solution was added dropwise to neutralize the reaction, and then allowed to stand and separate, and DCM was added to extract, and then the organic phase was dried over anhydrous sodium sulfate, and column chromatography was performed using a mixture of dichloromethane and petroleum ether (V 二氯甲烷 :V 石油醚 = 1:20) as the solvent, the filtrate was concentrated and solid was precipitated to obtain D091 (5.92 g, yield: 30%).

[0175] HPLC purity: greater than 99.9%;

[0176] Mass spectrum: calculated value 1058.29, tested value 1058.771;

[0177] Elemental analysis:

[0178] Calculated value C: 85.12%; H: 6.86%; N: 3.97%;

[0179] Tested value C: 85.33%; H: 6.71%; N: 3.99%.

[0180] Example 4

[0181] Compound D125 was prepared, and the specific steps are as follows:

[0182]

[0183] (1) Under a nitrogen protection system, compound 2,4-dibromo-1-iodobenzene (48.64 g, 134.45 mmol), o-nitrophenylboronic acid pinacol ester (33.28 g, 134.45 mmol), potassium carbonate (34.80 g, 252.08 mmol) were weighed into a reaction system, then 800 ml of a toluene solution, 20 ml of ultrapure water were added to the reaction system, followed by the addition of tetrakis(triphenylphosphine)palladium (2.92 g, 2.52 mmol), heating at 90°C, stirring uniformly and reacting for 18 hours. After the reaction was stopped, the system was cooled to room temperature, pure water was added, the organic phase was extracted with DCM, and the organic phase was dried with anhydrous sodium sulfate. After being concentrated to dryness, a solid powder was obtained. A mixture of dichloromethane and petroleum ether (V 二氯甲烷 :V 石油醚 = 1:10) was used as a solvent, and silica gel column chromatography was performed. The filtrate was concentrated, and a solid was precipitated to obtain D125-1 (28.8 g, yield: 60%).

[0184] (2) Under a nitrogen protection system, compound D125-1 (28.8 g, 80.68 mmol), triphenylphosphine (46.54 g, 177.47 mmol), dichlorobenzoyl chloride (DCB) (300 ml) were weighed into a reaction system, and heating reflux was performed for 18 hours. After the reaction was stopped, the system was cooled to room temperature, pure water was added, the reaction solution was extracted with DCM, dried, and concentrated to obtain a solid powder. A mixture of dichloromethane and petroleum ether (V 二氯甲烷 :V 石油醚 = 1:6) was used as a solvent, and silica gel column chromatography was performed. The filtrate was concentrated, and a solid was precipitated to obtain D125-2 (26.22 g, yield: 60%).

[0185] (3) Under a nitrogen protection system, compound D125-2 (20.48 g, 62.54 mmol), iodobenzene (12.76 g, 62.54 mmol), sodium tert-butoxide (7.69 g, 80.06 mmol) were weighed into a reaction system, then 300 ml of a toluene solution was added to the reaction system, followed by the addition of tris(dibenzylideneacetone)dipalladium (0.37 g, 0.40 mmol), 50% tri-tert-butylphosphine (0.32 g, 0.80 mmol), heating reflux, stirring uniformly and reacting for 18 hours. After the reaction was stopped, the system was cooled to room temperature, pure water was added, the reaction solution was extracted with DCM, dried, and concentrated to obtain a solid powder. A mixture of dichloromethane and petroleum ether (V 二氯甲烷 :V 石油醚= 1 : 15) as the solvent, and the filtrate was concentrated to obtain solid to obtain D125-3 (17.56 g, yield: 70%).

[0186] (4) Under a nitrogen protection system, compound D125-3 (17.56 g, 43.77 mmol), 5-(tert-butyl)-N-(4-(tert-butyl)phenyl)benzo[b]thiophen-3-amine (32.50 g, 96.29 mmol), and sodium tert-butoxide (6.38 g, 66.44 mmol) were placed into a reaction system, 150 ml of a toluene solution was then added into the reaction system, followed by the addition of tris(dibenzylideneacetone)dipalladium (0.91 g, 0.99 mmol) and Xant-phos (1.15 g, 1.98 mmol), and heating to 70°C for 18 hours. After the reaction was stopped, the system was cooled to room temperature, pure water and DCM were added to extract the reaction solution, dried, concentrated, and column chromatography was performed using a mixture of dichloromethane and petroleum ether (V 二氯甲烷 :V 石油醚 = 1 : 20) as the solvent, and the filtrate was concentrated to obtain solid to obtain D125-4 (25.21 g, yield: 63%).

[0187] (5) Under a nitrogen protection system, D125-4 (25.21 g, 27.57 mmol) and tert-butylbenzene (250 ml) were dissolved, and the system was cooled to -40°C. 1.3 mol / L tert-butyllithium (63.62 ml, 82.71 mmol) was slowly added dropwise into the system, and after the dropwise addition was completed, the system was warmed to 70°C, and reacted for 16 hours. The system was cooled to -40°C, and boron tribromide (20.72 g, 82.71 mmol) was added dropwise. After the dropwise addition was completed, the system was warmed to 30°C, and reacted for 16 hours. The system was cooled to -40°C, and N,N-diisopropylethylamine (10.68 g, 82.71 mmol) was added dropwise. After the dropwise addition was completed, the system was warmed to 90°C, and reacted for 18 hours. After the reaction was completed, the system was cooled to -30°C, and potassium acetate saturated solution was added dropwise into the system to neutralize the reaction. After standing, the solution was separated, and DCM was added to extract the organic phase. The organic phase was dried over anhydrous sodium sulfate, and column chromatography was performed using a mixture of dichloromethane and petroleum ether (V 二氯甲烷 :V 石油醚 = 1 : 20) as the solvent, and the filtrate was concentrated to obtain solid to obtain D125-4 (25.21 g, yield: 63%).

[0188] HPLC purity: greater than 99.9%;

[0189] Mass spectrometry: calculated value 922.11, measured value 921.98;

[0190] Elemental analysis:

[0191] Calculated C: 80.76%; H: 6.56%; N: 4.56%;

[0192] Test value C: 80.57%; H: 6.77%; N: 4.49%.

[0193] Example 5

[0194] The compound D324 was prepared, and the specific steps were as follows:

[0195]

[0196]

[0197] D001-2 was synthesized by the method in Example 1.

[0198] (1) Under the nitrogen protection system, compound D001-2 (15.09 g, 53.36 mmol), 1-iodobenzene-2,3,4,5,6-D5 (11.16 g, 53.36 mmol), sodium tert-butoxide (7.69 g, 80.06 mmol) were weighed into the reaction system, then 500 ml of toluene solution was added to the reaction system, followed by the addition of tris(dibenzylideneacetone)dipalladium (0.37 g, 0.40 mmol), 50% tri-tert-butyl phosphine (0.32 g, 0.80 mmol), heated to reflux, stirred uniformly and reacted for 18 hours. After the reaction stopped, the system was cooled to room temperature, pure water was added, and the reaction solution was extracted with DCM, dried, concentrated, and a solid powder was obtained. A mixture of dichloromethane and petroleum ether (V 二氯甲烷 :V 石油醚 = 1:15) was used as the solvent, and silica gel column chromatography was performed. The filtrate was concentrated and a solid was precipitated to obtain D324-1 (11.58 g, yield: 60%).

[0199] (2) Under the nitrogen protection system, compound D324-1 (15.31 g, 42.34 mmol), 5-(tert-butyl)-N-(4-(tert-butyl)phenyl)benzo[b]thiophen-3-amine (14.82 g, 42.34 mmol), sodium tert-butoxide (6.38 g, 64.04 mmol) were weighed into the reaction system, then 150 ml of toluene solution was added to the reaction system, followed by the addition of tris(dibenzylideneacetone)dipalladium (0.88 g, 0.96 mmol), Xant-phos (1.11 g, 1.92 mmol), heated to 70°C and reacted for 18 hours. After the reaction stopped, the system was cooled to room temperature, pure water was added, and the reaction solution was extracted with DCM, dried, concentrated, and a mixture of dichloromethane and petroleum ether (V 二氯甲烷 :V 石油醚= 1 :20) as solvent, and the filtrate was concentrated to obtain solid to obtain D324-2 (16.23 g, yield: 62%).

[0200] (3) Under the nitrogen protection system, D324-2 (15.12 g, 24.46 mmol), 4', 5-di-tert-butyl-[1,1'-biphenyl]-2-amine (6.88 g, 24.46 mmol), sodium tert-butoxide (4.7 g, 48.92 mmol) were weighed into the reaction system, then 150 ml of toluene solution was added to the reaction system, followed by the addition of tris(dibenzylideneacetone)dipalladium (0.45 g, 0.49 mmol), 50% tri-tert-butylphosphine (0.4 g, 0.98 mmol), heated to 100°C for 18 hours, and after the reaction stopped, the system was cooled to room temperature, pure water and DCM were added to extract the reaction solution, dried, concentrated, and column chromatography was performed using a mixture of dichloromethane and petroleum ether (V 二氯甲烷 :V 石油醚 = 1 :20) as solvent, and the filtrate was concentrated to obtain solid to obtain D324-2 (16.23 g, yield: 62%).

[0201] (4) Under the nitrogen protection system, D324-3 (20.11 g, 23.30 mmol), 4-tert-butyl-1-iodobenzene (12.12 g, 46.60 mmol), sodium tert-butoxide (4.48 g, 46.60 mmol) were weighed into the reaction system, then 150 ml of toluene solution was added to the reaction system, followed by the addition of tris(dibenzylideneacetone)dipalladium (0.42 g, 0.46 mmol), 50% tri-tert-butylphosphine (0.37 g, 0.92 mmol), heated to 60°C for 18 hours, and after the reaction stopped, the system was cooled to room temperature, pure water and DCM were added to extract the reaction solution, dried, concentrated, and column chromatography was performed using a mixture of dichloromethane and petroleum ether (V 二氯甲烷 :V 石油醚 = 1 :20) as solvent, and the filtrate was concentrated to obtain solid to obtain D324-2 (16.23 g, yield: 62%).

[0202] (8) Under nitrogen protection system, D324-4 (17.40 g, 17.47 mmol) and tert-butyl benzene (200 ml) were weighed, and after dissolution, the system was cooled to -40 °C, and 1.3 mol / L tert-butyllithium (40.32 ml, 48.93 mmol) was slowly added dropwise, and after the addition was completed, the system was warmed to 70 °C, and reacted for 16 hours, and then cooled to -40 °C, and boron tribromide (13.13 g, 48.93 mmol) was added dropwise, and after the dropwise addition was completed, the system was warmed to 30 °C, and reacted for 16 hours, and then cooled to -40 °C, and N,N-diisopropylethylamine (6.77 g, 48.93 mmol) was added dropwise, and after the dropwise addition was completed, the system was warmed to 90 °C, and reacted for 18 hours, and after the reaction was completed, the system was cooled to -30 °C, and potassium acetate saturated solution was added dropwise to neutralize the reaction, and after standing, the liquid was separated, and the organic phase was dried over anhydrous sodium sulfate, and then the solvent was removed by rotary evaporation, and the residue was dissolved in dichloromethane and petroleum ether mixed solution (V 二氯甲烷 :V 石油醚 = 1:20) as the solvent, and then purified by silica gel column chromatography, and the filtrate was concentrated to obtain a solid, and then D324 (5.61 g, yield: 32%) was obtained.

[0203] HPLC purity: greater than 99.9%;

[0204] Mass spectrum: the calculated value is 1003.27, and the tested value is 1003.44;

[0205] Elemental analysis:

[0206] The calculated value of C is 83.80%; H is 7.74%; and N is 4.19%;

[0207] The tested value of C is 83.52%; H is 7.82%; and N is 4.11%.

[0208] Examples 6-15

[0209] According to the synthesis method in examples 1-5, only the corresponding reactants are replaced, the target compounds of examples 7-16 can be synthesized, and the results of FD-MS (i.e. mass spectrum) of the target compounds are shown in Table 1.

[0210] Table 1: Results of FD-MS of target compounds of examples 6-15

[0211]

[0212]

[0213] Device example 1

[0214] The structure of the prepared OLED device is: ITO anode / HIL / HTL / EML / HBL / ETL

[0215] / EIL / cathode

[0216] a. ITO anode: ITO (indium tin oxide) glass substrate with a coating thickness of 1500 A was cleaned twice in distilled water, ultrasonically washed for 30 min, and then cleaned repeatedly twice in distilled water, ultrasonically washed for 10 min. After washing, the substrate was dried and then transferred to a plasma cleaning machine for washing for 5 min. The substrate was then sent to an evaporation machine, and other functional layers were evaporated on the substrate as an anode.

[0217] b. HIL (hole injection layer): 2-TNATA (i.e., N1-(2-naphthyl)-N4,N4-di(4-(2-naphthyl(phenyl)amino)phenyl)-N1-phenylbenzene-1,4-diamine) was vacuum evaporated. The hole injection layer was formed.

[0218] c. HTL (hole transport layer): NPB (i.e., N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine) was vacuum evaporated on the hole injection layer. The hole transport layer was formed.

[0219] d. EML (emitting layer): The host emitting material BH and the compound in Synthesis Example 1 were co-deposited on the hole transport layer region in a mass ratio of 96:4 to form an emitting layer EML with a thickness of about 30 nm, wherein the structure of BH is:

[0220]

[0221] e. HBL (hole blocking layer): DPVBi was vacuum evaporated on the emitting layer. The hole blocking layer was formed.

[0222] f. ETL (electron transport layer): Alq3 was vacuum evaporated on the hole blocking layer. The electron transport layer was formed.

[0223] g. EIL (electron injection layer): LiF was vacuum evaporated on the electron transport layer. The electron injection layer was formed.

[0224] h. Cathode: Al was evaporated. The cathode was formed, and thus an organic electroluminescent device was obtained.

[0225] ​The organic electroluminescent devices of compounds D003, D009, D025, D029, D039, D044, D100, D144, D249, D252, D369, D379, D380, D432 and D458 were prepared by the same method as described in device example 1 except that compound D001 was replaced by compound D003, D009, D025, D029, D039, D044, D100, D144, D249, D252, D369, D379, D380, D432 and D458, respectively.

[0226] Device comparative example 1

[0227] The structure of the prepared OLED device was: ITO anode / HIL / HTL / EML / HBL / ETL

[0228] / EIL / cathode

[0229] a. ITO anode: ITO (indium tin oxide) glass substrate with a coating thickness of 1500 nm was cleaned twice in distilled water, ultrasonic washing for 30 min, then washed repeatedly twice with distilled water, ultrasonic washing for 10 min, after washing, ultrasonic washing with methanol, acetone, isopropanol (5 min each time), dried, then transferred to the plasma cleaning machine for washing for 5 min, and then sent to the evaporation machine. The substrate was used as anode, and other functional layers were evaporated on it. b. HIL (hole injection layer): 2-TNATA (i.e. N1-(2-naphthyl)-N4, N4-di(4-(2-naphthyl(phenyl)amino)phenyl)-N1-phenylbenzene-1,4-diamine) was vacuum evaporated

[0230] to form a hole injection layer.

[0231] c. HTL (hole transport layer): NPB (i.e. N, N'-diphenyl-N, N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine) was vacuum evaporated on the hole injection layer to form a hole transport layer.

[0232] d. EML (emitting layer): The mixture of host material BH and dopant material BD-1 was vacuum evaporated on the hole transport layer as the emitting layer, wherein the weight ratio of the host material and the dopant material was 96:4, and the thickness was 80 nm , wherein BD-1 has the following structure:

[0233]

[0234] e. HBL (hole blocking layer): BAlq was vacuum evaporated on the emitting layer to form a hole blocking layer.

[0235] ​f、ETL (electron transport layer): vacuum deposition of Alq3 on the hole blocking layer An electron transport layer is formed.

[0236] g、EIL (electron injection layer): vacuum deposition of LiF on the electron transport layer An electron injection layer is formed.

[0237] h、Cathode: evaporation of Al A cathode is formed, and an organic electroluminescent device is obtained.

[0238] The driving voltage, luminous efficiency and lifetime of the organic electroluminescent devices obtained from the devices of Examples 1-16 and Device Comparative Example 1 above are characterized at a brightness of 1000 (nits), and the test results are as shown in Table 2 below:

[0239] Table 2:

[0240]

[0241]

[0242] As can be seen from Table 2, compared with Comparative Example 1, the driving voltage of the device provided by the present application is 3.1V-3.8V, which is significantly smaller than the driving voltage of Comparative Example 1, and the luminous efficiency is much higher than that of Comparative Example 1, and the lifetime (600-780) is 7-9 times that of Comparative Example 1. Therefore, it can be seen that the organic electroluminescent device prepared by using the compound provided by the present application as a blue light material has a significantly reduced driving voltage, and the luminous efficiency and lifetime are significantly improved compared with the organic electroluminescent device prepared by using the comparative compound BD-1 as a light-emitting layer material.

[0243] The various embodiments in the specification are described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the various embodiments can be referred to each other. For the device disclosed in the embodiments, since it corresponds to the method disclosed in the embodiments, it is described simply, and the relevant parts can be referred to the description of the method.

[0244] The above description of the disclosed embodiments enables a person skilled in the art to implement or use the present application. Various modifications to the embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to the embodiments shown herein, but will conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. An organic electroluminescent compound having any of the following structures:

2. An organic electroluminescent device, comprising an anode, a cathode, and a plurality of organic layers deposited between the anode and the cathode, wherein at least one organic layer comprises the organic electroluminescent compound of claim 1.

Images