Organic electroluminescent compound and use thereof

Abstract

The application relates to the technical field of display, in particular to an organic electroluminescent compound and application thereof. The organic electroluminescent compound provided by the application has a structure shown in formula (1), and the type of substituent group is further limited based on the structure of formula (1), so that the structure of the compound is improved and the chemical stability is improved, the carrier mobility of the organic electroluminescent compound is more balanced, and further, the organic electroluminescent device containing the organic electroluminescent compound has a lower driving voltage, a higher luminous efficiency and a longer service life.

Description

Technical Field

[0001] This invention relates to the field of display technology, and more specifically to an organic electroluminescent compound and its applications. Background Technology

[0002] Organic light-emitting diodes (OLEDs) are devices that convert electrical energy into light by applying electricity to organic light-emitting materials. They generally have a structure comprising an anode, a cathode, and an organic layer between the anode and cathode. The organic layer of an organic OLED can consist of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer (containing a host material and dopant materials), an electron buffer layer, a hole blocking layer, an electron transport layer, and an electron injection layer. The materials used in the organic layer are classified according to their function as hole injection materials, hole transport materials, electron blocking materials, light-emitting materials, electron buffer materials, hole blocking materials, electron transport materials, and electron injection materials. In these organic OLEDs, due to the application of voltage, holes are injected from the anode into the light-emitting layer, and electrons are injected from the cathode into the light-emitting layer. The recombination of holes and electrons forms high-energy excitons. With this energy, the organic light-emitting compound reaches an excited state, and light is emitted by the energy generated when the excited state of the organic light-emitting compound returns to its ground state.

[0003] The most important factor determining the luminescence efficiency of organic EL devices is the luminescent material. The luminescent material must possess high quantum efficiency and high electron and hole mobility, and the resulting luminescent material layer must be uniform and stable. Luminescent materials are classified according to the color of their emission into blue, green, and red luminescent materials, as well as yellow and orange luminescent materials. Furthermore, luminescent materials can also be classified according to their function into host materials and dopant materials.

[0004] However, existing organic electroluminescent materials have poor spatial structure and chemical stability, which leads to problems such as high driving voltage, low luminous efficiency and short lifespan in organic electroluminescent devices containing these materials, severely limiting the application of organic electroluminescent devices. Summary of the Invention

[0005] The purpose of this invention is to overcome the poor spatial structure and chemical stability of existing organic electroluminescent materials, which result in high driving voltage, low luminous efficiency, and short lifespan of organic electroluminescent devices containing such materials, and to provide an organic compound and its application.

[0006] In this invention, Indicates a connection key.

[0007] The solution adopted in this invention is as follows:

[0008] An organic electroluminescent compound, characterized in that the organic electroluminescent compound has the structure shown in formula (1):

[0009] Compounds having the following formula (1):

[0010]

[0011] In equation (1), X 1 X 2 X 3 Each independently selected from CR 1 CR 2 or CR 3 R 1 Selected from equation (1-1), R 2 Selected from equation (1-2), R 3 Selected from substituted or unsubstituted C6-C60 aryl groups;

[0012] X 4 X 5 X 6 Selected from N;

[0013]

[0014] In equation (1-1), Ar 1 Selected from substituted or unsubstituted C6-C60 aryl groups;

[0015] n1 is an integer selected from 0 to 6;

[0016]

[0017] Ar 2 Selected from substituted or unsubstituted C6-C60 aryl groups or substituted or unsubstituted C1-C60 heteroaryl groups;

[0018] n2 is an integer selected from 0 to 6;

[0019] The substituents in the substituted C6-C60 aryl and substituted C1-C60 heteroaryl are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C60 alkyl, C6-C60 aryl, and C1-C60 heteroaryl.

[0020] Substituents

[0021] In this application, the term "substituent" has its common meaning as known in the art, referring to a chemical moiety covalently attached to or, where appropriate, fused to a parent nucleus group.

[0022] Replaced or not replaced

[0023] In this application, the term "substituted or unsubstituted" means that the functional group described after the term may or may not have substituents (hereinafter, for ease of description, substituents are collectively referred to as Rc). For example, "substituted or unsubstituted aryl" refers to an aryl group having a substituent Rc or an unsubstituted aryl group. The aforementioned substituent, i.e., Rc, can be, for example, deuterium, halogen, cyano, C1-C60 alkyl, C3-C60 cycloalkyl, C6-C60 aryl, or C1-C60 heteroaryl. Optionally, it can be, for example, deuterium, a halogen group, cyano, alkyl, haloalkyl, trialkylsilyl, deuterated alkyl, aryl, heteroaryl, etc. Of course, the number of substituents Rc can be one or more. When two substituents Rc are attached to the same atom, the two substituents Rc can exist independently or be connected to each other to form a ring with the atom; when two adjacent substituents Rc exist on a functional group, the adjacent substituents Rc can exist independently or fuse with the functional group to which they are attached to form a ring.

[0024] The definition of "unsubstituted" is as follows: it refers to being replaced by hydrogen atoms, and the hydrogen atoms in this invention include protium, deuterium, and tritium.

[0025] C1-C60, C3-C60, C6-C60

[0026] In this application, C1-C60, C3-C60, and C6-C60 define the range of carbon atoms, and the number of carbon atoms is any integer within the defined range. For example, C6-C60 aryl means that the number of carbon atoms representing the aryl group can be any integer within the range of 6-60, such as 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, and 60.

[0027] alkyl

[0028] In this application, the term "alkyl" refers, whether as part of other terms or used alone, to a saturated hydrocarbon group, which may be straight-chain or branched. The term "C1-C60 alkyl" is derived from a monovalent substituent of a straight-chain or branched saturated hydrocarbon having 1 to 60 carbon atoms, preferably 1 to 40 carbon atoms, and more preferably 1 to 20 carbon atoms. Examples of such substituents include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl.

[0029] Aryl, aryl

[0030] In this application, the terms "aryl" and "arylene" include monocyclic, polycyclic, or fused-ring aryl groups, wherein the rings may be interrupted by short non-aromatic units and may contain a spirostructure. Aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracene, fluorene, and spirodifluorene. Arylene groups include, but are not limited to, phenylene, biphenylene, terphenylene, naphthylene, phenanthrylene, anthracene, fluorene, and spirodifluorene. Arylene refers to a divalent or polyvalent group formed by the further loss of one or more hydrogen atoms from an aryl group.

[0031] heteroaryl, hypoaryl

[0032] In this application, the terms "hybrid aryl" and "heteroaryl" include monocyclic, polycyclic, or fused-ring heteroaryl groups, wherein the rings may be interrupted by short non-aromatic units, and the heteroatoms include nitrogen, oxygen, and sulfur. Heteroaryl groups include, but are not limited to, furanyl, phenylthio, pyrroleyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetraazinyl, triazolyl, tetraazolyl, furazolidyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiopheneyl, isobenzofuranyl, dibenzofuranyl, dibenzothiopheneyl, benzimidazolyl, and benzyl. Benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazoleyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cenolinyl, quinazolinyl, quinoxalinyl, carbazoleyl, phenoxazinyl, phenthiazinyl, phenanthidyl, benzo[m]dioxacyclopentenyl, dihydroacridyl, and their derivatives; heteroaryl groups include, but are not limited to, furanyl, phenylthio, and pyrroleyl. Imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazolyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl Azolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, ininazole, benzothiadiazolyl, quinolinyl, isoquinolinyl, cenolinyl, quinazolinyl, quinoxolinyl, carbazolyl, phenoxazinyl, phenthiazinyl, phenanthridyl, phenanthridyl, benzo[m]dioxacyclopentenyl, dihydroacridyl, and their derivatives, etc. As used herein, the term "substituted" means that a hydrogen atom in the compound is replaced by another substituent. This position is not limited to a specific position, as long as the hydrogen at that position can be replaced by a substituent. When two or more substituents are present, the two or more substituents can be the same or different.

[0033] halogen

[0034] In this application, the term "halogen" refers to an atom selected from fluorine, chlorine, bromine, and iodine.

[0035] hydrogen

[0036] In this application, unless otherwise stated, hydrogen atoms include protium, deuterium, and tritium.

[0037] Preferably, in equation (1), X 1 X 2 X 3 One of them is selected from CR 1 One of them is selected from CR 2 Or, another one selected from CR 3 .

[0038] Preferably, the organic electroluminescent compound has the structure shown in formula (2):

[0039]

[0040] In equations (2) and (3), R 3 Ar 1 Ar 2 The definitions of n1 and n2 are the same as those defined above.

[0041] In this application, D is performed using equation (2) as an example. n1 This indicates that there are n1 D (deuterium) substitutions on the naphthyl group.

[0042] Preferred, Ar 1 Selected from substituted or unsubstituted C6-C50 aryl groups.

[0043] The substituents in the substituted C6-C50 aryl groups are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C50 alkyl, C6-C50 aryl, and C1-C50 heteroaryl.

[0044] Preferred, Ar 1 Selected from substituted or unsubstituted C6-C25 aryl groups.

[0045] The substituents in the substituted C6-C25 aryl groups are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C25 alkyl, C6-C25 aryl, and C1-C25 heteroaryl.

[0046] Preferred, Ar 1 Selected from substituted or unsubstituted C6-C12 aryl groups.

[0047] The substituents in the substituted C6-C12 aryl group are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C12 alkyl, C6-C12 aryl, and C1-C12 heteroaryl.

[0048] Preferred, Ar 1 Selected from substituted or unsubstituted naphthyl groups.

[0049] The substituents in the substituted naphthyl group are selected from deuterium.

[0050] Preferably, the organic electroluminescent compound has the following structure:

[0051]

[0052] In equations (3) to (4), n3, n4, n5, and n6 may be the same or different, and each is independently selected from integers from 0 to 7; R 3 Ar 2 The definitions of n1 and n2 are the same as those above.

[0053] Preferred, R 3 Selected from substituted or unsubstituted C6-C50 aryl groups.

[0054] The substituents in the substituted C6-C50 aryl groups are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C50 alkyl, C6-C50 aryl, and C1-C50 heteroaryl.

[0055] Preferred, R 3 Selected from substituted or unsubstituted C6-C25 aryl groups.

[0056] The substituents in the substituted C6-C25 aryl groups are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C25 alkyl, C6-C25 aryl, and C1-C25 heteroaryl.

[0057] Preferred, R 3 Selected from substituted or unsubstituted C6-C12 aryl groups.

[0058] The substituents in the substituted C6-C12 aryl group are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C12 alkyl, C6-C12 aryl, and C1-C12 heteroaryl.

[0059] R 3 Selected from C6-C12 aryl groups, the molecules have less internal repulsion, are more stable, and have better toughness, thereby improving the film-forming properties of the compounds. This results in organic electroluminescent devices having lower driving voltage, higher luminous efficiency, and longer lifespan.

[0060] Preferred, R 3 Selected from the group consisting of the following groups:

[0061]

[0062]

[0063] Preferred, Ar 2 Selected from substituted or unsubstituted C6-C50 aryl groups or substituted or unsubstituted C1-C50 heteroaryl groups;

[0064] The substituents in the substituted C6-C50 aryl and substituted C6-C50 heteroaryl are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C50 alkyl, C6-C50 aryl, and C1-C50 heteroaryl.

[0065] Preferred, Ar 2 Selected from substituted or unsubstituted C6-C25 aryl or substituted or unsubstituted C6-C25 heteroaryl;

[0066] The substituents in the substituted C6-C25 aryl and substituted C6-C25 heteroaryl are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C25 alkyl, C6-C25 aryl, and C1-C25 heteroaryl.

[0067] The substituents in the substituted C6-C50 aryl and substituted C6-C50 heteroaryl are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C50 alkyl, C6-C50 aryl, and C1-C50 heteroaryl.

[0068] The substituents in the substituted C6-C25 aryl and substituted C6-C25 heteroaryl are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C25 alkyl, C6-C25 aryl, and C1-C25 heteroaryl.

[0069] Preferred, Ar 2 Selected from the group consisting of the following groups:

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076] In this application, For example, D1-D5 indicates that there are 1, 2, 3, 4, or 5 deuterium substitutions on the benzene ring. Preferably, Ar... 2 It is not naphthyl.

[0077] Preferably, n1 and n2 are each independently selected from integers from 0 to 5.

[0078] Preferably, n1 and n2 are each independently selected from integers from 0 to 4.

[0079] Preferably, n1 and n2 are each independently selected from integers from 0 to 3.

[0080] Preferably, n1 and n2 are each independently selected from integers from 0 to 2.

[0081] Preferably, n3, n4, n5 and n6 are each independently selected from integers from 0 to 6.

[0082] Preferably, n3, n4, n5 and n6 are each independently selected from integers from 0 to 5.

[0083] Preferably, n3, n4, n5 and n6 are each independently selected from integers from 0 to 4.

[0084] Preferably, n3, n4, n5 and n6 are each independently selected from integers from 0 to 3.

[0085] Preferably, n3, n4, n5 and n6 are each independently selected from integers from 0 to 2.

[0086] Preferably, the compound is selected from one of the following structures:

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097] The present invention also provides a method for synthesizing the above-mentioned organic electroluminescent compound, the synthetic route of which is shown below:

[0098] General formula for the synthesis of intermediate A:

[0099]

[0100] General formula for the synthesis of intermediate B:

[0101]

[0102] General formula for the synthesis of compound N:

[0103]

[0104] In the formula, X and Y are halogens; R 3 Ar 1 Ar 2 The definition is the same as the definition above.

[0105] The present invention also provides an organic electroluminescent material comprising the above-mentioned organic electroluminescent compound.

[0106] The present invention also provides an organic electroluminescent device, wherein the organic electroluminescent device comprises the above-mentioned organic electroluminescent compound or the above-mentioned organic electroluminescent material.

[0107] Preferably, the organic electroluminescent device includes a first electrode, a second electrode disposed opposite to the first electrode, and at least one organic layer between the first electrode and the second electrode, wherein the organic layer comprises the aforementioned organic electroluminescent compound or the aforementioned organic electroluminescent material.

[0108] Preferably, the organic layer can be composed of a single-layer structure or a multi-layer structure with two or more layers stacked on top of each other. For example, the organic electroluminescent device may include one or more of the following sequentially arranged layers: a hole injection layer, a hole transport layer, a light-emitting auxiliary layer, a light-emitting layer, an electron transport layer, and an electron injection layer.

[0109] Preferably, the light-emitting layer comprises the above-mentioned organic electroluminescent compound or the above-mentioned organic electroluminescent material.

[0110] Preferably, the organic electroluminescent device may be, for example, an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode sequentially stacked on a substrate.

[0111] Preferably, the anode comprises an anode material, preferably a material with a large work function that facilitates hole injection into the first hole transport layer. For example, the anode material may include: metals such as nickel, platinum, vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; or conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole, and polyaniline, but is not limited thereto.

[0112] Preferably, the hole injection layer is used to enhance the ability to inject holes into the hole transport layer. The hole injection layer can be selected from benzidine derivatives, starburst-like aryl amine compounds, phthalocyanine derivatives, or other materials; this application does not impose any special limitations on this. The material of the hole injection layer can, for example, be selected from the following compounds or any combination thereof:

[0113]

[0114]

[0115] Preferably, the hole transport layer may include one or more hole transport materials. The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light-emitting layer. The material of the hole transport layer may be selected from carbazole polymers, carbazole-linked triarylamine compounds, or other types of compounds. This application does not impose any special limitations on this. The material of the hole transport layer may, for example, be selected from the following compounds or any combination thereof:

[0116]

[0117] Preferably, the light-emitting layer is a material capable of receiving holes and electrons from the hole transport layer and the electron transport layer respectively, and combining them to emit light in the visible light region.

[0118] Preferably, the light-emitting layer can be composed of a single light-emitting material, or it can include a host material and a guest material. For example, the light-emitting layer includes a host material and a guest material. Holes injected into the light-emitting layer and then electrons injected into the light-emitting layer can recombine in the light-emitting layer to form excitons. The excitons transfer energy to the host material, and the host material transfers energy to the guest material, thereby causing the guest material to emit light.

[0119] Preferably, the host material of the light-emitting layer may include metal chelating compounds, bis(phenylacetyl) derivatives, aromatic amine derivatives, dibenzofuran derivatives, and other types of materials. For example, the host material may include the above-mentioned nitrogen-containing compounds or the above-mentioned organic electroluminescent materials.

[0120] Preferably, the guest material of the luminescent layer may comprise a compound having a condensed aryl ring or a derivative thereof, a compound having a heteroaryl ring or a derivative thereof, an aromatic amine derivative, or other types of materials, which are not limited herein by this application. The guest material is also referred to as a dopant or dopant, and can be classified into fluorescent dopant and phosphorescent dopant according to the type of luminescence.

[0121] Preferably, the electron transport layer can be a single-layer structure or a multi-layer structure, and may include one or more electron transport materials. The electron transport layer is a layer that receives electrons from the cathode or an electron injection layer formed on the cathode, transports electrons to the light-emitting layer, and suppresses hole transfer from the light-emitting layer. The electron transport material is suitably one that can effectively receive electron injection from the cathode and transfer electrons to the light-emitting layer, and has a high electron mobility. The electron transport layer may be selected from, but is not limited to, Al complexes of 8-hydroxyquinoline, complexes containing Alq3, organic free radical compounds, hydroxyflavonoid-metal complexes, etc., but is not limited to these.

[0122] Preferably, the electron transport layer includes, but is not limited to, the following structures:

[0123]

[0124] Preferably, the electron injection layer is used to enhance the ability to inject electrons into the electron transport layer. The electron injection layer may include fluorenone, anthraquinone dimethane, biphenylquinone, thiamethane dioxide, azole, diazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenemethane, anthrone, and their derivatives; inorganic materials such as alkali metal sulfides and alkali metal halides; or may include complexes of alkali metals and organic compounds.

[0125] Preferably, the cathode is a material with a small work function that facilitates electron injection into the functional layers. Specific examples of cathode materials include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; or multilayer materials such as LiF / Al, Liq / Al, LiO2 / Al, LiF / Ca, LiF / Al, and BaF2 / Ca.

[0126] The present invention also provides an application of the organic electroluminescent device as described above in optical fiber equipment, lighting equipment, electrophotographic photosensitive equipment, photoelectric converters, organic solar cells, switching element equipment, organic light-emitting field-effect transistors, image sensors or dye lasers.

[0127] The above technical solutions can be freely combined.

[0128] The beneficial effects of this invention are:

[0129] The present invention provides an organic electroluminescent compound having the structure shown in formula (1). Based on the structure of formula (1), further limiting the types of substituents can improve the structure of the compound and enhance its chemical stability, thereby making the carrier mobility of the organic electroluminescent compound more balanced. As a result, the organic electroluminescent device containing the organic electroluminescent compound has a lower driving voltage, higher luminous efficiency, and longer lifetime.

[0130] Furthermore, the present invention provides an organic electroluminescent compound having the structure shown in formula (2). Based on the triazine group, an α-naphthyl group and a β-naphthyl group are introduced, thereby better maintaining the molecular spatial structure (lower degree of distortion) and higher chemical stability (not easy to undergo electrochemical polymerization). At the same time, the α-naphthyl group and the β-naphthyl group are in different planes from the triazine group, and the molecular stacking and rigidity are appropriate, which can effectively improve the carrier transport rate and increase the film-forming properties of the compound. As a result, the organic electroluminescent device containing the organic electroluminescent compound has a lower driving voltage, higher luminous efficiency and longer lifetime. Attached Figure Description

[0131] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0132] Figure 1 This is a structural diagram of the organic electroluminescent device in the device embodiment of the present invention;

[0133] 1 – Substrate; 2 – Anode; 3 – Hole injection layer; 4 – Hole transport layer; 5 – Light emission layer; 6 – Electron transport layer; 7 – Electron injection layer; 8 – Cathode. Detailed Implementation

[0134] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0135] Those skilled in the art will recognize that the chemical reactions described herein can be suitably used to prepare many of the heterocyclic compounds of this application, and other methods for preparing the compounds of this application are considered to be within the scope of this application. For example, the synthesis of those non-illustrative compounds according to this application can be successfully accomplished by those skilled in the art through modification methods, such as appropriately protecting interfering groups, utilizing other known reagents besides those described herein, or making some conventional modifications to the reaction conditions. Compounds for which synthetic methods are not mentioned in this application are commercially available starting materials.

[0136] Synthesis of intermediate A1:

[0137]

[0138] Take a 100 mL three-necked round-bottom flask, add a stir bar and a reflux tube, and under nitrogen protection, add the following ingredients in sequence: SA1 (1.0 mmol), 1-naphthoboronic acid RA1 (1.1 mmol), Pd(dppf)Cl2 (0.03 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL). Heat to 90 °C and react for 5 h. After the reaction is complete, cool to room temperature, quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, remove the solvent using a rotary evaporator, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 1:50) to obtain intermediate A1-1 (yield 82%).

[0139] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate A1-1 (1 mmol), pinacol diboronate (1.2 mmol), Pd(dppf)Cl2 (0.03 mmol), potassium acetate (2.5 mmol), and 1,4-dioxane (10 mL) in sequence. Heat to 90 °C and react for 5 h. After the reaction is completed, cool to room temperature, quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, remove the solvent using a rotary evaporator, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 1:50) to obtain intermediate A1-2 (yield 78%).

[0140] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate A1-2 (1 mmol), EA1 (1.2 mmol), Pd(PPh3)2Cl2 (0.03 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL). Heat to 45 °C and react for 4 h. After the reaction is complete, cool to room temperature, filter, and wash the filter cake twice with deionized water. The crude product is then purified twice by recrystallization from ethyl acetate and tetrahydrofuran to obtain compound A1 (70% yield).

[0141] Intermediate A2 to intermediate An are synthesized using the same method as intermediate A1, the difference being the substitution of related raw materials. For details, please refer to Table 1 for the raw material table for the synthesis of intermediates A2 to An.

[0142] Table 1. Raw materials for the synthesis of intermediates A2 to An

[0143]

[0144] Synthesis of intermediate B1

[0145]

[0146] Take a 100 mL three-necked round-bottom flask, add a stir bar and a reflux tube, and under nitrogen protection, add the following ingredients in sequence: SB1 (1.0 mmol), phenylboronic acid RB1 (1.1 mmol), Pd(dppf)Cl2 (0.03 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL). Heat to 90 °C and react for 5 h. After the reaction is complete, cool to room temperature, quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, remove the solvent using a rotary evaporator, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 1:50) to obtain intermediate B1-1 (yield 85%).

[0147] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate B1-1 (1 mmol), pinacol diboronate (1.2 mmol), Pd(dppf)Cl2 (0.03 mmol), potassium acetate (2.5 mmol), and 1,4-dioxane (10 mL) in sequence. Heat to 90 °C and react for 5 h. After the reaction is completed, cool to room temperature, quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, remove the solvent using a rotary evaporator, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 1:50) to obtain intermediate B1 (yield 76%).

[0148] Intermediates B2 to Bn are synthesized using the same method as intermediate B1, with the difference being the substitution of relevant raw materials. For details, please refer to Table 2 for the raw material table for the synthesis of intermediates B2 to Bn.

[0149] Table 2. Raw material list for the synthesis of intermediates B2 to Bn

[0150]

[0151]

[0152]

[0153]

[0154]

[0155] Synthesis Example 1

[0156] This embodiment provides the synthesis of N-4, and its synthetic route is shown below:

[0157]

[0158] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate A1 (1 mmol), B1 (1.1 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL) in sequence. Heat to 90 °C and react for 5 h. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then purify the crude product twice by recrystallization from o-dichlorobenzene to obtain compound N-4 (yield 65%).

[0159] Elemental analysis: C 45 H 29 Theoretical N3 values: C, 88.35; H, 4.78; N, 6.87; Measured values: C, 88.33; H, 4.79; N, 6.88; HRMS(ESI) m / z [M+H] + Theoretical value: 611.75; Measured value: 612.73.

[0160] Synthesis Example 2

[0161] This embodiment provides the synthesis of N-20, and its synthetic route is shown below:

[0162]

[0163] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate A1 (1 mmol), B20 (1.1 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL) in sequence. Heat to 90 °C and react for 5 h. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then purify the crude product twice by recrystallization from o-dichlorobenzene to obtain compound N-20 (yield 63%).

[0164] Elemental analysis: C 49 H 31 N3. Theoretical values: C, 88.93; H, 4.72; N, 6.35; Measured values: C, 88.95; H, 4.71; N, 6.34; HRMS(ESI) m / z [M+H] + Theoretical value: 661.81; Measured value: 662.83.

[0165] Synthesis Example 3

[0166] This embodiment provides the synthesis of N-38, and its synthetic route is shown below:

[0167]

[0168] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate A1 (1 mmol), B38 (1.1 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL) in sequence. Heat to 90 °C and react for 5 h. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then purify the crude product twice by recrystallization from o-dichlorobenzene to obtain compound N-38 (yield 67%).

[0169] Elemental analysis: C 57 H 35 N3. Theoretical values: C, 89.85; H, 4.63; N, 5.52; Measured values: C, 89.87; H, 4.62; N, 5.51; HRMS(ESI) m / z [M+H] + Theoretical value: 761.93; Measured value: 762.91.

[0170] Synthesis Example 4

[0171] This embodiment provides the synthesis of N-47, and its synthetic route is shown below:

[0172]

[0173] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate A1 (1 mmol), B47 (1.1 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL) in sequence. Heat to 90 °C and react for 5 h. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then purify the crude product twice by recrystallization from o-dichlorobenzene to obtain compound N-47 (yield 68%).

[0174] Elemental analysis: C 51 H 31 N₃O. Theoretical values: C, 87.28; H, 4.45; N, 5.99; O, 2.28; Measured values: C, 87.25; H, 4.46; N, 6.02; HRMS(ESI) m / z [M+H] + Theoretical value: 701.83; Measured value: 702.85.

[0175] Synthesis Example 5

[0176] This embodiment provides the synthesis of N-73, and its synthetic route is shown below:

[0177]

[0178] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate A1 (1 mmol), B73 (1.1 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL) in sequence. Heat to 90 °C and react for 5 h. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then purify the crude product twice by recrystallization from o-dichlorobenzene to obtain compound N-73 (yield 72%).

[0179] Elemental analysis: C 53 H 33 N5. Theoretical values: C, 86.04; H, 4.50; N, 9.47; Measured values: C, 86.07; H, 4.48; N, 9.46; HRMS(ESI) m / z[M+H]+: Theoretical value: 739.88; Measured value: 740.85.

[0180] Synthesis Example 6

[0181] This embodiment provides the synthesis of N-82, and its synthetic route is shown below:

[0182]

[0183] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate A1 (1 mmol), B82 (1.1 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL) in sequence. Heat to 90 °C and react for 5 h. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then purify the crude product twice by recrystallization from o-dichlorobenzene to obtain compound N-82 (yield 64%).

[0184] Elemental analysis: C 51 H 33 N3. Theoretical values: C, 89.05; H, 4.84; N, 6.11; Measured values: C, 89.07; H, 4.83; N, 6.10; HRMS(ESI) m / z [M+H] + Theoretical value: 687.85; Measured value: 688.82.

[0185] Synthesis Example 7

[0186] This embodiment provides the synthesis of N-107, and its synthetic route is shown below:

[0187]

[0188] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate A1 (1 mmol), B107 (1.1 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL). Heat to 90 °C and react for 5 h. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then purify the crude product twice by recrystallization from o-dichlorobenzene to obtain compound N-107 (yield 67%).

[0189] Elemental analysis: C 57 H 35 N₃O. Theoretical values: C, 88.01; H, 4.54; N, 5.40; O, 2.06; Measured values: C, 88.04; H, 4.53; N, 5.38; HRMS(ESI) m / z [M+H] + Theoretical value: 777.93; Measured value: 778.92.

[0190] Synthesis Example 8

[0191] This embodiment provides the synthesis of N-119, and its synthetic route is shown below:

[0192]

[0193] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate A119 (1 mmol), B1 (1.1 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL). Heat to 90 °C and react for 5 h. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then purify the crude product twice by recrystallization from o-dichlorobenzene to obtain compound N-119 (yield 67%).

[0194] Elemental analysis: C 45 H 22 D7N3. Theoretical values: C, 87.35; H, 5.86; N, 6.79; Measured values: C, 87.35; H, 5.86; N, 6.79; HRMS(ESI) m / z [M+H] + Theoretical value: 618.79; Measured value: 619.77.

[0195] Synthesis Example 9

[0196] This embodiment provides the synthesis of N-120, and its synthetic route is shown below:

[0197]

[0198] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate A120 (1 mmol), B20 (1.1 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL). Heat to 90 °C and react for 5 h. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then purify the crude product twice by recrystallization from o-dichlorobenzene to obtain compound N-120 (yield 69%).

[0199] Elemental analysis: C 45 H 23 D6N3. Theoretical values: C, 87.49; H, 5.71; N, 6.80; Measured values: C, 87.47; H, 5.72; N, 6.81; HRMS(ESI) m / z [M+H] + Theoretical value: 617.78; Measured value: 618.76.

[0200] Synthesis Example 10

[0201] This embodiment provides the synthesis of N-121, and its synthetic route is shown below:

[0202]

[0203] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate A1 (1 mmol), B121 (1.1 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL). Heat to 90 °C and react for 5 h. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then purify the crude product twice by recrystallization from o-dichlorobenzene to obtain compound N-121 (yield 61%).

[0204] Elemental analysis: C 45 H 24 D5N3. Theoretical values: C, 87.63; H, 5.56; N, 6.81; Measured values: C, 87.65; H, 5.55; N, 6.80; HRMS(ESI) m / z [M+H] + Theoretical value: 616.78; Measured value: 617.75.

[0205] Synthesis Example 11

[0206] This embodiment provides the synthesis of N-163, and its synthetic route is shown below:

[0207]

[0208] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate A1 (1 mmol), B163 (1.1 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL). Heat to 90 °C and react for 5 h. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then purify the crude product twice by recrystallization from o-dichlorobenzene to obtain compound N-163 (yield 63%).

[0209] Elemental analysis: C 55 H 33 N₃O. Theoretical values: C, 87.86; H, 4.42; N, 5.59; O, 2.13; Measured values: C, 87.83; H, 4.43; N, 5.61; HRMS(ESI) m / z [M+H] + Theoretical value: 751.89; Measured value: 752.87.

[0210] Synthesis Example 12

[0211] This embodiment provides the synthesis of N-28, and its synthetic route is shown below:

[0212]

[0213] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate A1 (1 mmol), B28 (1.1 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL) in sequence. Heat to 90 °C and react for 5 h. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then purify the crude product twice by recrystallization from o-dichlorobenzene to obtain compound N-28 (yield 64%).

[0214] Elemental analysis: C 53 H 33 N3. Theoretical values: C, 89.42; H, 4.67; N, 5.90; Measured values: C, 89.44; H, 4.68; N, 5.87; HRMS(ESI) m / z [M+H] + Theoretical value: 711.27; Measured value: 712.24.

[0215] Synthesis Example 13

[0216] This embodiment provides the synthesis of N-31, and its synthetic route is shown below:

[0217]

[0218] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate A1 (1 mmol), B31 (1.1 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL) in sequence. Heat to 90 °C and react for 5 h. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then purify the crude product twice by recrystallization from o-dichlorobenzene to obtain compound N-31 (yield 62%).

[0219] Elemental analysis: C 53 H 33 N3. Theoretical values: C, 89.42; H, 4.67; N, 5.90; Measured values: C, 89.43; H, 4.68; N, 5.88; HRMS(ESI) m / z [M+H] + Theoretical value: 711.27; Measured value: 712.31.

[0220] Synthesis Example 14

[0221] This embodiment provides the synthesis of N-33, and its synthetic route is shown below:

[0222]

[0223] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate A1 (1 mmol), B33 (1.1 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL) in sequence. Heat to 90 °C and react for 5 h. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then purify the crude product twice by recrystallization from o-dichlorobenzene to obtain compound N-33 (yield 60%).

[0224] Elemental analysis: C 53 H 33 N3. Theoretical values: C, 89.42; H, 4.67; N, 5.90; Measured values: C, 89.44; H, 4.66; N, 5.89; HRMS(ESI) m / z [M+H] + Theoretical value: 711.27; Measured value: 712.25.

[0225] Synthesis Example 15

[0226] This embodiment provides the synthesis of N-37, and its synthetic route is shown below:

[0227]

[0228] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate A1 (1 mmol), B37 (1.1 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL). Heat to 90 °C and react for 5 h. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then purify the crude product twice by recrystallization from o-dichlorobenzene to obtain compound N-37 (yield 61%).

[0229] Elemental analysis: C 57 H 35 N3. Theoretical values: C, 89.85; H, 4.63; N, 5.52; Measured values: C, 89.86; H, 4.64; N, 5.50; HRMS(ESI) m / z [M+H] + Theoretical value: 761.28; Measured value: 762.14.

[0230] Synthesis Example 16

[0231] This embodiment provides the synthesis of N-54, and its synthetic route is shown below:

[0232]

[0233] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate A1 (1 mmol), B54 (1.1 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL) in sequence. Heat to 90 °C and react for 5 h. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then purify the crude product twice by recrystallization from o-dichlorobenzene to obtain compound N-54 (yield 63%).

[0234] Elemental analysis: C 51 H 31 N3S. Theoretical values: C, 85.33; H, 4.35; N, 5.85; S, 4.47; Measured values: C, 85.34; H, 4.36; N, 5.84; S, 4.46; HRMS(ESI) m / z [M+H] + Theoretical value: 717.22; Measured value: 718.34.

[0235] Synthesis Example 17

[0236] This embodiment provides the synthesis of N-61, and its synthetic route is shown below:

[0237]

[0238] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate A1 (1 mmol), B61 (1.1 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL) in sequence. Heat to 90 °C and react for 5 h. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then purify the crude product twice by recrystallization from o-dichlorobenzene to obtain compound N-61 (yield 59%).

[0239] Elemental analysis: C 55 H 33 N₃O. Theoretical values: C, 87.86; H, 4.42; N, 5.59; O, 2.13; Measured values: C, 87.87; H, 4.43; N, 5.57; HRMS(ESI) m / z [M+H] + Theoretical value: 751.26; Measured value: 752.24.

[0240] Synthesis Example 18

[0241] This embodiment provides the synthesis of N-75, and its synthetic route is shown below:

[0242]

[0243] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate A1 (1 mmol), B75 (1.1 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL) in sequence. Heat to 90 °C and react for 5 h. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then purify the crude product twice by recrystallization from o-dichlorobenzene to obtain compound N-75 (yield 62%).

[0244] Elemental analysis: C 48 H 30 N4. Theoretical values: C, 86.98; H, 4.56; N, 8.45; Measured values: C, 86.99; H, 4.57; N, 8.43; HRMS(ESI) m / z [M+H] + Theoretical value: 662.25; Measured value: 663.21.

[0245] Synthesis Example 19

[0246] This embodiment provides the synthesis of N-96, and its synthetic route is shown below:

[0247]

[0248] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate A1 (1 mmol), B96 (1.1 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL) in sequence. Heat to 90 °C and react for 5 h. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then purify the crude product twice by recrystallization from o-dichlorobenzene to obtain compound N-96 (yield 66%).

[0249] Elemental analysis: C 55 H 35 N3. Theoretical values: C, 89.52; H, 4.78; N, 5.69; Measured values: C, 89.54; H, 4.79; N, 5.66; HRMS(ESI) m / z [M+H] + Theoretical value: 737.28; Measured value: 738.21.

[0250] Synthesis Example 20

[0251] This embodiment provides the synthesis of N-112, and its synthetic route is shown below:

[0252]

[0253] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate A1 (1 mmol), B112 (1.1 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL). Heat to 90 °C and react for 5 h. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then purify the crude product twice by recrystallization from o-dichlorobenzene to obtain compound N-112 (yield 67%).

[0254] Elemental analysis: C 57 H 35 N₃O. Theoretical values: C, 88.01; H, 4.54; N, 5.40; O, 2.06; Measured values: C, 88.00; H, 4.53; N, 5.38; HRMS(ESI) m / z [M+H] + Theoretical value: 777.28; Measured value: 778.14.

[0255] Synthesis Example 21

[0256] This embodiment provides the synthesis of N-160, and its synthetic route is shown below:

[0257]

[0258] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate A1 (1 mmol), B160 (1.1 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL). Heat to 90 °C and react for 5 h. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then purify the crude product twice by recrystallization from o-dichlorobenzene to obtain compound N-160 (yield 60%).

[0259] Elemental analysis: C 55 H 27 D6N3O. Theoretical values: C, 87.16; H, 5.19; N, 5.54; O, 2.11; Measured values: C, 87.18; H, 5.18; N, 5.53; HRMS(ESI) m / z [M+H] + Theoretical value: 757.30; Measured value: 758.32.

[0260] Synthesis Example 22

[0261] This embodiment provides the synthesis of N-167, and its synthetic route is shown below:

[0262]

[0263] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate A119 (1 mmol), B167 (1.1 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL). Heat to 90 °C and react for 5 h. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then purify the crude product twice by recrystallization from o-dichlorobenzene to obtain compound N-167 (yield 66%).

[0264] Elemental analysis: C 44 H 21 D7N4. Theoretical values: C, 85.27; H, 5.69; N, 9.04; Measured values: C, 85.28; H, 5.70; N, 9.02; HRMS(ESI) m / z [M+H] + Theoretical value: 619.28; Measured value: 620.13.

[0265] Synthesis Example 23

[0266] This embodiment provides the synthesis of N-183, and its synthetic route is shown below:

[0267]

[0268] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate A1 (1 mmol), B183 (1.1 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL). Heat to 90 °C and react for 5 h. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then purify the crude product twice by recrystallization from o-dichlorobenzene to obtain compound N-183 (yield 68%).

[0269] Elemental analysis: C 51 H 24 D9N3. Theoretical values: C, 87.90; H, 6.07; N, 6.03; Measured values: C, 87.91; H, 6.08; N, 6.01; HRMS(ESI) m / z [M+H] + Theoretical value: 696.32; Measured value: 697.33.

[0270] Synthesis Example 24

[0271] This embodiment provides the synthesis of N-205, and its synthetic route is shown below:

[0272]

[0273] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate A119 (1 mmol), B205 (1.1 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL). Heat to 90 °C and react for 5 h. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then purify the crude product twice by recrystallization from o-dichlorobenzene to obtain compound N-205 (yield 67%).

[0274] Elemental analysis: C 55 H 28 D7N3. Theoretical values: C, 88.68; H, 5.68; N, 5.64; Measured values: C, 88.69; H, 5.69; N, 5.62; HRMS(ESI) m / z [M+H] + Theoretical value: 744.33; Measured value: 745.15.

[0275] Device Examples

[0276] The materials used to prepare the following device embodiments or device comparative examples are shown in Table 3 below.

[0277] Table 3. Some compounds used in device examples or device comparison examples.

[0278]

[0279] Device Example 1

[0280] This embodiment provides an organic electroluminescent device, such as... Figure 1 As shown, the device includes an anode 2, a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, an electron injection layer 7, and a cathode 8, which are sequentially stacked on a substrate 1. The device structure is: anode (indium tin oxide (ITO) coated glass substrate) / hole injection layer (HIL) / hole transport layer (HTL) / light-emitting layer (EML) / electron transport layer (ETL) / electron injection layer (EIL) / cathode (Al).

[0281] The specific preparation process is as follows:

[0282] 1) Substrate cleaning:

[0283] The glass substrate coated with transparent ITO was ultrasonically treated in an aqueous cleaning agent (the composition and concentration of the aqueous cleaning agent: ethylene glycol solvent ≤10wt%, triethanolamine ≤1wt%), then rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol (volume ratio of acetone and ethanol 1:1), baked in a clean environment until all moisture was removed, and then cleaned with ultraviolet light and ozone.

[0284] 2) Preparation of organic layer:

[0285] The ITO transparent substrate was transferred to an evaporation equipment and vacuumed to 1×10⁻⁶. -6 Up to 2×10 -4 Pa, hole injection layer (HIL) / hole transport layer (HTL) / light emission layer (EML) / electron transport layer (ETL) / electron injection layer (EIL) / thick cathode (Al) are sequentially deposited on the anode film.

[0286] in:

[0287] The hole injection layer (HIL) is a mixture of HAT-CN and HT-1, with a mass ratio of HAT-CN to HT-1 of 3:97, a thickness of 10 nm, and a total evaporation rate of 0.1 nm / s.

[0288] The hole transport layer (HTL) is made of HT-1 material, has a thickness of 80 nm, and a total evaporation rate of 0.1 nm / s.

[0289] The light-emitting layer (EML) is vacuum-deposited by co-evaporation. The material of the light-emitting layer includes a host material and a guest material, wherein the guest material is RD and the host material is composed of N-4 and R-1 compounds in synthesis example 1. The specific ratio of the host material and the guest material is shown in Table 4 below. The thickness is 35 nm and the total evaporation rate is 0.1 nm / s.

[0290] The electron transport layer (ETL) is a binary mixture of ET and LiQ in a mass ratio of 1:1, with a thickness of 30 nm and a total evaporation rate of 0.1 nm / s.

[0291] The electron injection layer (EIL) is made of LiQ with a thickness of 1 nm and a total evaporation rate of 0.1 nm / s.

[0292] The cathode is made of aluminum with a thickness of 90 nm and a deposition rate of 1 nm / s.

[0293] Device Examples 2 to 24

[0294] Compared with Device Example 1, the difference is that compound N-4 in the light-emitting layer is replaced with the compounds obtained in Synthesis Examples 2 to 24. The specific materials of the light-emitting layer are shown in Table 4.

[0295] Device Comparison Example 1

[0296] Similar to Device Example 1, the difference is that material N-4 in Device Example 1 is replaced with the following structure REF-1, and the specific ratio of the host material and the guest material is shown in Table 4 below.

[0297]

[0298] Device Comparison Example 2

[0299]

[0300] Table 4

[0301]

[0302]

[0303] Device Test Examples

[0304] The organic electroluminescent devices obtained in Device Examples 1-24 and Device Comparative Examples 1 and 2 in the device examples were tested.

[0305] Instruments: The current, voltage, brightness, emission spectrum and other characteristics of the device were tested simultaneously using a PR 650 spectral scanning luminance meter and a Keithley K 2400 digital source meter system;

[0306] Test conditions: Photoelectric property test conditions: current density 10 mA / cm² 2 .

[0307] Lifetime test: Current density 50mA / cm 2 The recording time (in hours) when the device brightness drops to 95% of its original brightness.

[0308] The lifetime T95 of Comparative Example 1 is set to 100. The test results of lifetime T95 of Examples 1-24 relative to Comparative Example 1 are shown in Table 5. The driving voltage and current efficiency of Examples 1-24, Comparative Examples 1 and 2 are shown in Table 5.

[0309] Table 5

[0310]

[0311]

[0312] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. An organic electroluminescent compound, characterized in that, The organic electroluminescent compound has the structure shown in formula (1): Compounds having the following formula (1): In equation (1), X 1 X 2 X 3 Each independently selected from CR 1 CR 2 or CR 3 R 1 Selected from equation (1-1), R 2 Selected from equation (1-2), R 3 Selected from substituted or unsubstituted C6-C60 aryl groups; X 4 X 5 X 6 Selected from N; In equation (1-1), Ar 1 Selected from substituted or unsubstituted C6-C60 aryl groups; n1 is an integer selected from 0 to 6; Ar 2 Selected from substituted or unsubstituted C6-C60 aryl groups or substituted or unsubstituted C1-C60 heteroaryl groups; n2 is an integer selected from 0 to 6; The substituents in the substituted C6-C60 aryl and substituted C1-C60 heteroaryl are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C60 alkyl, C6-C60 aryl, and C1-C60 heteroaryl.

2. The organic electroluminescent compound according to claim 1, characterized in that, The organic electroluminescent compound has the structure shown in formula (2): In equation (2), R 3 Ar 1 Ar 2 The definitions of n1 and n2 are the same as those defined in claim 1.

3. The organic electroluminescent compound according to claim 1 or 2, characterized in that, Ar 1 Selected from substituted or unsubstituted C6-C50 aryl groups; The substituents in the substituted C6-C50 aryl groups are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C50 alkyl, C6-C50 aryl, and C1-C50 heteroaryl. Preferred, Ar 1 Selected from substituted or unsubstituted C6-C25 aryl groups; The substituents in the substituted C6-C25 aryl group are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C25 alkyl, C6-C25 aryl, and C1-C25 heteroaryl. Preferred, Ar 1 Selected from substituted or unsubstituted C6-C12 aryl groups; The substituents in the substituted C6-C12 aryl group are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C12 alkyl, C6-C12 aryl, and C1-C12 heteroaryl. Preferred, Ar 1 Selected from substituted or unsubstituted naphthyl groups; The substituents in the substituted naphthyl group are selected from deuterium.

4. The organic electroluminescent compound according to any one of claims 1-3, characterized in that, The organic electroluminescent compound has the following structure: In equations (3) to (4), n3, n4, n5, and n6 may be the same or different, and each is an integer independently selected from 0 to 7; R 3 Ar 2 The definitions of n1 and n2 are the same as those defined in claim 1.

5. The organic electroluminescent compound according to any one of claims 1-4, characterized in that, R 3 Selected from substituted or unsubstituted C6-C50 aryl groups; The substituents in the substituted C6-C50 aryl groups are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C50 alkyl, C6-C50 aryl, and C1-C50 heteroaryl. Preferred, R 3 Selected from substituted or unsubstituted C6-C25 aryl groups; The substituents in the substituted C6-C25 aryl group are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C25 alkyl, C6-C25 aryl, and C1-C25 heteroaryl. Preferred, R 3 Selected from substituted or unsubstituted C6-C12 aryl groups; The substituents in the substituted C6-C12 aryl group are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C12 alkyl, C6-C12 aryl, and C1-C12 heteroaryl. Preferred, R 3 Selected from the group consisting of the following groups:

6. The organic electroluminescent compound according to any one of claims 1-5, characterized in that, Ar 2 Selected from substituted or unsubstituted C6-C50 aryl groups or substituted or unsubstituted C1-C50 heteroaryl groups; The substituents in the substituted C6-C50 aryl and substituted C6-C50 heteroaryl are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C50 alkyl, C6-C50 aryl, and C1-C50 heteroaryl. Preferred, Ar 2 Selected from substituted or unsubstituted C6-C25 aryl or substituted or unsubstituted C6-C25 heteroaryl; The substituents in the substituted C6-C25 aryl and substituted C6-C25 heteroaryl are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C25 alkyl, C6-C25 aryl, and C1-C25 heteroaryl. Preferred, Ar 2 Selected from the group consisting of the following groups:

7. The organic electroluminescent compound according to any one of claims 1-6, characterized in that, n1 and n2 are each independent integers selected from 0 to 5; Preferably, n1 and n2 are each independently selected from integers from 0 to 4; Preferably, n1 and n2 are each independently selected from integers from 0 to 3; Preferably, n1 and n2 are each independently selected from integers from 0 to 2; Preferably, n3, n4, n5, and n6 are each independently selected from integers from 0 to 6; Preferably, n3, n4, n5, and n6 are each independently selected from integers from 0 to 5; Preferably, n3, n4, n5, and n6 are each independently selected from integers from 0 to 4; Preferably, n3, n4, n5, and n6 are each independently selected from integers from 0 to 3; Preferably, n3, n4, n5 and n6 are each independently selected from integers from 0 to 2.

8. The organic electroluminescent compound according to any one of claims 1-7, characterized in that, The organic electroluminescent compound is selected from one of the following structures:

9. An organic electroluminescent material, characterized in that, The organic luminescent material comprises the organic electroluminescent compound as described in any one of claims 1-8.

10. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes a first electrode, a second electrode disposed opposite to the first electrode, and at least one organic layer between the first electrode and the second electrode, wherein the organic layer comprises an organic electroluminescent compound as described in any one of claims 1-8 or an organic electroluminescent material as described in claim 9.

11. An organic electroluminescent device according to claim 10, characterized in that, The organic layer includes a light-emitting layer, which comprises an organic electroluminescent compound as described in any one of claims 1-8 or an organic electroluminescent material as described in claim 9.

12. The application of an organic electroluminescent compound as described in any one of claims 1-8, an organic electroluminescent material as described in claim 9, or an organic electroluminescent device as described in claim 10 in fiber optic devices, lighting devices, electrophotographic photosensitive devices, photoelectric converters, organic solar cells, switching element devices, organic light-emitting field-effect transistors, image sensors, or dye lasers.

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