Heterocyclic compound and organic electroluminescent device

Abstract

The invention belongs to the technical field of luminescent materials, and discloses a heterocyclic compound and an organic electroluminescent device. The structural general formula of the heterocyclic compound is as shown in a formula (1): # imgabs0 # formula (1). The heterocyclic compound provided by the invention has the advantages of low driving voltage, high luminous efficiency, long device life and the like, and can be used as an electron transport material, a hole blocking layer material and an N-type charge generation layer material in OLED luminescent devices.

Description

Technical Field

[0001] The present application belongs to the technical field of luminescent materials, and in particular relates to a heterocyclic compound and an organic electroluminescent device. Background Art

[0002] At present, organic electroluminescent devices (OLEDs), as a new generation of display technology, have received more and more attention in both display and lighting technology, and have a wide range of application prospects. However, compared with market application requirements, the luminous efficiency, driving voltage, service life and other performance of OLEDs still need to be further improved.

[0003] Generally speaking, the basic structure of OLED is a thin film of organic functional materials with various functions sandwiched between metal electrodes, like a sandwich structure. Driven by electric current, holes and electrons are injected from the positive and negative electrodes respectively. After moving a certain distance, the holes and electrons are recombined in the light-emitting layer and released in the form of light or heat, thus making the OLED emit light. However, organic functional materials are the core components of OLEDs, and the thermal stability, photochemical stability, electrochemical stability, quantum yield, film formation stability, crystallinity, color saturation, etc. of the materials are the main factors affecting the performance of the device.

[0004] Patent document 1 (CN113840822A) records Electron transport compounds connected by triazine rings and tripyridine rings. These compounds can be used as electron transport materials for light-emitting devices, and the efficiency of the devices needs to be improved. Patent document 2 (WO2014010824A1) records A type of naphthalene-linked bistriazine electron transport / hole blocking material, the device performance of which needs to be further improved, especially the life span still does not meet the application requirements; Patent document 3 (CN114057660A) records A type of bistriazine material connected by steric hindered phenyl groups. The efficiency and life of devices with this type of structure also need to be improved.

[0005] Therefore, there is an urgent need to provide a new organic light-emitting material that helps to improve the performance of light-emitting devices. Summary of the invention

[0006] The present application aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present application proposes a heterocyclic compound and an organic electroluminescent device.

[0007] A first aspect of the present application provides a heterocyclic compound.

[0008] In some embodiments, a heterocyclic compound has a general structural formula as shown in Formula (1): Formula (1), Wherein, ring A is selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted phenanthrene ring, or a substituted or unsubstituted cyclic structure represented by formula (1-1): Formula (1-1); Wherein, Ring B and Ring C are independently selected from a benzene ring or a naphthalene ring, X is CRaRb, O, S or Se; Ra and Rb are independently selected from hydrogen, C1-C30 alkyl, C1-C30 heteroalkyl, C3-C30 cycloalkyl, C3-C30 heterocycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C3-C30 alkylsilyl or C6-C30 arylsilyl; X1-X6 are independently selected from N or CR1, and at least one of X1-X3 is N, and at least one of X4-X6 is N; L1 and L2 are independently selected from a C6-C60 arylene group substituted with a substituent or a C5-C60 heteroarylene group substituted with a substituent, and the substituents in L1 and L2 contain at least one deuterium; R1 is selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboryl, C6-C60 arylboryl, C6-C60 arylphosphino or C6-C60 arylamine; Ar1, Ar2, Ar3, Ar4 are independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C9-C30 cycloalkyl and aryl; The substitution in Ar1, Ar2, Ar3, and Ar4 is substituted by at least one of deuterium, halogen, cyano, isocyano, phosphino, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl substituted amine, C1-C6 hydrocarbon substituted or unsubstituted C6-C30 aryl, C1-C6 hydrocarbon substituted or unsubstituted C3-C30 heteroaryl, wherein the number of substitutions ranges from a single substitution to a maximum number of substitutions; The substitution in the ring A is substituted by at least one selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboryl, C6-C60 arylboryl, C6-C60 arylphosphino or C6-C60 arylamine, wherein the number of substitutions is from a single substitution to the maximum number of substitutions; The heteroatoms in the heteroarylene group, heteroalkyl group, heterocycloalkyl group and heteroaryl group are independently selected from at least one of O, S, N, Se, Si and Ge.

[0009] Compared with the prior art, the beneficial effects of this application are as follows: The heterocyclic compound of the present invention has the advantages of low driving voltage, high luminous efficiency, long device life, etc., and can be used as an electron transport material, a hole blocking layer material, and an N-type charge generation layer material in an OLED light-emitting device. At the same time, it has a low melting point, and as a molten material, it is beneficial to improve the evaporation stability of the material. The heterocyclic compound is used as an electron transport material, a hole blocking layer material, and an N-type charge generation layer material, and has the prospect of being applied to the LED, OLED, and AMOLED industries. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1 This is a schematic structural diagram of an organic electroluminescent device 1 according to an embodiment of the present application; Figure 2 FIG. 2 is a schematic structural diagram of an organic electroluminescent device 2 according to an embodiment of the present application. DETAILED DESCRIPTION

[0011] In order to make the technical solution described in this application more clearly understood by those skilled in the art, the following examples are listed for illustration. It should be noted that the following examples do not limit the scope of protection claimed in this application.

[0012] Unless otherwise specified, the raw materials, reagents or devices used in the following examples can be obtained from conventional commercial sources or by existing known methods.

[0013] In some embodiments, a heterocyclic compound has a general structural formula as shown in Formula (1): Formula (1), Wherein, ring A is selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted phenanthrene ring, or a substituted or unsubstituted cyclic structure represented by formula (1-1): Formula (1-1); Wherein, Ring B and Ring C are independently selected from a benzene ring or a naphthalene ring, X is CRaRb, O, S or Se, * represents the connection site between Ring A and L1 and L2; Ra and Rb are independently selected from hydrogen, C1-C30 alkyl, C1-C30 heteroalkyl, C3-C30 cycloalkyl, C3-C30 heterocycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C3-C30 alkylsilyl or C6-C30 arylsilyl; X1-X6 are independently selected from N or CR1, and at least one of X1-X3 is N, and at least one of X4-X6 is N; L1 and L2 are independently selected from a C6-C60 arylene group substituted with a substituent or a C5-C60 heteroarylene group substituted with a substituent, and the substituents in L1 and L2 contain at least one deuterium; R1 is selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboryl, C6-C60 arylboryl, C6-C60 arylphosphino or C6-C60 arylamine; Ar1, Ar2, Ar3, Ar4 are independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C9-C30 cycloalkyl and aryl; The substitution in Ar1, Ar2, Ar3, and Ar4 is substituted by at least one of deuterium, halogen, cyano, isocyano, phosphino, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl substituted amine, C1-C6 hydrocarbon substituted or unsubstituted C6-C30 aryl, C1-C6 hydrocarbon substituted or unsubstituted C3-C30 heteroaryl, wherein the number of substitutions ranges from a single substitution to a maximum number of substitutions; The substitution in the ring A is substituted by at least one selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboryl, C6-C60 arylboryl, C6-C60 arylphosphino or C6-C60 arylamine, wherein the number of substitutions is from a single substitution to the maximum number of substitutions; The heteroatoms in the heteroarylene group, heteroalkyl group, heterocycloalkyl group and heteroaryl group are independently selected from at least one of O, S, N, Se, Si and Ge.

[0014] In some embodiments, the annular structure represented by formula (1-1) is selected from a dibenzofuran ring, a fluorene ring or a naphthobenzofuran ring.

[0015] In some embodiments, the ring A structure represented by formula (1) is selected from any one of the following structures: ; Wherein, X is CRaRb, O, S or Se; * represents the connection site between ring A and L1 and L2 in formula (1); Ra and Rb are each independently selected from hydrogen, C1-C20 alkyl, C1-C20 heteroalkyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C20 aryl, C3-C20 heteroaryl, C3-C20 alkylsilyl or C6-C20 arylsilyl; R2 and R3 are each independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboryl, C6-C60 arylboryl, C6-C60 arylphosphino or C6-C60 arylamine; a and b both represent integers of 0-4. When a is an integer of 2-4, each R2 is the same or different; when b is an integer of 2-4, each R3 is the same or different.

[0016] In some embodiments, the C6-C60 aryl phosphino group is selected from a C6-C60 monoaryl phosphino group or a C6-C60 diaryl phosphino group.

[0017] In some embodiments, Ra and Rb are independently selected from hydrogen, C1-C6 alkyl, C1-C6 heteroalkyl, C3-C12 cycloalkyl, C3-C12 heterocycloalkyl, C6-C20 aryl, and C3-C20 heteroaryl.

[0018] In some embodiments, R2 and R3 are independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C30 alkyl, C1-C30 heteroalkyl, C2-C30 alkenyl, C2-C30 alkynyl, C3-C30 cycloalkyl, C3-C30 heterocycloalkyl, C6-C40 aryl, C3-C40 heteroaryl, C1-C30 alkoxy, C6-C40 aryloxy, C3-C30 alkylsilyl, C6-C40 arylsilyl, C1-C30 alkylboryl, C6-C40 arylboryl, C6-C40 arylphosphinyl or C6-C40 arylamine.

[0019] In some embodiments, the ring A structure shown in formula (1) is selected from one of the following structures:

[0020] ; Wherein, R2 and R3 are independently selected from hydrogen, deuterium, halogen, cyano, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl; a and b both represent integers of 0-4. When a is an integer of 2-4, each R2 is the same or different; when b is an integer of 2-4, each R3 is the same or different.

[0021] In some embodiments, the substituents of L1 and L2 satisfy one of the following conditions: (1) The substituent in L1 or L2 is deuterium; (2) The substituents in L1 and L2 are deuterium-containing substituents; (3) The substituents in L1 and L2 contain at least one deuterium and at least one of halogen, cyano, isocyano, phosphino, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl substituted amine, C1-C6 hydrocarbon substituted or unsubstituted C6-C30 aryl, and C1-C6 hydrocarbon substituted or unsubstituted C3-C30 heteroaryl.

[0022] In some embodiments, L1 and L2 are independently selected from a C6-C40 arylene group substituted with a substituent or a C5-C40 heteroarylene group substituted with a substituent, and the substituent in L1 and L2 contains at least one deuterium.

[0023] In some embodiments, L1 and L2 are independently selected from a C6-C30 arylene group substituted with a substituent or a C5-C30 heteroarylene group substituted with a substituent, and the substituent in L1 and L2 contains at least one deuterium.

[0024] In some embodiments, L1 and L2 are independently selected from a C6-C20 arylene group substituted with a substituent or a C5-C20 heteroarylene group substituted with a substituent, and the substituent in L1 and L2 contains at least one deuterium.

[0025] In some embodiments, the substituents in L1 and L2 are at least one of deuterium and deuterium-substituted C1-C6 alkyl, the number of the substituents is tri-substituted to the maximum number of substitutions, and the number of deuterium substitutions in the deuterium-substituted C1-C6 alkyl is mono-substituted to the maximum number of substitutions.

[0026] In some embodiments, the structures of L1 and L2 are the same.

[0027] In some embodiments, L1 and L2 are independently selected from deuterated phenylene, deuterated biphenylene, deuterated naphthylene or deuterated pyridylene, and the number of deuterations ranges from single substitution to the maximum number of substitutions.

[0028] In some embodiments, X1-X3 contain at least two Ns, and X4-X6 contain at least two Ns.

[0029] In some embodiments, all of X1-X6 are N.

[0030] In some embodiments, R1 is selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C20 alkyl, C1-C20 heteroalkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C1-C20 alkoxy, C6-C30 aryloxy, C3-C20 alkylsilyl, C6-C30 arylsilyl, C1-C20 alkylboryl, C6-C30 arylboryl, C6-C30 arylphosphino, or C6-C30 arylamine.

[0031] In some embodiments, R1 is selected from hydrogen, deuterium, halogen, cyano, C1-C6 alkyl, C1-C6 heteroalkyl, C3-C12 cycloalkyl, C3-C12 heterocycloalkyl, C6-C20 aryl, C3-C20 heteroaryl.

[0032] In some embodiments, Ar1, Ar2, Ar3, and Ar4 are independently selected from substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl, and substituted or unsubstituted C9-C20 cycloalkyl and aryl.

[0033] In some embodiments, the substitution in Ar1, Ar2, Ar3, and Ar4 is by at least one of deuterium, halogen, cyano, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 hydrocarbon substituted or unsubstituted C6-C20 aryl, and C1-C6 hydrocarbon substituted or unsubstituted C3-C20 heteroaryl, wherein the number of substitutions ranges from a single substitution to a maximum number of substitutions.

[0034] In some embodiments, Ar1, Ar2, Ar3, and Ar4 are independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted 9,9-diphenylfluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted chrysene, substituted or unsubstituted carbazolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, Substituted or unsubstituted fluoranthene group, substituted or unsubstituted benzoxazolyl group, substituted or unsubstituted benzimidazolyl group, substituted or unsubstituted benzotriazolyl group, substituted or unsubstituted triphenylene group, substituted or unsubstituted benzopyridinyl group, substituted or unsubstituted cyclohexylphenyl group, wherein the substitution in Ar1, Ar2, Ar3 and Ar4 is substituted by at least one of deuterium, fluorine, cyano, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 hydrocarbon substituted or unsubstituted C6-C12 aryl, C1-C6 hydrocarbon substituted or unsubstituted C3-C12 heteroaryl, wherein the number of substitutions is from single substitution to the maximum number of substitutions.

[0035] In some embodiments, Ar1 and Ar3 have the same structure, and Ar2 and Ar4 have the same structure.

[0036] In some embodiments, the ring A contains at least one deuterium atom.

[0037] In some embodiments, the heterocyclic compound represented by formula (1) satisfies at least one of the following conditions: (1) The six-membered rings where X1-X3 and X4-X6 are located are independently selected from one of the following structural formulas: ; (2) The six-membered ring where X1-X3 is located has the same structure as the six-membered ring where X4-X6 is located; (3) L1 and L2 are independently selected from one of the following structural formulas: ; (4) The structural formula of L1 and L2 is the same; (5) Ring A is selected from one of the following structural formulas: ; (6) Ar1-Ar4 are independently selected from one of the following structural formulas: ; (7) The structural formulas of Ar1 and Ar3 are the same, and the structural formulas of Ar2 and Ar4 are the same; (8) The structural formulas of the following two groups of Ring A in Formula (1) are the same; , .

[0038] In some embodiments, the heterocyclic compound represented by formula (1) is selected from one of the following structural formulas, or one of the following structural formulas in which hydrogen is partially or completely replaced by deuterium or fluorine:

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048] .

[0049] A second aspect of the present application provides an organic electroluminescent device.

[0050] Specifically, an organic electroluminescent device includes the above heterocyclic compound.

[0051] In some embodiments, an organic electroluminescent device includes: an anode, a cathode, and an organic layer between the anode and the cathode; The organic layer includes a light-emitting layer and at least one of an electron transport layer, a hole blocking layer, and an N-type charge generation layer; The material of at least one of the electron transport layer, the hole blocking layer or the N-type charge generation layer contains the heterocyclic compound. For example, in some embodiments, the organic layer includes an electron transport layer, and the material of the electron transport layer contains the heterocyclic compound. Alternatively, the organic layer includes a hole blocking layer, and the material of the hole blocking layer contains the heterocyclic compound. Alternatively, the organic layer includes an N-type charge generation layer, and the material of the N-type charge generation layer contains the heterocyclic compound.

[0052] The third aspect of the present application provides application of the above compound in the semiconductor field.

[0053] Specifically, the heterocyclic compound is used in the preparation of semiconductor devices.

[0054] In some embodiments, the semiconductor device comprises an optoelectronic device.

[0055] definition Unless otherwise specified, the scientific and technical terms used herein have the meanings commonly understood by those skilled in the art, but for a better understanding of the present invention, the definitions of some terms are provided below. When the definitions of terms provided by the present invention are inconsistent with the meanings commonly understood by those skilled in the art, the definitions and interpretations of the terms provided by the present invention shall prevail.

[0056] In the present specification, the "carbon number ab" in the expression "substituted or unsubstituted X group having ab carbon numbers" means the carbon number when the X group is unsubstituted, and does not include the carbon number of the substituent when the X group is substituted.

[0057] The maximum number of substitutions refers to the maximum number of hydrogen atoms that the group can contain when there are no substituents other than hydrogen.

[0058] The alkyl group is a linear or branched saturated hydrocarbon group, and the number of carbon atoms can be 1 to 60, 1 to 40, 1 to 30, 1 to 20, 1 to 12, 1 to 6, or 1 to 3. Non-limiting examples of the alkyl group include methyl, ethyl, propyl, butyl, heptyl, decyl, and the like.

[0059] Cycloalkyl is an alkyl group with a cyclic structure, which may include monocyclic, polycyclic and spiroalkyl groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl and the like.

[0060] Specific examples of the alkenyl group include vinyl, propenyl, allyl, 1-butadienyl, 2-butadienyl, 1-hexatrienyl, 2-hexatrienyl, and 3-hexatrienyl.

[0061] Heteroalkyl refers to an alkyl group in which at least one carbon atom is replaced by a non-carbon atom, but does not include a case where a carbon atom serving as a connection site is replaced by a non-carbon atom (e.g., alkoxy, alkylsilyl). Examples include mercaptomethylmethane, methoxymethane, ethoxymethane, tert-butoxymethane, N,N-dimethylmethane, butylene oxide, cyclopentyl, hexylene oxide, etc., preferably methoxymethane and cyclopentyl.

[0062] Aryl refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing a hydrogen atom, and can be a monocyclic aromatic group or a polycyclic aromatic group. In the polycyclic aromatic group, at least one ring is an aromatic ring system. In the polycyclic aromatic group, multiple rings can be connected to each other via a single bond or can be fused to each other. For example, aryl is selected from phenyl, naphthyl, anthracenyl, phenanthrenyl, naphthyl, pyrenyl, perylene, chrysene, acenaphthenyl, benzopyrenyl, benzo [c] phenanthrenyl, benzo [g] chrysene, fluorenyl, spirobifluorenyl, benzofluorenyl, dibenzofluorenyl, biphenyl, terphenyl, quaterphenyl or fluoranthenyl.

[0063] Heteroaryl refers to a monovalent group of a heterocyclic aromatic system in which at least one carbon atom of an aryl group is replaced by a non-carbon atom, wherein the non-carbon atom can be selected from O, S, N, Se, Si or Ge, but does not include the case where the aryl group uses a non-carbon atom as the attachment site (such as aryloxy, arylsilyl, arylamine). For example, pyrrolyl, pyrrolopyrrolyl, furopyrrolyl, thienopyrrolyl, pyridyl, pyrazolyl, pyrimidinyl, pyrazinyl, triazinyl, pyridazinyl, phenazinyl, phenothiazinyl, phenoxazinyl, indolyl, isoindolyl, imidazolyl, benzimidazolyl, triazolyl, tetrazolyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, furanofuranyl, azadibenzofuranyl, thienofuranyl, diazadibenzofuranyl, benzo[B]naphtho[1,2-D]furan 1-4-dinitro-1, 1-di-1 ...

[0064] The arylene group and the heteroarylene group correspond to divalent groups having the same structures as the aryl group and the heteroaryl group, respectively.

[0065] The following embodiments are only for facilitating the understanding of the technical invention and should not be regarded as specific limitations of the present invention.

[0066] The raw materials and solvents involved in the synthesis of the compounds of the present invention were purchased from suppliers such as Alfa and Acros, which are well known to those skilled in the art.

[0067] The following compound Ax is the abbreviation of heterocyclic compound Ax. For example, compound A4 is the abbreviation of heterocyclic compound.

[0068] The synthetic route of compound A4 is as follows: ; Synthesis of compound A4-3: Compound A4-1 (15.00 g, 47.12 mmol), compound A4-2 (5.79 g, 47.12 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4, 0.55 g, 0.47 mmol), potassium carbonate (16.28 g, 117.80 mmol), tetrahydrofuran (THF, 350 mL), and deionized water (125 mL) were added to a 1000 mL three-necked round-bottom flask, and the vacuum was replaced with nitrogen three times. Then, the system was heated to 60°C for 3 hours. The reaction was monitored by TLC (thin layer chromatography, ethyl acetate:n-hexane = 1:20 as the developing solvent, 1:20 as the volume ratio). The consumption of compound A4-1 was complete. The mixture was cooled to room temperature, concentrated under reduced pressure to remove part of the solvent, ethyl acetate (200 mL) was added, and the mixture was washed three times with deionized water (100 mL*3). The mixture was separated, and the sample was mixed with silica gel and dry-loaded onto a column. Purification was performed by silica gel column chromatography (200-300 mesh silica gel, ethyl acetate:n-hexane = 1:20 as eluent, 1:20 as volume ratio). After elution, the mixture was concentrated under reduced pressure at 60 °C for 1 hour to obtain a white solid as compound A4-3 (9.32 g, mass purity: 99.42%, yield: 73.39%), and the mass spectrum result was 268.94 (M+H).

[0069] Synthesis of compound A4-5: Compound A4-3 (9.00 g, 33.39 mmol), compound A4-4 (4.07 g, 33.39 mmol), tetrakis(triphenylphosphine)palladium (0.39 g, 0.33 mmol), potassium carbonate (11.54 g, 83.48 mmol), tetrahydrofuran (225 mL), and deionized water (75 mL) were added to a 500 mL three-necked round-bottom flask, and the vacuum was replaced with nitrogen three times. Then, the system was heated to 75 °C for 3 hours. The reaction was monitored by TLC (ethyl acetate: n-hexane = 1:15 as the developing solvent). Compound A4-3 was completely consumed; The mixture was cooled to room temperature, concentrated under reduced pressure to remove part of the solvent, ethyl acetate (200 mL) was added, and the mixture was washed three times with deionized water (100 mL*3). The mixture was separated, and the sample was mixed with silica gel and dry-loaded onto a column. Purification was performed by silica gel column chromatography (200-300 mesh silica gel, ethyl acetate:n-hexane = 1:15 as eluent). After elution, the mixture was concentrated under reduced pressure at 60 °C for 1 hour to obtain a white solid, which was compound A4-5 (6.27 g, mass purity: 99.36%, yield: 70.40%), and the mass spectrum result was 267.06 (M+H).

[0070] Synthesis of compound A4-8: Compound A4-6 (15.00 g, 76.74 mmol), compound A4-7 (21.43 g, 84.41 mmol), 1,1-bis(diphenylphosphino)ferrocenepalladium dichloride (Pd(dppf)Cl2, 0.56 g, 0.77 mmol), potassium acetate (KOAc, 18.83 g, 191.84 mmol), 1,4-dioxane (350 mL) were added to a 500 mL three-necked round-bottom flask, and the vacuum was replaced with nitrogen three times. Then, the system was heated to 100 ° C for 4 hours. The reaction was monitored by TLC (ethyl acetate: n-hexane = 1:30 as the developing solvent). Compound A4-6 was completely consumed; The mixture was cooled to room temperature, concentrated under reduced pressure to remove the solvent, ethyl acetate (300 mL) was added, and the mixture was washed three times with deionized water (100 mL*3). The mixture was separated, mixed with silica gel and dry-loaded onto a column, and purified by silica gel column chromatography (200-300 mesh silica gel, ethyl acetate:n-hexane = 1:30 as eluent). After elution, the mixture was concentrated under reduced pressure at 50 °C for 1 hour to obtain an oily liquid, which was compound A4-8 (9.74 g, mass purity: 99.38%, yield: 79.13%), and the mass spectrum result was 161.04 (M+H).

[0071] Synthesis of compound A4-10: Compound A4-8 (9.35 g, 58.29 mmol), compound A4-9 (5.50 g, 23.31 mmol), 1,1-bis(diphenylphosphino)ferrocenepalladium dichloride (0.18 g, 0.17 mmol), potassium carbonate (8.06 g, 58.29 mmol), toluene (Tol, 250 mL), ethanol (EtOH, 50 mL), and deionized water (50 mL) were added to a 500 mL three-necked round-bottom flask, and the vacuum nitrogen was replaced three times. Then, the system was heated to 70 ° C for 16 hours. The reaction was monitored by TLC (dichloromethane: n-hexane = 1:10 as the developing solvent). The compound A4-9 was completely consumed; The temperature was lowered to 60°C, and the solvent was removed by concentration under reduced pressure. Ethyl acetate (300 mL) was added, and the mixture was washed three times with deionized water (100 mL*3). The mixture was separated, and the sample was mixed with silica gel and dry-loaded onto a column. Purification was performed by silica gel column chromatography (200-300 mesh silica gel, dichloromethane:n-hexane = 1:10 as eluent). After elution, the mixture was concentrated under reduced pressure at 60°C for 1 hour to obtain a white solid as compound A4-10 (4.60 g, mass purity: 99.63%, yield: 64.22%), and the mass spectrum result was 307.08 (M+H).

[0072] Synthesis of compound A4-11: Compound A4-10 (4.50 g, 14.65 mmol), compound A4-7 (7.81 g, 30.76 mmol), tris(dibenzylideneacetone)dipalladium (Pd2(dba)3, 0.14 g, 0.15 mmol), 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (X-Phos, 0.14 g, 0.29 mmol), potassium acetate (3.59 g, 36.62 mmol), 1,4-dioxane (1,4-Dioxane, 200 mL) were added to a 500 mL three-necked round-bottom flask, and the vacuum was replaced with nitrogen three times. Then, the system was heated to 100 °C for 4 hours. The reaction was monitored by TLC (ethyl acetate: n-hexane = 1:15 as the developing solvent). The consumption of compound A4-10 was complete. The temperature was lowered to 60°C, and the solvent was removed by concentration under reduced pressure. Ethyl acetate (200 mL) was added, and the mixture was washed three times with deionized water (100 mL*3). The mixture was separated, and the sample was mixed with silica gel and dry-loaded onto a column. Purification was performed by silica gel column chromatography (200-300 mesh silica gel, ethyl acetate:n-hexane = 1:15 as eluent). After elution, the mixture was concentrated under reduced pressure at 60°C for 1 hour to obtain a white solid, which was compound A4-11 (5.31 g, mass purity: 99.49%, yield: 73.95%), and the mass spectrum result was 491.33 (M+H).

[0073] Synthesis of compound A4: Compound A4-11 (5.00 g, 10.20 mmol), compound A4-5 (5.71 g, 21.42 mmol), dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (Pd(aMphos)Cl2, 0.72 g, 0.10 mmol), potassium carbonate (3.52 g, 25.50 mmol), 1,4-dioxane (350 mL), and deionized water (50 mL) were added to a 500 mL three-necked round-bottom flask, and the vacuum was replaced with nitrogen three times. Then, the system was heated to 80 ° C for 6 hours. The reaction was monitored by TLC (dichloromethane: n-hexane = 1:5 as the developing solvent). The compound A4-11 was completely consumed; The temperature was lowered to 60°C, and the solvent was removed by concentration under reduced pressure. Ethyl acetate (300 mL) was added, and the mixture was washed three times with deionized water (100 mL*3). The mixture was separated, and the sample was mixed with silica gel and dry-loaded onto a column. Purification was performed by silica gel column chromatography (200-300 mesh silica gel, dichloromethane:n-hexane=1:5 as eluent). After elution, the mixture was concentrated under reduced pressure at 60°C for 1 hour to obtain a white solid as compound A4 (5.04 g, mass purity: 99.92%, yield: 70.57%). 5.04 grams of crude compound A4 was purified by sublimation to obtain sublimation-purified compound A4 (3.14 g, mass purity: 99.95%, yield: 62.30%). The mass spectrum result was 699.33 (M+H).

[0074] The NMR characterization results of compound A4 are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.79 – 8.72 (m, 4H), 8.70 (d, J = 2.9 Hz, 2H), 8.38 (d, J = 2.9 Hz, 2H), 8.32 – 8.25 (m, 8H), 7.96 (dd, J = 11.1, 6.9 Hz, 2H), 7.63 – 7.44 (m, 8H).

[0075] Compounds A15, A28, A29, A31, A71, A98, A111, A130, A149, A175, A178, A210, A234, A252, A319, A346, A416, A423, A441, A460, A464, and A470 were prepared using a synthetic method similar to that of compound A4, except that different raw materials were used, i.e., raw materials A4-6, A4-9, and A4-5 in the synthesis of compound A4 were replaced by other raw materials.

[0076] In the synthesis process of A15, A28, A29, A31, A71, A98, A111, and A130, the raw material A4-6 in the synthesis process of compound A4 is replaced by the following structural formulas in sequence: , , , , , , , .

[0077] The raw material A4-9 is replaced by the following structural formula in sequence: , , , , , , , .

[0078] The raw material A4-5 is replaced by the following structural formula in sequence: , , , , , , , .

[0079] In the synthesis process of A149, A175, A178, A210, A234, A252, A319, and A346, the raw material A4-6 in the synthesis process of compound A4 is replaced by the following structural formulas in sequence: , , , , , , , .

[0080] The raw material A4-9 is replaced by the following structural formula in sequence: , , , , , , , .

[0081] The raw material A4-5 is replaced by the following structural formula in sequence: , , , , , , , .

[0082] In the synthesis process of A416, A423, A441, A460, A464, and A470, the raw material A4-6 in the synthesis process of compound A4 is replaced by the following structural formulas in sequence: , , , , , .

[0083] The raw material A4-9 is replaced by the following structural formula in sequence: , , , , , , The raw material A4-5 is replaced by the following structural formula in sequence: , , , , , .

[0084] Among them, the CAS numbers of the following raw materials A4-5 are: 3842-55-5, 29509-91-9, 2511017-74-4, 2417550-95-7, 1342819-12-8, 1472062-94-4, 1883265-32-4, 149817-62-9, 1300115-09-6, 1689576-03-1 , , , , , , , , , .

[0085] The corresponding structural formulas of A4, A15, A28, A29, A31, A71, A98, A111, A130, A149, A175, A178, A210, A234, A252, A319, A346, A416, A423, A441, A460, A464 and A470 are as follows: , .

[0086] The yield of A15 was 70.11%; the mass spectrometry result (M+H) was 854.07; the NMR characterization result was 1 H NMR (400 MHz, CDCl3) δ 8.41 – 8.32 (m, 6H), 8.17 (t, J = 3.0 Hz, 2H), 7.96 (dd, J= 11.1, 6.9Hz, 2H), 7.79 – 7.66 (m, 6H), 7.64 – 7.57 (m, 4H), 7.54 – 7.45 (m, 10H), 7.42(d, J = 14.5 Hz, 2H).

[0087] The yield of A28 was 65.24%; the mass spectrometry result (M+H) was 726.88; the NMR characterization result was 1 H NMR (400 MHz, CDCl3)δ 8.40 – 8.32 (m, 8H), 8.22 (d, J = 2.9 Hz, 1H), 8.14 (d, J = 14.9 Hz, 1H),8.01 (dd, J = 15.0, 2.9 Hz, 1H), 7.54 – 7.46 (m, 12H).

[0088] The yield of A29 was 70.52%; the mass spectrometry result (M+H) was 777.35; the NMR characterization result was 1 H NMR (400 MHz, CDCl3)δ 8.39 – 8.33 (m, 8H), 8.26 (d, J = 3.1 Hz, 1H), 8.15 (d, J = 15.0 Hz, 1H), 7.78-7.72 (m, 2H), 7.54 – 7.45 (m, 14H), 7.45 – 7.39 (m, 1H), 7.35 (dd,J = 15.0, 2.9 Hz, 1H).

[0089] The yield of A31 was 63.84%; the mass spectrometry result (M+H) was 719.31; the NMR characterization result was 1 H NMR (400 MHz, CDCl3) δ8.40 – 8.32 (m, 8H), 7.94 (dd, J = 15.0, 9.9 Hz, 1H), 7.71 (dd, J =16.0, 3.0 Hz, 1H), 7.54 – 7.46 (m, 12H), 7.41 (dd, J = 16.0, 14.9, Hz, 1H).

[0090] The yield of A71 was 68.17%; the mass spectrometry result (M+H) was 751.93; the NMR characterization result was 1H NMR (400 MHz, CDCl3) δ 8.43 (dd, J = 14.9, 3.0 Hz, 2H), 8.40 – 8.31 (m, 8H), 7.87 – 7.80(m, 2H), 7.69 – 7.60 (m, 2H), 7.55 – 7.46 (m, 12H).

[0091] The yield of A98 was 72.26%; the mass spectrometry result (M+H) was 749.96; the NMR characterization result was 1 H NMR (400 MHz, CDCl3) δ 8.91 (dd, J = 14.5, 3.5 Hz, 1H), 8.38 – 8.29 (m, 4H), 8.21 (s, 2H), 8.02 (dd, J = 15.0, 2.9 Hz, 1H), 7.97 – 7.88 (m, 5H), 7.59 – 7.45 (m, 12H), 7.45 – 7.30 (m, 3H).

[0092] The yield of A111 was 76.32%; the mass spectrometry result (M+H) was 584.77; the NMR characterization result was 1 H NMR (400 MHz, CDCl3) δ 8.93 (dd, J = 14.5, 3.6 Hz, 1H), 8.42 – 8.31 (m, 8H), 8.03 (dd, J =15.0, 2.9 Hz, 1H), 7.94 (s, 1H), 7.54 – 7.41 (m, 14H), 7.35 (s, 1H).

[0093] The yield of A130 was 69.42%, and the mass spectrometry result (M+H) was 751.93; the NMR characterization result was 1 H NMR (400 MHz, CDCl3) δ 8.98 (s, 2H), 8.39 – 8.32 (m, 8H), 7.54 – 7.46 (m, 12H), 7.33 (s, 2H), 7.27 (d, J = 18.0 Hz, 2H).

[0094] The yield of A149 was 78.47%; the mass spectrometry result (M+H) was 852.05; the NMR characterization result was 1 H NMR (400 MHz, CDCl3) δ 9.09 (t, J = 3.0 Hz, 2H), 8.49 (dd,J = 15.0, 3.0 Hz, 2H), 8.40 – 8.32(m, 4H), 8.20 – 8.13 (m, 2H), 8.11 – 7.97 (m, 6H), 7.66 – 7.55 (m, 4H), 7.55– 7.46 (m, 8H), 7.43 – 7.35 (m, 2H).

[0095] The yield of A175 was 72.33%; the mass spectrometry result (M+H) was 932.1; the NMR characterization result was 1 H NMR (400 MHz, CDCl3)δ 8.51 (dd, J = 13.1, 4.8 Hz, 1H), 8.40 – 8.32 (m, 4H), 8.07 (d, J =15.0 Hz, 1H), 7.98 (dd, J = 14.5, 3.4 Hz, 2H), 7.83 – 7.74 (m, 2H), 7.63 –7.45 (m, 14H), 7.43 – 7.35 (m, 3H), 7.32 (dd, J = 14.7, 3.4 Hz, 2H), 6.92 (t,J = 2.8 Hz, 1H).

[0096] The yield of A178 was 67.25%; the mass spectrometry result (M+H) was 903.40; the NMR characterization result was 1 H NMR (400 MHz, CDCl3)δ 8.51 (dd, J = 13.1, 4.8 Hz, 1H), 8.40 – 8.32 (m, 4H), 8.07 (d, J =15.0 Hz, 1H), 8.00 – 7.93 (m, 4H), 7.83 – 7.72 (m, 6H), 7.54 – 7.45 (m, 10H), 7.45 – 7.36 (m, 3H), 7.29 – 7.21 (m, 4H), 6.79 (s, 1H).

[0097] The yield of A210 was 74.56%; the mass spectrometry result (M+H) was 801.99; the NMR characterization result was 1 H NMR (400 MHz, CDCl3)δ 9.08 (dd, J = 14.5, 3.4 Hz, 2H), 8.40 – 8.32 (m, 8H), 8.17 (dd, J= 14.5,3.4 Hz, 2H), 7.74-7.67 (m, 2H), 7.66 – 7.58 (m, 2H), 7.54 – 7.46 (m, 12H).

[0098] The yield of A234 was 68.86%; the mass spectrometry result (M+H) was 801.99; the NMR characterization result was 1 H NMR (400 MHz, CDCl3) δ 9.11 (d, J = 15.0 Hz, 2H), 8.43 (dd, J = 15.0, 2.9 Hz, 2H), 8.40 –8.30 (m, 8H), 7.92 (t, J = 1.6 Hz, 2H), 7.70-7.66 (m, 2H), 7.54 – 7.46 (m, 12H).

[0099] The yield of A252 was 75.62%; the mass spectrometry result (M+H) was 791.96; the NMR characterization result was 1 H NMR (400 MHz, CDCl3) δ 8.38 – 8.31 (m, 8H), 8.10 (d, J = 2.8 Hz, 1H), 7.67 (s, 1H), 7.64 –7.53 (m, 3H), 7.52 – 7.45 (m, 13H).

[0100] The yield of A319 was 73.81%; the mass spectrometry result (M+H) was 904.17; the NMR characterization result was 1 H NMR (400 MHz, CDCl3) δ 8.53 – 8.45 (m, 4H), 8.41 – 8.32 (m, 4H), 7.98 (dd, J = 14.5, 3.4Hz, 1H), 7.86 – 7.76 (m, 2H), 7.57 – 7.46 (m, 7H), 7.41 – 7.35 (m, 5H), 7.35 – 7.27 (m, 1H), 1.33 (s, 18H).

[0101] The yield of A346 was 76.77%; the mass spectrometry result (M+H) was 854.02; the NMR characterization result was 1H NMR (400 MHz, CDCl3)δ 8.41 – 8.32 (m, 4H), 8.08-8.02 (m, 1H), 7.92 – 7.89 (m, 1H), 7.81 –7.71 (m, 4H), 7.68 (d, J = 2.0 Hz, 2H), 7.55 – 7.39 (m, 9H), 7.36 – 7.26 (m, 2H), 7.25 – 7.15 (m, 1H), 1.69 (s, 6H).

[0102] The yield of A416 was 66.35%; the mass spectrometry result (M+H) was 701.87; the NMR characterization result was 1 H NMR (400 MHz, CDCl3) δ 9.18 (dd, J = 14.9, 3.0 Hz, 4H), 9.14 (s, 4H), 8.55 (dd, J = 15.0,2.9 Hz, 4H), 7.78-7.70 (m, 4H), 7.28 – 7.18 (m, 8H).

[0103] The yield of A423 was 72.62%; the mass spectrometry result (M+H) was 751.93; the NMR characterization result was 1 H NMR (400 MHz, CDCl3)δ 9.18 (dd, J = 14.9, 3.0 Hz, 4H), 9.14 (s, 4H), 8.58-8.50 (m, 5H), 8.24 (d, J = 2.9 Hz, 1H), 8.14 (dd, J = 15.0, 2.8 Hz, 1H), 7.88 – 7.82 (m,1H), 7.81 – 7.69 (m, 5H), 7.35 (dd, J = 15.0, 2.9 Hz, 1H), 7.28-7.20 (m, 4H).

[0104] The yield of A441 was 71.34%; the mass spectrometry result (M+H) was 705.9; the NMR characterization result was 1 H NMR (400 MHz, CDCl3)δ 8.41 – 8.32 (m, 8H), 7.54 – 7.45 (m, 12H).

[0105] The yield of A460 was 74.40%; the mass spectrum result (M+H) was 778.09.

[0106] The yield of A464 was 75.93%; the mass spectrometry result (M+H) was 806.02; the NMR characterization result was 1 H NMR (400 MHz, CDCl3)δ 8.40 – 8.33 (m, 8H), 7.96 (dd, J = 11.1, 6.9 Hz, 2H), 7.60 (dd, J =11.0, 6.9 Hz, 2H), 7.53 – 7.48 (m, 12H).

[0107] The yield of A470 was 76.92%; the mass spectrometry result (M+H) was 912.18; the NMR characterization result was 1 H NMR (400 MHz, CDCl3)δ 8.41 – 8.30 (m, 8H), 8.08 – 8.02 (m, 2H), 7.55 – 7.46 (m, 14H), 7.41 (s, 2H).

[0108] The synthetic route of compound A389 is as follows: ; Synthesis of compound A389-3: Compound A389-1 (10.00 g, 27.95 mmol), compound A389-2 (4.48 g, 27.95 mmol), tetrakis(triphenylphosphine)palladium (0.32 g, 0.28 mmol), sodium hydroxide (2.79 g, 69.87 mmol), tetrahydrofuran (300 mL), and deionized water (100 mL) were added to a 500 mL three-necked round-bottom flask, and the vacuum was replaced with nitrogen three times. Then, the system was heated to 75 °C for 4 hours. The reaction was monitored by TLC (ethyl acetate:n-hexane = 1:15 as the developing solvent). Compound A389-1 was completely consumed. After the reaction was completed, a large amount of solid was precipitated, which was directly filtered to obtain 12 g of solid. Tetrahydrofuran (500 mL) was added to dissolve and clarify the solid. Silica gel (60 g, 200-300 mesh chromatography column silica gel) was filtered once. The filtrates were combined and concentrated at 50 ° C for 1 hour to obtain 10 g of white solid. Toluene (90 mL) was added, and the oil temperature was raised to 105 ° C to dissolve and clarify. The temperature naturally dropped to room temperature and stirred for 1 hour, filtered, and dried in vacuo at 70 ° C for 3 hours to obtain a white solid as compound A389-3 (9.15 g, mass purity: 99.37%, yield: 74.76%), mass spectrum result: 438.12 (M+H).

[0109] Synthesis of compound A389-4: Compound A389-3 (9.00 g, 20.55 mmol), compound A4-7 (5.22 g, 20.55 mmol), tris(dibenzylideneacetone)dipalladium (0.19 g, 0.21 mmol), 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (0.20 g, 0.41 mmol), potassium acetate (5.04 g, 51.38 mmol), 1,4-dioxane (350 mL) were added to a 500 mL three-necked round-bottom flask, and the vacuum was replaced with nitrogen three times. Then, the system was heated to 100 °C for 4 hours. The reaction was monitored by TLC (ethyl acetate: n-hexane = 1:15 as the developing solvent). Compound A389-3 was completely consumed. The mixture was cooled to room temperature, concentrated under reduced pressure to remove part of the solvent, ethyl acetate (200 mL) was added, and the mixture was washed three times with deionized water (100 mL*3). The mixture was separated, and the sample was mixed with silica gel and dry-loaded onto a column. Purification was performed by silica gel column chromatography (200-300 mesh silica gel, ethyl acetate:n-hexane = 1:15 as eluent). After elution, the mixture was concentrated under reduced pressure at 60 °C for 1 hour to obtain a white solid as compound A389-4 (8.24 g, mass purity: 99.29%, yield: 75.73%), and the mass spectrum result was 530.25 (M+H).

[0110] Synthesis of compound A389-6: Referring to the synthesis and purification method of compound A389-3, it is only necessary to change the corresponding raw materials to obtain the target compound A389-6 (9.37 g, mass purity: 99.50%, yield: 72.12%), mass spectrum result: 348.11 (M+H).

[0111] Synthesis of compound A389-7: Referring to the synthesis and purification method of compound A389-4, it is only necessary to change the corresponding raw materials to obtain the target compound A389-7 (8.24 g, mass purity: 99.39%, yield: 75.73%), mass spectrum result: 440.24 (M+H).

[0112] Synthesis of compound A389-9: Compound A389-7 (9.00 g, 20.48 mmol), compound A389-8 (6.30 g, 20.48 mmol), 1,1'-bis(diphenylphosphino)ferrocenepalladium dichloride (0.15 g, 0.20 mmol), potassium carbonate (7.08 g, 51.21 mmol), toluene (250 mL), ethanol (50 mL), and deionized water (50 mL) were added to a 500 mL three-necked round-bottom flask, and the vacuum was replaced with nitrogen three times. Then, the system was heated to 75 °C for 6 hours. The reaction was monitored by TLC (ethyl acetate: n-hexane = 1:15 as the developing solvent). Compound A389-7 was completely consumed; After the reaction was completed, a large amount of solid was precipitated, which was directly filtered to obtain 10 g of solid. Tetrahydrofuran (300 mL) was added to dissolve and clarify the solid. Silica gel (60 g, 200-300 mesh chromatography column silica gel) was filtered once. The filtrates were combined and concentrated at 50 ° C for 1 hour to obtain 8 g of white solid. Toluene (60 mL) was added, and the oil temperature was raised to 105 ° C to dissolve and clarify. The temperature naturally dropped to room temperature and stirred for 1 hour, filtered, and dried in vacuo at 70 ° C for 3 hours to obtain a white solid as compound A389-9 (7.68 g, mass purity: 99.54%, yield: 69.42%), mass spectrum result: 540.21 (M+H).

[0113] Synthesis of compound A389: Compound A389-9 (7.00 g, 12.96 mmol), compound A389-4 (6.86 g, 12.96 mmol), dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (0.10 g, 0.13 mmol), potassium carbonate (4.48 g, 32.40 mmol), 1,4-dioxane (250 mL), and deionized water (50 mL) were added to a 500 mL three-necked round-bottom flask, and the vacuum nitrogen was replaced three times. Then, the system was heated to 80 ° C for 4 hours. The reaction was monitored by TLC (dichloromethane:n-hexane = 1:3 as the developing solvent). Compound A389-9 was completely consumed; After the reaction was completed, a large amount of solid was precipitated, which was directly filtered to obtain 11g of solid. Tetrahydrofuran (350mL) was added to dissolve and clarify silica gel (60g, 200-300 mesh chromatography column silica gel). The filtrates were combined and concentrated at 50°C for 1 hour to obtain 9.5g of white solid. Toluene (100mL) was added, and the oil temperature was raised to 110°C to dissolve and clarify. The mixture was naturally cooled to room temperature and stirred for 1 hour, filtered, and vacuum dried at 70°C for 3 hours to obtain a white solid compound A389 (7.64g, mass purity: 99.94%, yield: 64.98%). 7.64g of crude compound A389 was sublimated and purified to obtain sublimation pure compound A389 (6.05g, mass purity: 99.94%, yield: 79.18%), and the mass spectrum result was 907.39 (M+H).

[0114] The NMR characterization results of compound A389 are: 1 H NMR (400 MHz, CDCl3) δ 8.39 – 8.31 (m,7H), 8.09 (d, J = 14.9 Hz, 1H), 7.98 (dd, J = 14.6, 3.4 Hz, 1H), 7.88 (d, J =3.0 Hz, 1H), 7.81 – 7.70 (m, 4H), 7.59 – 7.52 (m, 2H), 7.52 – 7.45 (m, 9H), 7.44 – 7.26 (m, 3H), 1.69 (s, 6H).

[0115] Compounds A490 and A492 were prepared using a synthetic method similar to that of compound A389, except that different raw materials were used, i.e., raw materials A389-1, A389-5, and A389-8 in the synthesis of compound A389 were replaced by other raw materials, respectively.

[0116] During the synthesis of A490 and A492, the raw material A389-1 during the synthesis of compound A389 was used in sequence , Instead, the raw material A389-5 is used in turn , Instead, the raw material A389-8 is used in turn , replace.

[0117] The structural formula of A490 and A492 is: .

[0118] The corresponding yield of A490 was 68.35%, the corresponding mass spectrometry result (M+H) was 749.96, and the corresponding NMR characterization result was 1 HNMR (400 MHz, CDCl3) times: δ 8.89 (dd, J = 15.0, 3.1 Hz, 2H), 8.37 (dd, J = 15.0,2.9 Hz, 4H), 8.23 ​​(s, 2H), 7.97 – 7.91 (m, 6H), 7.70 (t, J = 15.0 Hz, 2H), 7.55(dd, J = 3.2, 1.4 Hz, 4H), 7.54 – 7.45 (m, 8H).

[0119] The corresponding yield of A492 was 70.49%, the corresponding mass spectrum result (M+H) was 700.89, and the corresponding NMR characterization results were δ 9.18 (dd, J = 14.9, 3.0 Hz, 2H), 9.14 (s, 2H), 8.55 (dd, J = 15.0, 2.9Hz, 2H), 8.39 – 8.32 (m, 2H), 8.23 ​​(s, 1H), 8.10 (t, J = 3.0 Hz, 1H), 7.97 –7.91 (m, 2H), 7.79 – 7.66 (m, 3H), 7.64 – 7.58 (m, 2H), 7.58 – 7.45 (m, 6H),7.27-7.19 (m, 2H).

[0120] Application example: Fabrication of organic electroluminescent devices As attached Figure 1 As shown, an organic electroluminescent device 1 includes a stacked glass substrate 1, an anode 2, a hole injection layer 3, a first hole transport layer 4 (HTL1), a second hole transport layer 5 (HTL2), a light-emitting layer 6, a hole blocking layer 7 (HBL), an electron transport layer 8 (ETL), and a cathode 9.

[0121] A method for preparing an organic electroluminescent device 1 comprises the following steps: A glass substrate 1 having an ITO transparent electrode (anode 2) on its surface is provided, wherein the thickness of the anode is 100 nm; Compound HATCN is evaporated on the surface of the anode 2 to form a hole injection layer 3, and the thickness of the hole injection layer 3 is 5 nm; Compound HTM1 is evaporated on the surface of the hole injection layer 3 to form a first hole transport layer 4 (HTL1), and the thickness of the first hole transport layer 4 is 60 nm; Compound HTM2 is evaporated on the surface of the first hole transport layer 4 to form a second hole transport layer 5 (HTL2), and the thickness of the second hole transport layer 5 is 10 nm; Co-evaporating a host material and a guest material on the surface of the second hole transport layer 5 (the weight ratio of the host material to the guest material is 97%:3%) to form a light-emitting layer 6, and the thickness of the light-emitting layer 6 is 25 nm; A hole blocking material is evaporated on the surface of the light emitting layer 6 to form a hole blocking layer 7 (HBL), and the thickness of the hole blocking layer 7 is 5 nm; An electron transport material is evaporated on the surface of the hole blocking layer 7 to form an electron transport layer 8 (ETL), and the thickness of the electron transport layer 8 is 350 nm; Metal Mg / Ag (the weight ratio of Mg to Ag is 1:9) is evaporated on the surface of the electron transport layer 8 to form a cathode 9 with a thickness of 100 nm, thereby obtaining an organic electroluminescent device 1 .

[0122] The hole blocking material is the heterocyclic compound of the present application or the comparative compound, and the electron transport material is the electron transport material ETL or the heterocyclic compound of the present application: LiQ (weight ratio 1:1).

[0123] Among them, the structural formulas of HATCN, HTM1, HTM2, host material (BH), guest material (BD), ETL, LiQ and comparative compounds 1-3 are as follows: .

[0124] evaluate: The above organic electroluminescent device 1 was tested for device performance, and the heterocyclic compound prepared in the present application and the comparative compounds 1-3 were used as hole blocking materials and electron transport materials for comparison, respectively. A constant current power supply (Keithley 2400) was used to flow a fixed current density through the light-emitting element, and the luminescence spectrum was tested using a spectroscopic radiation system (CS 2000). At the same time, the luminescence spectrum was measured at 10 mA / cm 2 The IVL (current-voltage-luminance) performance of the device was measured at 1000 nits, and the LT95 device life was tested at 1000 nits. The results are shown in Table 1 below (the examples in Table 1 use the heterocyclic compounds of the present application, and the comparative examples use comparative compounds).

[0125] Table 1

[0126] From the data comparison in Table 1 above, it can be seen that the heterocyclic compound of the present application is applied to the organic electroluminescent device 1 as a hole blocking layer material and an electron transport layer material, and exhibits more superior performance in driving voltage, luminous efficiency and device life than the comparative compounds 1-3.

[0127] like Figure 2 As shown, it is a schematic diagram of the structure of an organic electroluminescent device 2, including a glass substrate 01, an anode 02, a hole injection layer 03, a first hole transport layer 04, a first electron blocking layer 05, a first light-emitting layer 06, a first electron transport layer 07, an N-type charge generation layer 08, a P-type charge generation layer 09, a second hole transport layer 10, a second electron blocking layer 11, a second light-emitting layer 12, a second electron transport layer 13, an electron injection layer 14, and a cathode 15, which are stacked in sequence.

[0128] The method for manufacturing an organic electroluminescent device 2 comprises the following steps: A glass substrate 01 having an ITO transparent electrode (anode 02) on the surface is provided, and the thickness of the anode is 1000 nm; Compound HATCN is evaporated on the surface of the anode 02 to form a hole injection layer 03 with a thickness of 20 nm; HTM1 is evaporated on the surface of the hole injection layer 03 to form a first hole transport layer 04 with a thickness of 10 nm; HTM2 is evaporated on the surface of the first hole transport layer 04 to form a first electron blocking layer 05 with a thickness of 5 nm; Co-evaporating a host material (BH) and a guest material (BD) on the surface of the first electron blocking layer 05 to form a first light-emitting layer 06, wherein the weight ratio of the host material (BH) to the guest material (BD) is 97:3, and the thickness of the first light-emitting layer 06 is 20 nm; Co-evaporating ETL and LiQ on the surface of the first light-emitting layer 06 to form a first electron transport layer 07, wherein the weight ratio of ETL and LiQ is 1:1, and the thickness of the first electron transport layer 07 is 35 nm; A heterocyclic compound and Yb are co-evaporated on the surface of the first electron transport layer 07 to form an N-type charge generation layer 08 (referred to as an N-CGL layer). The types of heterocyclic compounds in the N-CGL layer of each embodiment and comparative example are shown in Table 2. The weight ratio of the heterocyclic compound to Yb is 95:5. The thickness of the N-type charge generation layer 08 is 100 nm. HATCN is evaporated on the surface of the N-type charge generation layer 08 to form a P-type charge generation layer 09 with a thickness of 10 nm; HTM1 is evaporated on the surface of the P-type charge generation layer 09 to form a second hole transport layer 10 with a thickness of 10 nm; HTM2 is evaporated on the surface of the second hole transport layer 10 to form a second electron blocking layer 11 with a thickness of 5 nm; Co-evaporating a host material (BH) and a guest material (BD) on the surface of the second electron blocking layer 11 to form a second light-emitting layer 12, wherein the weight ratio of the host material (BH) to the guest material (BD) is 97:3, and the thickness of the second light-emitting layer 12 is 20 nm; Co-evaporating ETL and LiQ on the surface of the second light-emitting layer 12 to form a second electron transport layer 13, wherein the weight ratio of ETL and LiQ is 1:1, and the thickness of the second electron transport layer 13 is 35 nm; Yb is evaporated on the surface of the second electron transport layer 13 to form an electron injection layer 14 with a thickness of 1 nm; Ag was evaporated on the surface of the electron injection layer 14 to form a cathode 15 with a thickness of 1000 nm, thereby obtaining an organic electroluminescent device 2 .

[0129] evaluate: The prepared organic electroluminescent device 2 was subjected to device performance testing. A constant current power supply (Keithley 2400) was used to flow a fixed current density through the light-emitting element, and a spectroradiometer (CS 2000) was used to test the luminescence spectrum. At the same time, the current density was 10 mA / cm 2 The IVL (current-voltage-luminance) performance of the device was measured at 1000 nits, and the life of the LT95 device was tested at 1000 nits. The test results are shown in Table 2 (the examples in Table 2 use the heterocyclic compounds of the present application, and the comparative examples use comparative compounds).

[0130] Table 2

[0131] As can be seen from Table 2, when the N-CGL layer prepared by the heterocyclic compound of the embodiment of the present application is used in a tandem organic electroluminescent device, the device operating voltage is significantly reduced compared with the comparative compounds 1-3, and the device power consumption is effectively reduced. At the same time, the current efficiency and device life are significantly improved. As an N-type charge generation layer material, the heterocyclic compound is suitable for OLED light-emitting devices and has the potential to be applied to the AMOLED industry.

[0132] The above results show that the heterocyclic compound of the present application has the advantages of high luminous efficiency, low voltage, long life, etc., and can be used in organic light-emitting devices. In particular, as a hole blocking layer material, an electron transport layer material, and an N-type charge generation layer material, it has the potential to be applied to the AMOLED industry.

Claims

1. A heterocyclic compound, characterized in that Its general structural formula is shown in formula (1): Formula (1), Wherein, ring A is selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted phenanthrene ring, or a substituted or unsubstituted cyclic structure represented by formula (1-1): Formula (1-1); Wherein, Ring B and Ring C are independently selected from a benzene ring or a naphthalene ring, X is CRaRb, O, S or Se, * represents the connection site between Ring A and L1 and L2; Ra and Rb are independently selected from hydrogen, C1-C30 alkyl, C1-C30 heteroalkyl, C3-C30 cycloalkyl, C3-C30 heterocycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C3-C30 alkylsilyl or C6-C30 arylsilyl; X1-X6 are independently selected from N or CR1, and at least one of X1-X3 is N, and at least one of X4-X6 is N; L1 and L2 are independently selected from a C6-C60 arylene group substituted with a substituent or a C5-C60 heteroarylene group substituted with a substituent, and the substituents in L1 and L2 contain at least one deuterium; R1 is selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboryl, C6-C60 arylboryl, C6-C60 arylphosphino or C6-C60 arylamine; Ar1, Ar2, Ar3, Ar4 are independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C9-C30 cycloalkyl and aryl; The substitution in Ar1, Ar2, Ar3, and Ar4 is substituted by at least one of deuterium, halogen, cyano, isocyano, phosphino, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl substituted amine, C1-C6 hydrocarbon substituted or unsubstituted C6-C30 aryl, C1-C6 hydrocarbon substituted or unsubstituted C3-C30 heteroaryl, wherein the number of substitutions ranges from a single substitution to a maximum number of substitutions; The substitution in the ring A is substituted by at least one selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboryl, C6-C60 arylboryl, C6-C60 arylphosphino or C6-C60 arylamine, wherein the number of substitutions is from a single substitution to the maximum number of substitutions; The heteroatoms in the heteroarylene group, heteroalkyl group, heterocycloalkyl group and heteroaryl group are independently selected from at least one of O, S, N, Se, Si and Ge.

2. The heterocyclic compound according to claim 1, characterized in that The ring A structure represented by the formula (1) is selected from any one of the following structures: ； Wherein, X is CRaRb, O, S or Se; * represents the connection site between ring A and L1 and L2 in formula (1); Ra and Rb are each independently selected from hydrogen, C1-C20 alkyl, C1-C20 heteroalkyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C20 aryl, C3-C20 heteroaryl, C3-C20 alkylsilyl or C6-C20 arylsilyl; R2 and R3 are each independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboryl, C6-C60 arylboryl, C6-C60 arylphosphino or C6-C60 arylamine; a and b both represent integers of 0-4. When a is an integer of 2-4, each R2 is the same or different; when b is an integer of 2-4, each R3 is the same or different.

3. The heterocyclic compound according to claim 1, characterized in that The ring A structure represented by the formula (1) is selected from one of the following structures: ; Wherein, R2 and R3 are independently selected from hydrogen, deuterium, halogen, cyano, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl; a and b both represent integers of 0-4. When a is an integer of 2-4, each R2 is the same or different; when b is an integer of 2-4, each R3 is the same or different; Or, the substituents of L1 and L2 satisfy one of the following conditions: (1) The substituent in L1 or L2 is deuterium; (2) The substituents in L1 and L2 are deuterium-containing substituents; (3) The substituents in L1 and L2 contain at least one deuterium and at least one of halogen, cyano, isocyano, phosphino, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl substituted amine, C1-C6 hydrocarbon substituted or unsubstituted C6-C30 aryl, and C1-C6 hydrocarbon substituted or unsubstituted C3-C30 heteroaryl.

4. The heterocyclic compound according to claim 1 or 2, characterized in that The L1 and L2 are independently selected from a C6-C40 arylene group substituted with a substituent or a C5-C40 heteroarylene group substituted with a substituent, and the substituents in L1 and L2 contain at least one deuterium; and / or, the substituent in L1 and L2 is at least one of deuterium and deuterium-substituted C1-C6 alkyl, the number of the substituent is tri-substituted to the maximum number of substitutions, and the number of deuterium substitutions in the deuterium-substituted C1-C6 alkyl is mono-substituted to the maximum number of substitutions; and / or, Ar1, Ar2, Ar3, Ar4 are independently selected from substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl, substituted or unsubstituted C6-C20 cycloalkyl and aryl; And / or, the substitution in Ar1, Ar2, Ar3, Ar4 is substitution by at least one of deuterium, halogen, cyano, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 hydrocarbon substituted or unsubstituted C6-C20 aryl, C1-C6 hydrocarbon substituted or unsubstituted C3-C20 heteroaryl, wherein the number of substitutions ranges from a single substitution to a maximum number of substitutions.

5. The heterocyclic compound according to claim 1 or 2, characterized in that The L1 and L2 are independently selected from deuterated phenylene, deuterated biphenylene, deuterated naphthylene or deuterated pyridylene, and the number of deuterations ranges from single substitution to the maximum number of substitutions; And / or, the annular structure represented by formula (1-1) is selected from a dibenzofuran ring, a fluorene ring or a naphthobenzofuran ring.

6. The heterocyclic compound according to claim 1 or 2, characterized in that There are at least two Ns in X1-X3 and at least two Ns in X4-X6; And / or, R1 is selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C20 alkyl, C1-C20 heteroalkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C1-C20 alkoxy, C6-C30 aryloxy, C3-C20 alkylsilyl, C6-C30 arylsilyl, C1-C20 alkylboryl, C6-C30 arylboryl, C6-C30 arylphosphino or C6-C30 arylamine.

7. The heterocyclic compound according to any one of claims 1 to 3, characterized in that X1-X6 are all N; or, Ar1, Ar2, Ar3, Ar4 are independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted 9,9-diphenylfluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted chrysene, substituted or unsubstituted carbazolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or Unsubstituted fluoranthene group, substituted or unsubstituted benzoxazolyl group, substituted or unsubstituted benzimidazolyl group, substituted or unsubstituted benzotriazolyl group, substituted or unsubstituted triphenylene group, substituted or unsubstituted benzopyridinyl group, substituted or unsubstituted cyclohexylphenyl group, wherein Ar1, Ar2, Ar3, Ar4 are substituted by at least one of deuterium, fluorine, cyano, C1-C10 alkyl, C3-C16 cycloalkyl, C1-C6 hydrocarbon substituted or unsubstituted C6-C12 aryl, C1-C6 hydrocarbon substituted or unsubstituted C3-C12 heteroaryl, wherein the number of substitutions is from single substitution to the maximum number of substitutions; Alternatively, the ring A contains at least one deuterium atom.

8. The heterocyclic compound according to any one of claims 1 to 3, characterized in that The heterocyclic compound represented by the formula (1) satisfies at least one of the following conditions: (1) The six-membered rings where X1-X3 and X4-X6 are located are independently selected from one of the following structural formulas: ； (2) The six-membered ring where X1-X3 is located has the same structure as the six-membered ring where X4-X6 is located; (3) L1 and L2 are independently selected from one of the following structural formulas: ； (4) The structural formula of L1 and L2 is the same; (5) Ring A is selected from one of the following structural formulas: ； (6) Ar1-Ar4 are independently selected from one of the following structural formulas: ； (7) The structural formulas of Ar1 and Ar3 are the same, and the structural formulas of Ar2 and Ar4 are the same; (8) The following two groups of ring A in formula (1) have the same structural formula 、 。 9. An organic electroluminescent device, characterized in that: The invention comprises the heterocyclic compound according to any one of claims 1 to 8.

10. The organic electroluminescent device according to claim 9, characterized in that: include: an anode, a cathode, and an organic layer between the anode and the cathode; The organic layer includes a light-emitting layer and at least one of an electron transport layer, a hole blocking layer, and an N-type charge generation layer; The material of at least one of the electron transport layer, the hole blocking layer or the N-type charge generation layer contains the heterocyclic compound according to any one of claims 1 to 8.

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