Organic electroluminescent composition and use thereof

Abstract

The present application relates to the technical field of display, in particular to an organic electroluminescent composition and application thereof. The organic electroluminescent composition provided by the present application comprises a first compound and a second compound, wherein the first compound comprises a compound represented by formula (I): and the second compound is a compound represented by formula (2): the organic electroluminescent device comprising the material has more excellent service life, and simultaneously has lower driving voltage and higher efficiency.

Description

Technical Field

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

[0002] Organic light-emitting diodes (OLEDs) convert electrical energy into light by applying electricity to organic light-emitting materials, and typically consist of an anode, a cathode, and an organic layer formed between these two electrodes. The organic layer of an organic EL device can include hole injection layers, hole transport layers, hole auxiliary layers, light-emitting auxiliary layers, electron blocking layers, light-emitting layers (containing host materials and dopant materials), electron buffer layers, hole blocking layers, electron transport layers, and electron injection layers, etc. The materials used in the organic layer can be categorized according to their functions, such as hole injection materials, hole transport materials, hole auxiliary materials, light-emitting auxiliary materials, electron blocking materials, light-emitting materials, electron buffer materials, hole blocking materials, electron transport materials, and electron injection materials. In an organic EL device, holes from the anode and electrons from the cathode are injected into the light-emitting layer by applying a voltage, and high-energy excitons are generated through the recombination of holes and electrons. The organic light-emitting compound moves to an excited state by energy and emits light by the energy when the organic light-emitting compound returns from the excited state to the ground state.

[0003] Currently, the high driving voltage and short lifespan of organic light-emitting diodes (OLEDs) are caused by the low stability of organic functional materials and the imbalance of carrier mobility, which seriously limits the application of OLEDs. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of existing organic electroluminescent materials, such as low stability and unbalanced carrier mobility, which result in high driving voltage and short lifespan of organic electroluminescent diodes, and to provide an organic electroluminescent material and its application.

[0005] In this invention, -* represents a connection key.

[0006] The solution adopted in this invention is as follows:

[0007] A composition for use in organic optoelectronic devices, comprising a first compound and a second compound;

[0008] The first compound has the structure shown in formula (1):

[0009]

[0010] In equation (1),

[0011] X 1 X 2 X3 Each independently selected from CR 1 CR 2 or CR 3 R 1 Selected from equation (1-1) or equation (1-2), R 2 Selected from equation (1-3) or equation (1-4), R 3 Selected from substituted or unsubstituted C6-C60 aryl groups;

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

[0013]

[0014]

[0015] Where R 1 When R is selected from equation (1-1), 2 Not for equation (1-4), when R 1 When R is selected from equation (1-2), 2 Not for equation (1-3);

[0016] Ar 1 Selected from substituted or unsubstituted C6-C60 aryl groups; n1 is selected from integers from 0 to 6;

[0017] Ar 2 Selected from substituted or unsubstituted C6-C60 aryl groups; n2 is selected from integers from 0 to 6;

[0018] Ar 3 Selected from substituted or unsubstituted C6-C60 aryl groups or substituted or unsubstituted C1-C60 heteroaryl groups; n3 is selected from integers from 0 to 6;

[0019] Ar 4 Selected from substituted or unsubstituted C6-C60 aryl groups or substituted or unsubstituted C1-C60 heteroaryl groups; n4 is selected from integers from 0 to 6;

[0020] The second compound has the structure shown in formula (2):

[0021]

[0022] in,

[0023] Ring A is a benzene ring;

[0024] Ar is selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C6-C60 aromatic amino, substituted or unsubstituted C3-C60 heteroaryl, and substituted or unsubstituted C3-C30 heteroaryl.

[0025] L is selected from substituted or unsubstituted C6-C30 arylene or substituted or unsubstituted C3-C30 heteroarylene;

[0026] The substituents in the substituted C6-C60 aryl, substituted C6-C60 aromatic amino, substituted C3-C60 heteroaryl, substituted C3-C30 heteroaryl, and substituted C1-C60 heteroaryl are selected from one or a combination of at least two of the following: deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C60 aromatic amino, and C3-C60 heteroaryl.

[0027] Understandable. In equation (1), ring A can be fused with ring C through points 1, 2; 2, 3; 3, 4; N can be directly connected to any substituted point in ring A, ring C, or ring D; and L can be connected to any substituted point in ring B.

[0028] Substituents

[0029] 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.

[0030] Replaced or not replaced

[0031] 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.

[0032] 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.

[0033] C1-C60, C3-C60, C6-C60

[0034] 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.

[0035] alkyl

[0036] 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.

[0037] Aryl, aryl

[0038] 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.

[0039] heteroaryl, hypoaryl

[0040] 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.

[0041] halogen

[0042] In this application, the term "halogen" refers to an atom selected from fluorine, chlorine, bromine, and iodine.

[0043] Organic electroluminescent composition

[0044] In this application, "organic electroluminescent composition" ”This refers to two or more materials that exist together or are prepared to exist together and can be used in an organic electroluminescent device. In this document, "existing together" means not only that the two or more materials are mixed, but also that the materials are separate. Furthermore, the compositional materials for an organic electroluminescent device are a concept that includes not only materials contained in the organic electroluminescent device before (e.g., before evaporation), but also materials contained in the organic electroluminescent device after (e.g., after evaporation). For example, the compositional material for an organic electroluminescent device may comprise two or more of the following: hole injection material, hole transport material, hole assist material, luminescence assist material, electron blocking material, luminescent material (both host material and dopant material); electron buffer material, hole blocking material, electron transport material, and electron injection material; or it may comprise two or more of the following: hole injection material, two or more of the following: hole transport material, two or more of the following: hole assist material, two or more of the following: luminescence assist material, two or more of the following: electron blocking material, two or more of the following: luminescent material (both host material and dopant material); two or more of the following: electron buffer material, two or more of the following: hole blocking material, two or more of the following: electron transport material, and two or more of the following: electron injection material. The compositional material for an organic electroluminescent device may be contained in any layer constituting the organic electroluminescent device. Two or more materials contained in the compositional material may be contained together in one layer, or they may each be contained in a separate layer. When two or more materials are contained in one layer, the layer may be formed by a co-evaporation method in which the materials are mixed, or by a co-evaporation method in which the materials are evaporated separately and simultaneously.

[0045] hydrogen

[0046] In this application, unless otherwise stated, hydrogen atoms include protium, deuterium, and tritium.

[0047] Preferably, the first compound has the structures shown in formulas (1-5) and (1-6):

[0048]

[0049] In the formula, R 3 Ar 1 Ar 2 Ar3, Ar 4 The definitions of n1 and n2 are the same as those defined above.

[0050] In this application, equation (1-3) is used as an example for D. n1 This indicates that there are n1 D (deuterium) substitutions on the naphthyl group.

[0051] Preferred, Ar 1 and Ar2 They may be the same or different, and each is independently selected from substituted or unsubstituted C6-C50 aryl groups.

[0052] The substituents in the substituted C6-C50 aryl groups are selected from one or a combination of at least two of the following: deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C50 aromatic amino, and C3-C50 heteroaryl.

[0053] Preferred, Ar 1 and Ar 2 They may be the same or different, and each is independently selected from substituted or unsubstituted C6-C25 aryl groups.

[0054] The substituents in the substituted C6-C25 aryl groups are selected from one or a combination of at least two of the following: deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C25 aryl, C3-C25 heteroaryl, C6-C25 aromatic amino, and C3-C25 heteroaromatic amino.

[0055] Preferred, Ar 1 and Ar 2 They may be the same or different, and each is independently selected from substituted or unsubstituted C6-C12 aryl groups.

[0056] 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.

[0057] Preferred, Ar 1 and Ar 2 They may be the same or different, and each is independently selected from substituted or unsubstituted naphthyl groups.

[0058] The substituents in the substituted naphthyl group are selected from deuterium.

[0059] Preferably, the first compound has the following structure:

[0060]

[0061] In equations (1-7) to (1-10), R 3 Ar 3 Ar 4 The definitions of n1, n2, n3, n4, n5, n6, n7, and n8 are the same as those above.

[0062] n5 to n8 are integers selected from 0 to 7.

[0063] Preferably, n5 to n8 are each independently selected from integers from 0 to 6.

[0064] Preferably, n5 to n8 are each independently selected from integers from 0 to 5.

[0065] Preferably, n5 to n8 are each independently selected from integers from 0 to 4.

[0066] Preferably, n5 to n8 are each independently selected from integers from 0 to 3.

[0067] Preferably, n5 to n8 are each independently selected from integers from 0 to 2.

[0068] Preferred, R 3 Selected from substituted or unsubstituted C6-C50 aryl groups.

[0069] The substituents in the substituted C6-C50 aryl groups are selected from one or a combination of at least two of the following: deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C50 aromatic amino, and C3-C50 heteroaryl.

[0070] Preferred, R 3 Selected from substituted or unsubstituted C6-C25 aryl groups.

[0071] The substituents in the substituted C6-C25 aryl groups are selected from one or a combination of at least two of the following: deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C25 aryl, C3-C25 heteroaryl, C6-C25 aromatic amino, and C3-C25 heteroaromatic amino.

[0072] Preferred, R 3 Selected from the group consisting of the following groups:

[0073]

[0074]

[0075]

[0076] Preferred, Ar 3 and Ar 4 They may be the same or different, and each is independently selected from substituted or unsubstituted C6-C50 aryl or substituted or unsubstituted C1-C50 heteroaryl;

[0077] The substituents in the substituted C6-C50 aryl and substituted C6-C50 heteroaryl are selected from one or a combination of at least two of the following: deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C60 aromatic amino, and C3-C50 heteroaromatic amino.

[0078] Preferred, Ar 3 and Ar 4 They may be the same or different, and each is independently selected from substituted or unsubstituted C6-C25 aryl or substituted or unsubstituted C6-C25 heteroaryl;

[0079] The substituents in the substituted C6-C25 aryl and substituted C6-C25 heteroaryl are selected from one or a combination of at least two of the following: deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C25 aryl, C3-C25 heteroaryl, C6-C25 aromatic amino, and C3-C25 heteroaromatic amino.

[0080] Preferred, Ar 3 and Ar 4 They are either the same or different, and each is independently selected from the group consisting of the following groups:

[0081]

[0082]

[0083]

[0084]

[0085]

[0086] In this application, For example, D1-D5 represent 1, 2, 3, 4, or 5 deuterium substitutions on the benzene ring. Preferably, n1 to n4 are each independently selected from integers from 0 to 5. Preferably, n1 to n4 are each independently selected from integers from 0 to 4. Preferably, n1 to n4 are each independently selected from integers from 0 to 3. Preferably, n1 to n4 are each independently selected from integers from 0 to 2. Preferably, the first compound is selected from one of the following structures:

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112] This invention also provides a method for synthesizing the first compound described above, the synthetic route of which is shown below: General formula for intermediate A synthesis:

[0113]

[0114] General formula for the synthesis of intermediate B:

[0115]

[0116] General formula for the synthesis of compound N:

[0117]

[0118]

[0119] In the formula, X and Y are halogens; R 3 Ar 1 Ar 2 Ar 3 Ar 4 The definitions of n1, n2, n3, and n4 are the same as those above.

[0120] Preferably, in the second compound, Ar is selected from substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C6-C25 aromatic amino, substituted or unsubstituted C3-C25 heteroaryl, and substituted or unsubstituted C3-C20 heteroaryl.

[0121] The substituents in the substituted C6-C25 aryl, substituted C6-C25 aromatic amino, substituted C3-C25 heteroaryl, and substituted C3-C20 heteroaryl are each independently selected from one or a combination of at least two of the following: deuterium, halogen, cyano, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C60 aromatic amino, and C3-C60 heteroaryl.

[0122] Preferably, Ar is selected from substituted or unsubstituted B groups, and the B group is selected from the following groups: phenyl, naphthyl, biphenyl, phenanthryl, fluoranthyl, ... , terphenyl, triphenylene, finadeninyl, phenylnaphthyl, naphthylphenyl, dimethylfluorenyl, phenylmethylfluorenyl, diphenylfluorenyl, pyridyl, pyridylphenyl, phenylpyridyl, spirodifluorenyl, benzodimethylfluorenyl, benzodiphenylfluorenyl, benzospirodifluorenyl, dibenzofuranyl, benzonaphthiofuranyl, benzonaphthiopheneyl, spiro[fluoren-9,9'-oxazanthyl]yl, phenylmethylfluorenyl, dinaphthiofuranyl, dinaphthiopheneyl, dibenzothiopheneyl, N,N-diphenylaniline;

[0123] Wherein, the substituent of the substituted B group is selected from one or a combination of at least two of the following: deuterium, halogen, cyano, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C60 aromatic amino, and C3-C60 heteroaryl.

[0124] Preferably, Ar is selected from phenyl, naphthyl, biphenyl, yl, phenanthrene, terphenyl, phenylnaphthyl, naphthylphenyl, dimethylfluorenyl, diphenylfluorenyl, spirodifluorenyl, finadenoyl, dibenzofuranyl, benzonaphthylfuranyl, N,N-diphenylaniline.

[0125] Preferably, in the second compound, L is selected from substituted or unsubstituted C6-C15 arylene groups; wherein each substituent in the substituted C6-C15 arylene group is independently selected from one or a combination of at least two of deuterium, halogen, and C1-C62 alkyl groups.

[0126] Preferably, L is selected from phenylene, biphenylene, and naphthylene;

[0127] Preferably, L is selected from phenylene or naphthylene.

[0128] Equation (2) is selected from one of the structures shown in Equations (2-1) to (2-6):

[0129]

[0130] Ar is defined as described above.

[0131] Preferably, the second compound is selected from any one of S-1 to S-208:

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140] Preferably, in the composition, the mass ratio of the first compound to the second compound is 1:9 to 9:1.

[0141] Preferably, in the composition, the mass ratio of the first compound to the second compound is 2:8 to 8:2.

[0142] Preferably, in the composition, the mass ratio of the first compound to the second compound is 3:7 to 7:3.

[0143] Preferably, in the composition, the mass ratio of the first compound to the second compound is 4:6 to 6:4.

[0144] The present invention also provides a light-emitting host material composition for an organic optoelectronic device, the light-emitting host material composition comprising the organic electroluminescent composition as described above.

[0145] The present invention also provides an organic electroluminescent device, wherein the organic electroluminescent device comprises the above-described organic electroluminescent composition or the above-described organic electroluminescent host material composition.

[0146] Preferably, the organic electroluminescent device includes a first electrode, a second electrode disposed opposite to the first electrode, and an organic layer between the first electrode and the second electrode, wherein the organic layer comprises the above-described organic electroluminescent composition or the above-described organic electroluminescent host material composition.

[0147] Preferably, the first electrode is the anode and the second electrode is the cathode.

[0148] 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.

[0149] Preferably, the light-emitting layer comprises the above-described organic electroluminescent composition or the above-described organic electroluminescent host material composition.

[0150] 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.

[0151] 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.

[0152] 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:

[0153]

[0154]

[0155] 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:

[0156]

[0157]

[0158] 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.

[0159] 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.

[0160] 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 light-emitting host material composition for organic optoelectronic devices or the above-mentioned composition for organic optoelectronic devices.

[0161] 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.

[0162] 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.

[0163] Preferably, the electron transport layer includes, but is not limited to, the following structures:

[0164]

[0165]

[0166] 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.

[0167] 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.

[0168] The present invention also provides an organic electroluminescent device, which includes an organic electroluminescent device as described above, an organic electroluminescent composition as described above, or an organic electroluminescent host material composition as described above.

[0169] Optionally, the organic electroluminescent device includes at least one of an optical fiber device, an illumination device, an electrophotographic photosensitive device, a photoelectric converter, an organic solar cell, a switching element device, an organic light-emitting field-effect transistor, an image sensor, or a dye laser.

[0170] The beneficial effects of this invention are:

[0171] In the organic electroluminescent composition provided by the present invention, the first compound comprises the compound represented by formula (1), and the second compound comprises the compound represented by formula (2). The interaction between the compound represented by formula (1) and the compound represented by formula (2) facilitates the matching of HOMO and LUMO energy levels with adjacent energy levels, thereby enabling the organic electroluminescent composition to obtain higher stability and more balanced carrier mobility. Consequently, the organic electroluminescent device containing this composition has a better lifetime, as well as a lower driving voltage and higher efficiency. Attached Figure Description

[0172] 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.

[0173] Figure 1 This is a structural diagram of the organic electroluminescent device in the device embodiment of the present invention;

[0174] 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

[0175] 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.

[0176] 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.

[0177] Synthesis of intermediate A1:

[0178]

[0179] 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%).

[0180] 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%).

[0181] 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).

[0182] 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.

[0183] Table 1. Raw materials for the synthesis of intermediates A2 to An

[0184]

[0185]

[0186]

[0187] Synthesis of intermediate B1

[0188]

[0189] 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%).

[0190] 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%).

[0191] Intermediates B2 to Bn are synthesized using the same method as intermediate B1, the difference being the substitution of related raw materials. For details, please refer to Table 2 for the raw material table for the synthesis of intermediates B2 to Bn.

[0192] Table 2. Raw material list for the synthesis of intermediates B2 to Bn

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201] Synthesis Example 1

[0202] This embodiment provides the synthesis of N-4, and its synthetic route is shown below:

[0203]

[0204] 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%).

[0205] 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.

[0206] Synthesis Example 2

[0207] This embodiment provides the synthesis of N-20, and its synthetic route is shown below:

[0208]

[0209] 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%).

[0210] 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.

[0211] Synthesis Example 3

[0212] This embodiment provides the synthesis of N-38, and its synthetic route is shown below:

[0213]

[0214] 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%).

[0215] 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.

[0216] Synthesis Example 4

[0217] This embodiment provides the synthesis of N-47, and its synthetic route is shown below:

[0218]

[0219] 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%).

[0220] 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.

[0221] Synthesis Example 5

[0222] This embodiment provides the synthesis of N-73, and its synthetic route is shown below:

[0223]

[0224] 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%).

[0225] 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.

[0226] Synthesis Example 6

[0227] This embodiment provides the synthesis of N-82, and its synthetic route is shown below:

[0228]

[0229] 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%).

[0230] 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.

[0231] Synthesis Example 7

[0232] This embodiment provides the synthesis of N-107, and its synthetic route is shown below:

[0233]

[0234] 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%).

[0235] 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.

[0236] Synthesis Example 8

[0237] This embodiment provides the synthesis of N-119, and its synthetic route is shown below:

[0238]

[0239] 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%).

[0240] 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.

[0241] Synthesis Example 9

[0242] This embodiment provides the synthesis of N-120, and its synthetic route is shown below:

[0243]

[0244] 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%).

[0245] 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.

[0246] Synthesis Example 10

[0247] This embodiment provides the synthesis of N-121, and its synthetic route is shown below:

[0248]

[0249] 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%).

[0250] 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.

[0251] Synthesis Example 11

[0252] This embodiment provides the synthesis of N-163, and its synthetic route is shown below:

[0253]

[0254] 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%).

[0255] 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.

[0256] Synthesis Example 12

[0257] This embodiment provides the synthesis of N-28, and its synthetic route is shown below:

[0258]

[0259] 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%).

[0260] 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.

[0261] Synthesis Example 13

[0262] This embodiment provides the synthesis of N-31, and its synthetic route is shown below:

[0263]

[0264] 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%).

[0265] 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.

[0266] Synthesis Example 14

[0267] This embodiment provides the synthesis of N-33, and its synthetic route is shown below:

[0268]

[0269] 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%).

[0270] 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.

[0271] Synthesis Example 15

[0272] This embodiment provides the synthesis of N-37, and its synthetic route is shown below:

[0273]

[0274] 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%).

[0275] 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.

[0276] Synthesis Example 16

[0277] This embodiment provides the synthesis of N-54, and its synthetic route is shown below:

[0278]

[0279] 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%).

[0280] 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.

[0281] Synthesis Example 17

[0282] This embodiment provides the synthesis of N-61, and its synthetic route is shown below:

[0283]

[0284] 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%).

[0285] 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.

[0286] Synthesis Example 18

[0287] This embodiment provides the synthesis of N-75, and its synthetic route is shown below:

[0288]

[0289] 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%).

[0290] 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.

[0291] Synthesis Example 19

[0292] This embodiment provides the synthesis of N-96, and its synthetic route is shown below:

[0293]

[0294] 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%).

[0295] 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.

[0296] Synthesis Example 20

[0297] This embodiment provides the synthesis of N-112, and its synthetic route is shown below:

[0298]

[0299] 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%).

[0300] 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.

[0301] Synthesis Example 21

[0302] This embodiment provides the synthesis of N-160, and its synthetic route is shown below:

[0303]

[0304] 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%).

[0305] 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.

[0306] Synthesis Example 22

[0307] This embodiment provides the synthesis of N-167, and its synthetic route is shown below:

[0308]

[0309] 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%).

[0310] 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.

[0311] Synthesis Example 23

[0312] This embodiment provides the synthesis of N-183, and its synthetic route is shown below:

[0313]

[0314] 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%).

[0315] 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.

[0316] Synthesis Example 24

[0317] This embodiment provides the synthesis of N-205, and its synthetic route is shown below:

[0318]

[0319] 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%).

[0320] 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.

[0321] Synthesis Example 25

[0322] This embodiment provides the synthesis of N-221, and its synthetic route is shown below:

[0323]

[0324] 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 A221 (1 mmol), B221 (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 hours. 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-221 (yield 62%).

[0325] Elemental analysis: C 45 H 29 N3. Theoretical values: C, 88.35; H, 4.78; N, 6.87; Measured values: C, 88.36; H, 4.79; N, 6.85; HRMS(ESI) m / z [M+H] + Theoretical value: 611.24; Measured value: 612.33.

[0326] Synthesis Example 26

[0327] This embodiment provides the synthesis of N-229, and its synthetic route is shown below:

[0328]

[0329] 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 A229 (1 mmol), B229 (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 hours. 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-229 (yield 63%).

[0330] Elemental analysis: C 49 H 24 D7N3. Theoretical values: C, 87.99; H, 5.72; N, 6.28; Measured values: C, 88.01; H, 5.71; N, 6.27; HRMS(ESI) m / z [M+H] + Theoretical value: 668.30; Measured value: 669.21.

[0331] Synthesis Example 27

[0332] This embodiment provides the synthesis of N-235, and its synthetic route is shown below:

[0333]

[0334] 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 A235 (1 mmol), B235 (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 hours. 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-235 (yield 64%).

[0335] Elemental analysis: C 49 H 25 D6N3. Theoretical values: C, 88.13; H, 5.58; N, 6.29; Measured values: C, 88.15; H, 5.57; N, 6.28; HRMS(ESI) m / z [M+H] + Theoretical value: 667.29; Measured value: 668.14.

[0336] Synthesis Example 28

[0337] This embodiment provides the synthesis of N-244, and its synthetic route is shown below:

[0338]

[0339] 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 A244 (1 mmol), B244 (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 hours. 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-244 (yield 65%).

[0340] 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: 712.24.

[0341] Synthesis Example 29

[0342] This embodiment provides the synthesis of N-261, and its synthetic route is shown below:

[0343]

[0344] 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 A221 (1 mmol), B261 (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 hours. 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-261 (yield 60%).

[0345] Elemental analysis: C 51 H 31 N₃O. Theoretical values: C, 87.28; H, 4.45; N, 5.99; O, 2.28; Measured values: C, 87.29; H, 4.46; N, 5.97; HRMS(ESI) m / z [M+H] + Theoretical value: 701.25; Measured value: 702.19.

[0346] Synthesis Example 30

[0347] This embodiment provides the synthesis of N-281, and its synthetic route is shown below:

[0348]

[0349] 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 A229 (1 mmol), B281 (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 hours. 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-281 (yield 62%).

[0350] Elemental analysis: C 57 H 28 D7N3. Theoretical values: C, 89.03; H, 5.50; N, 5.46; Measured values: C, 89.04; H, 5.51; N, 5.44; HRMS(ESI) m / z [M+H] + Theoretical value: 768.33; Measured value: 769.23.

[0351] Synthesis Example 31

[0352] This embodiment provides the synthesis of N-289, and its synthetic route is shown below:

[0353]

[0354] 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 A221 (1 mmol), B289 (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 hours. 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-289 (yield 61%).

[0355] 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: 687.27; Measured value: 688.15.

[0356] Synthesis Example 32

[0357] This embodiment provides the synthesis of N-308, and its synthetic route is shown below:

[0358]

[0359] 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 A229 (1 mmol), B308 (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 hours. 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-308 (yield 66%).

[0360] 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: 745.32.

[0361] Synthesis Example 33

[0362] This embodiment provides the synthesis of N-313, and its synthetic route is shown below:

[0363]

[0364] 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 A229 (1 mmol), B313 (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 hours. 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-313 (yield 64%).

[0365] 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: 745.23.

[0366] Synthesis Example 34

[0367] This embodiment provides the synthesis of N-344, and its synthetic route is shown below:

[0368]

[0369] 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 A229 (1 mmol), B344 (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 hours. 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-344 (yield 65%).

[0370] Elemental analysis: C 59 H 30 D7N3. Theoretical values: C, 89.14; H, 5.58; N, 5.29; Measured values: C, 89.16; H, 5.59; N, 5.26; HRMS(ESI) m / z [M+H] + Theoretical value: 794.34; Measured value: 795.16.

[0371] Synthesis Example 35

[0372] This embodiment provides the synthesis of N-356, and its synthetic route is shown below:

[0373]

[0374] 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 A235 (1 mmol), B356 (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 hours. 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-356 (yield 60%).

[0375] Elemental analysis: C 44 H 22 D6N4. Theoretical values: C, 85.41; H, 5.54; N, 9.05; Measured values: C, 85.43; H, 5.53; N, 9.04; HRMS(ESI) m / z [M+H] + Theoretical value: 618.27; Measured value: 619.16.

[0376] Synthesis Example 36

[0377] This embodiment provides the synthesis of N-363, and its synthetic route is shown below:

[0378]

[0379] 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 A235 (1 mmol), B363 (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 hours. 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-363 (yield 59%).

[0380] Elemental analysis: C 48 H 24 D6N4. Theoretical values: C, 86.20; H, 5.42; N, 8.38; Measured values: C, 86.22; H, 5.43; N, 8.35; HRMS(ESI) m / z [M+H] + Theoretical value: 668.28; Measured value: 669.34.

[0381] Synthesis Example 37

[0382] This embodiment provides the synthesis of N-370, and its synthetic route is shown below:

[0383]

[0384] 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 A235 (1 mmol), B370 (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 hours. 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-370 (yield 57%).

[0385] Elemental analysis: C 52 H 26 D6N4. Theoretical values: C, 86.88; H, 5.33; N, 7.79; Measured values: C, 86.89; H, 5.35; N, 7.76; HRMS(ESI) m / z [M+H] + Theoretical value: 718.30; Measured value: 719.19.

[0386] Synthesis Example 38

[0387] This embodiment provides the synthesis of N-374, and its synthetic route is shown below:

[0388]

[0389] 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 A374 (1 mmol), B221 (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 hours. 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-374 (yield 64%).

[0390] Elemental analysis: C 54 H 30 D7N3. Theoretical values: C, 88.25; H, 6.03; N, 5.72; Measured values: C, 88.26; H, 6.04; N, 5.70; HRMS(ESI) m / z [M+H] + Theoretical value: 734.34; Measured value: 735.22.

[0391] Synthesis Example 39

[0392] This embodiment provides the synthesis of N-382, and its synthetic route is shown below:

[0393]

[0394] 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 A382 (1 mmol), B382 (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 hours. 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-382 (yield 63%).

[0395] 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: 712.14.

[0396] Synthesis Example 40

[0397] This embodiment provides the synthesis of N-383, and its synthetic route is shown below:

[0398]

[0399] 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 A383 (1 mmol), B383 (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 hours. 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-383 (yield 61%).

[0400] Elemental analysis: C 57 H 28 D7N3. Theoretical values: C, 89.03; H, 5.50; N, 5.46; Measured values: C, 89.05; H, 5.51; N, 5.43; HRMS(ESI) m / z [M+H] + Theoretical value: 768.33; Measured value: 769.17.

[0401] Synthesis Example 41

[0402] This embodiment provides the synthesis of N-401, and its synthetic route is shown below:

[0403]

[0404] 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 A401 (1 mmol), B401 (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 hours. 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-401 (yield 60%).

[0405] Elemental analysis: C 53 H 33 N3. Theoretical values: C, 89.42; H, 4.67; N, 5.90; Measured values: C, 89.41; H, 4.65; N, 5.87; HRMS(ESI) m / z [M+H] + Theoretical value: 711.27; Measured value: 712.14.

[0406] Synthesis Example 42

[0407] This embodiment provides the synthesis of N-404, and its synthesis route is shown below:

[0408]

[0409] 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 A404 (1 mmol), B404 (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 hours. 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-404 (yield 65%).

[0410] Elemental analysis: C 53 H 26 D7N3. Theoretical values: C, 88.55; H, 5.61; N, 5.85; Measured values: C, 88.56; H, 5.63; N, 5.82; HRMS(ESI) m / z [M+H] + Theoretical value: 718.31; Measured value: 719.22.

[0411] Synthesis Example 43

[0412] This embodiment provides the synthesis of N-415, and its synthetic route is shown below:

[0413]

[0414] 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 A401 (1 mmol), B415 (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 hours. 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-415 (yield 59%).

[0415] Elemental analysis: C 51 H 31 N3S. Theoretical values: C, 85.33; H, 4.35; N, 5.85; S, 4.47; Measured values: C, 85.35; H, 4.36; N, 5.84; S, 4.45; HRMS(ESI) m / z [M+H] + Theoretical value: 717.22; Measured value: 718.12.

[0416] Synthesis Example 44

[0417] This embodiment provides the synthesis of N-428, and its synthetic route is shown below:

[0418]

[0419] 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 A404 (1 mmol), B428 (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 hours. 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-428 (yield 58%).

[0420] Elemental analysis: C 55 H 26 D7N3O. Theoretical values: C, 87.04; H, 5.31; N, 5.54; O, 2.11; Measured values: C, 87.05; H, 5.32; N, 5.52; HRMS(ESI) m / z [M+H] + Theoretical value: 758.31; Measured value: 759.35.

[0421] Synthesis Example 45

[0422] This embodiment provides the synthesis of N-438, and its synthetic route is shown below:

[0423]

[0424] 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 A438 (1 mmol), B438 (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 hours. 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-438 (yield 59%).

[0425] Elemental analysis: C 57 H 29 D6N3. Theoretical values: C, 89.15; H, 5.38; N, 5.47; Measured values: C, 89.16; H, 5.39; N, 5.45; HRMS(ESI) m / z [M+H] + Theoretical value: 767.32; Measured value: 768.25.

[0426] Synthesis Example 46

[0427] This embodiment provides the synthesis of N-499, and its synthetic route is shown below:

[0428]

[0429] 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 A499 (1 mmol), B382 (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 hours. 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-499 (yield 65%).

[0430] 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: 687.27; Measured value: 688.09.

[0431] Device Examples

[0432] The materials used to prepare the following device embodiments or device comparative examples are shown in Table 3 below.

[0433] Table 3. Some compounds used in device examples or device comparison examples.

[0434]

[0435]

[0436]

[0437] Device Example 1

[0438] 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).

[0439] The specific preparation process is as follows:

[0440] 1) Substrate cleaning:

[0441] 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.

[0442] 2) Preparation of organic layer:

[0443] 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.

[0444] in:

[0445] 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.

[0446] 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.

[0447] 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 S-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.

[0448] 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.

[0449] 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.

[0450] The cathode is made of aluminum with a thickness of 90 nm and a deposition rate of 1 nm / s.

[0451] Device Examples 2 to 52

[0452] Device Examples 2 to 52 each provide an organic electroluminescent device. Compared with Device Example 1, the difference lies in the replacement of the main material in the light-emitting layer. The specific materials and proportions of the light-emitting layers in Device Examples 2 to 52 are shown in Table 4.

[0453] Device Comparison Example 1

[0454] This invention provides an organic electroluminescent device as a comparative example. Compared with device embodiment 1, the difference is that material N-4 in device embodiment 1 is replaced with the following structure REF-1. The main material and guest material of the light-emitting layer and their specific ratios are shown in Table 4 below.

[0455]

[0456] Device Comparison Example 2

[0457] This invention provides an organic electroluminescent device as a comparative example. The difference between this device and device embodiment 1 is that, similar to device embodiment 1, the material N-4 in device embodiment 1 is replaced with the following structure REF-1. The main material and guest material of the light-emitting layer and their specific ratios are shown in Table 4 below.

[0458]

[0459] Device Comparison Example 3 - Device Comparison Example 18

[0460] This device comparative example provides an organic electroluminescent device. Compared with device example 1, the difference is that the main material in the light-emitting layer is replaced. The specific materials and proportions of the light-emitting layers in device comparative examples 3-18 are shown in Table 4.

[0461] Table 4

[0462]

[0463]

[0464]

[0465] Device Test Examples

[0466] The organic electroluminescent devices obtained in Device Examples 1-52 and Device Comparative Examples 1-18 of the device examples were tested.

[0467] 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;

[0468] Test conditions: Photoelectric property test conditions: current density 10 mA / cm² 2 .

[0469] Lifetime test: current density 50mA / cm 2 The recording time (in hours) when the device brightness drops to 95% of its original brightness.

[0470] The lifetime T95 of Comparative Example 1 is set to 100. The test results of lifetime T95 of Device Examples 1-52 relative to Comparative Example 1 are shown in Table 5.

[0471] With the current efficiency of Comparative Example 1 set to 100, the test results of lifetime T95 of Device Examples 1-52 relative to Comparative Example 1 are shown in Table 5.

[0472] The driving voltages of Device Examples 1-52 and Device Comparative Examples 1-18 are shown in Table 5. With the current efficiency of Device Comparative Example 1 as the baseline and denoted as 100, the relative current efficiency data of Device Examples 1-52 and Device Comparative Examples 2-18 relative to Device Comparative Example 1 are shown in Table 5. With the lifetime of Device Comparative Example 1 as the baseline and denoted as 100, the relative lifetime data of Device Examples 1-52 and Device Comparative Examples 2-18 relative to Device Comparative Example 1 are shown in Table 5.

[0473] Table 5

[0474]

[0475]

[0476]

[0477] 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 composition, characterized in that, The composition comprises a first compound and a second compound; The first compound has the structure shown in 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) or equation (1-2), R 2 Selected from equation (1-3) or equation (1-4), R 3 Selected from substituted or unsubstituted C6-C60 aryl groups; X 4 X 5 X 6 Selected from N; Where R 1 When R is selected from equation (1-1), 2 Not for equation (1-4), when R 1 When R is selected from equation (1-2), 2 Not for equation (1-3); Ar 1 Selected from substituted or unsubstituted C6-C60 aryl groups; n1 is selected from integers from 0 to 6; Ar 2 Selected from substituted or unsubstituted C6-C60 aryl groups; n2 is selected from integers from 0 to 6; Ar 3 Selected from substituted or unsubstituted C6-C60 aryl groups or substituted or unsubstituted C1-C60 heteroaryl groups; n3 is selected from integers from 0 to 6; Ar 4 Selected from substituted or unsubstituted C6-C60 aryl groups or substituted or unsubstituted C1-C60 heteroaryl groups; n4 is selected from integers from 0 to 6; The second compound has the structure shown in formula (2): in, Ring A is a benzene ring; Ar is selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C6-C60 aromatic amino, substituted or unsubstituted C3-C60 heteroaryl, and substituted or unsubstituted C3-C30 heteroaryl. L is selected from substituted or unsubstituted C6-C30 arylene or substituted or unsubstituted C3-C30 heteroarylene; The substituents in the substituted C6-C60 aryl, substituted C6-C60 aromatic amino, substituted C3-C60 heteroaryl, substituted C3-C30 heteroaryl, and substituted C1-C60 heteroaryl are selected from one or a combination of at least two of the following: deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C60 aromatic amino, and C3-C60 heteroaryl.

2. The organic electroluminescent composition according to claim 1, characterized in that, The first compound has the structures shown in formulas (1-5) and (1-6): In the formula, R 3 Ar 1 Ar 2 Ar 3 Ar 4 The definitions of n1 and n2 are the same as those in claim 1.

3. A composition for an organic optoelectronic device according to claim 1 or 2, characterized in that, Ar 1 and Ar 2 They are identical or different, and each is independently selected from substituted or unsubstituted C6-C50 aryl groups. The substituents in the substituted C6-C50 aryl groups are selected from one or a combination of at least two of the following: deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C50 aromatic amino, and C3-C50 heteroaryl. Preferred, Ar 1 and Ar 2 They are identical or different, and each is independently selected from substituted or unsubstituted C6-C25 aryl groups. The substituents in the substituted C6-C25 aryl group are selected from one or a combination of at least two of the following: deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C25 aryl, C3-C25 heteroaryl, C6-C25 aromatic amino, and C3-C25 heteroaromatic amino. Preferred, Ar 1 and Ar 2 They may be the same or different, and each is independently 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 and Ar 2 The same or different, and each independently selected from substituted or unsubstituted naphthyl groups, The substituents in the substituted naphthyl group are selected from deuterium.

4. The organic electroluminescent composition according to any one of claims 1-3, characterized in that, The first compound has the following structure: In equations (1-7) to (1-10), R 3 Ar 3 Ar 4 The definitions of n1, n2, n3, n4, n5, n6, n7, and n8 are the same as those in claim 1. n5 to n8 are integers selected from 0 to 7; Preferably, n5 to n8 are each independently selected from integers from 0 to 6; Preferably, n5 to n8 are each independently selected from integers from 0 to 5; Preferably, n5 to n8 are each independently selected from integers from 0 to 4; Preferably, n5 to n8 are each independently selected from integers from 0 to 3; Preferably, n5 to n8 are each independently selected from integers from 0 to 2.

5. The organic electroluminescent composition 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 a combination of at least two of the following: deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C50 aromatic amino, and C3-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 a combination of at least two of the following: deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C25 aryl, C3-C25 heteroaryl, C6-C25 aromatic amino, and C3-C25 heteroaromatic amino. Preferred, R 3 Selected from the group consisting of the following groups:

6. The organic electroluminescent composition according to any one of claims 1-5, characterized in that, Ar 3 and Ar 4 They are either the same or different, and each is independently selected from substituted or unsubstituted C6-C50 aryl groups or substituted or unsubstituted C1-C50 heteroaryl groups. Wherein, the substituents in the substituted C6-C50 aryl and substituted C6-C50 heteroaryl are selected from one or a combination of at least two of the following: deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C60 aromatic amino, and C3-C50 heteroaryl. Preferred, Ar 3 and Ar 4 They are identical or different, and each is independently selected from substituted or unsubstituted C6-C25 aryl or substituted or unsubstituted C6-C25 heteroaryl. Wherein, the substituents in the substituted C6-C25 aryl and substituted C6-C25 heteroaryl are selected from one or a combination of at least two of the following: deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C25 aryl, C3-C25 heteroaryl, C6-C25 aromatic amino, and C3-C25 heteroaromatic amino. Preferred, Ar 3 and Ar 4 They are either the same or different, and each is independently selected from the group consisting of the following groups:

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

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

9. The organic electroluminescent composition according to any one of claims 1-8, characterized in that, In the second compound, Ar is selected from substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C6-C25 arylamine, substituted or unsubstituted C3-C25 heteroaryl, and substituted or unsubstituted C3-C20 heteroaryl. The substituents in the substituted C6-C25 aryl, substituted C6-C25 aromatic amino, substituted C3-C25 heteroaryl, and substituted C3-C20 heteroaryl are each independently selected from one or a combination of at least two of the following: deuterium, halogen, cyano, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C60 aromatic amino, and C3-C60 heteroaryl. Preferably, Ar is selected from substituted or unsubstituted B groups, and the B group is selected from the following groups: phenyl, naphthyl, biphenyl, phenanthryl, fluoranthyl, ... , terphenyl, triphenylene, finadeninyl, phenylnaphthyl, naphthylphenyl, dimethylfluorenyl, phenylmethylfluorenyl, diphenylfluorenyl, pyridyl, pyridylphenyl, phenylpyridyl, spirodifluorenyl, benzodimethylfluorenyl, benzodiphenylfluorenyl, benzospirodifluorenyl, dibenzofuranyl, benzonaphthiofuranyl, benzonaphthiopheneyl, spiro[fluoren-9,9'-oxazanthyl]yl, phenylmethylfluorenyl, dinaphthiofuranyl, dinaphthiopheneyl, dibenzothiopheneyl, N,N-diphenylaniline; Wherein, the substituent of the substituted B group is selected from one or a combination of at least two of the following: deuterium, halogen, cyano, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C60 aromatic amino, and C3-C60 heteroaryl. Preferably, Ar is selected from phenyl, naphthyl, biphenyl, yl, phenanthrene, terphenyl, phenylnaphthyl, naphthylphenyl, dimethylfluorenyl, diphenylfluorenyl, spirodifluorenyl, finadenoyl, dibenzofuranyl, benzonaphthylfuranyl, N,N-diphenylaniline.

10. The organic electroluminescent composition according to any one of claims 1-9, characterized in that, In the second compound, L is selected from substituted or unsubstituted C6-C15 arylene groups; wherein each substituent in the substituted C6-C15 arylene group is independently selected from one or a combination of at least two of deuterium, halogen, and C1-C62 alkyl groups. Preferably, L is selected from phenylene, biphenylene, and naphthylene; Preferably, L is selected from phenylene or naphthylene.

11. The organic electroluminescent composition according to any one of claims 1-10, characterized in that, Equation (2) is selected from one of the structures shown in Equations (2-1) to (2-6):

12. The organic electroluminescent composition according to any one of claims 1-11, characterized in that, The second compound is selected from any one of S-1 to S-208:

13. The organic electroluminescent composition according to any one of claims 1-12, characterized in that, The mass ratio of the first compound to the second compound is 1:9 to 9:1; Preferably, in the composition, the mass ratio of the first compound to the second compound is 2:8-8:2; Preferably, in the composition, the mass ratio of the first compound to the second compound is 3:7-7:3; Preferably, in the composition, the mass ratio of the first compound to the second compound is 4:6 to 6:

4.

14. An organic electroluminescent host material composition, characterized in that, The light-emitting host material composition comprises the organic electroluminescent composition as described in any one of claims 1-13.

15. An organic electroluminescent device, characterized in that, The organic electroluminescent device comprises the organic electroluminescent composition as described in any one of claims 1-13 or the organic electroluminescent host material composition as described in claim 14; Preferably, the organic electroluminescent device includes a first electrode, a second electrode disposed opposite to the first electrode, and an organic layer between the first electrode and the second electrode, wherein the organic layer comprises an organic electroluminescent composition as described in any one of claims 1-13 or an organic electroluminescent host material composition as described in claim 14; Preferably, the organic layer includes a light-emitting layer, which comprises an organic electroluminescent composition as described in any one of claims 1-13 or an organic electroluminescent host material composition as described in claim 14.

16. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes the organic electroluminescent device as described in claim 15, the organic electroluminescent composition as described in any one of claims 1-13, or the organic electroluminescent host material composition as described in claim 14.

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